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    • 专利摘要:
    An object of the present invention is to obtain an ethylene copolymer composition excellent in transparency, mechanical strength and moldability. This ethylene-based copolymer composition is composed of an ethylene-α-olefin copolymer and a high pressure radical method low density polyethylene. The ethylene-α-olefin copolymer is a copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms and also has the following characteristics: The melt tension (MT) and the melt flow rate (MFR) is satisfied and the relationship 9.0 × MFR -0.65>MT> 2.2 × MFR -0.84; Flow activation energy ((E a ) × 10 -4 J / molK), α-olefin carbon number (C) in the copolymer and α-olefin content (x mol%) in the copolymer was (0.039Ln (C-2) Satisfies the relationship +0.0096) × x + 2.87 <E a × 10 −4 ≦ (0.039Ln (C-2) +0.1660) × x + 2.87; The haze of the inflation film produced from the copolymer composition satisfies a specific relationship. The ethylene copolymer composition is used for the production of molded articles such as films, sheets, packaging materials, injection molded articles, foamed molded articles and fibers. These molded bodies are excellent in mechanical strength, heat safety or transparency.
    公开号:KR20010012350A
    申请号:KR1019997010302
    申请日:1999-03-10
    公开日:2001-02-15
    发明作者:다까하시마모루；나까가와다까시；스기무라겐지；요시쓰구겐
    申请人:나까니시 히로유끼；미쓰이 가가쿠 가부시키가이샤；
    IPC主号:
    专利说明:

    Ethylene-based copolymer composition and its use {ETHYLENE COPOLYMER COMPOSITION AND USE THEREOF}
    Ethylene-based copolymers are molded by various molding methods, and are used for various purposes. Ethylene-based copolymers also require different properties depending on the molding method and application. For example, if the inflation film is to be formed at high speed, the melt tension (melt tension (MT)) higher than the molecular weight of the ethylene copolymer is not selected in order to stably and rapidly form the foam without fluctuation or bubble breakage of the bubble. Can not be done. Similar properties are necessary to prevent sagging or tearing down in blow molding, or to minimize the width reduction in T die molding.
    However, a method of improving moldability by improving the melt tension and expansion ratio (die swell ratio) of an ethylene copolymer obtained using a Ziegler-type catalyst, in particular a titanium catalyst, is disclosed in Japanese Patent Application Laid-Open No. 56-908100 or Japanese Patent Application Laid-Open No. 60-90. 106106 is proposed. In general, however, ethylene copolymers, particularly low density polyethylene copolymers, obtained using titanium catalysts have a wide composition distribution and often contain components that cause stickiness when used in molded products such as films. It was desired to further reduce the sticky ingredients.
    In addition, among the ethylene copolymers produced using the Ziegler type catalyst, the ethylene copolymers obtained using the chromium catalyst have a relatively high melt tension, but improvement of thermal stability has been desired.
    The ethylene copolymer obtained by the catalyst for olefin polymerization containing a transition metal metallocene compound has high melt tension and good thermal stability, and is therefore expected to meet the above requirements. However, in the ethylenic copolymer obtained by the metallocene catalyst, the melt tension (MT) and the flow activation energy (E a ) are generally in a proportional relationship.
    The polymer having high melt tension has good moldability because of excellent bubble stability as described above. However, the flow activation energy E a is high, which means that the temperature dependence of the molding conditions is large. For this reason, a stain arises in the molded object obtained, unless shaping | molding conditions are controlled very precisely and uniformly. For example, in the case of a film, transparency may fall.
    On the other hand, when the flow activation energy E a is low, staining in the molded body can be prevented, but the melt tension is low, so that the bubble becomes unstable and the moldability is poor.
    The present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide an ethylene copolymer composition having excellent transparency and mechanical strength, and to provide an ethylene copolymer composition having excellent moldability. It is an object to provide a use of the system copolymer.
    Disclosure of the Invention
    The ethylenic copolymer composition (A) according to the present invention comprises (A) an ethylene-α-olefin copolymer and (E) a high pressure radical method low density polyethylene,
    The ethylene-α-olefin copolymer (A) is a copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms and also has the following characteristics:
    (A-i) Melt tension (MT) and melt flow rate (MFR) at 190
    9.0 × MFR -0.65>MT> 2.2 × MFR -0.84
    Satisfy the relationship represented by
    (A-ii) the flow activation energy ((E a ) × 10 -4 J / molK) obtained from the shift factor of the time-temperature overlap of the flow curve, the carbon number (C) of the α-olefin in the copolymer, and the copolymer Content rate of (alpha) -olefin in (x mol%)
    (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 −4 ≤ (0.039Ln (C-2) +0.1660) × x + 2.87
    Satisfy the relationship represented by
    (A-iii) When the copolymer is inflation-formed to produce a film having a thickness of 30 μm, the haze of the film has the following relationship,
    When the fluidity index (FI) and the melt flow rate (MFR), defined as the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 6 dyne / cm 2, satisfy FI ≧ 100 × MFR,
    If carbon number (C) of an alpha olefin is 6,
    Haze 〈0.45 / (1-d) × log (3 × MT 1.4 ) × (C-3) 0.1
    If the carbon number (C) of the α-olefin is 7 or 8,
    Haze 〈0.50 / (1-d) × log (3 × MT 1.4 )
    When the fluidity index (FI) and the melt flow rate (MFR) defined by the shear rate when the shear stress at 190 ° C reaches 2.4 × 10 6 dyne / cm 2 satisfy the FI <100 × MFR,
    If carbon number (C) of an alpha olefin is 6,
    Haze 〈0.25 / (1-d) × log (3 × MT 1.4 ) × (C-3) 0.1
    If the carbon number (C) of the α-olefin is 7 or 8,
    Haze <0.50 / (1-d) × log (3 × MT 1.4 )
    (Where d denotes density (g / cm 3) and MT denotes melt tension (g))
    Satisfying
    The high pressure radical low density polyethylene (E) has the following properties:
    (E-i) Melt flow rate measured at 190 ° C and 2.16 kg load ranges from 0.1 to 50 g / 10 minutes,
    (E-ii) The molecular weight distribution (Mw / Mn: Mw = weight average molecular weight, Mn = number average molecular weight) and melt flow rate (MFR) measured by gel permeation chromatography
    7.5 × log (MFR) -1.2≤Mw / Mn≤7.5 × log (MFR) +12.5
    Satisfies the relationship indicated by.
    The ethylene-α-olefin copolymer (A) is, for example
    (a) an organoaluminum oxy compound,
    (b-I) at least one transition metal compound selected from transition metal compounds represented by the following general formula (I),
    ML 1 x ------ (I)
    (Wherein M is a transition metal atom selected from Group 4 of the periodic table, L 1 is a ligand that coordinates to transition metal atom M, and at least two ligands L 1 of these are at least one member selected from hydrocarbons of 3 to 10 carbon atoms) Is a substituted cyclopentadienyl group having a group of, and ligands L 1 other than the substituted cyclopentadienyl group are a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is Is the valence of the transition metal M)
    (b-II) at least one transition metal compound selected from transition metal compounds represented by the following general formula (II),
    ML 2 x ------ (II)
    (Wherein M is a transition metal atom selected from Group 4 of the periodic table, L 2 is a ligand that coordinates to transition metal atom M, and at least two of them, L 2, is a methylcyclopentadienyl group or an ethylcyclopentadienyl group) And ligands L 2 other than the methylcyclopentadienyl group or the ethylcyclopentadienyl group are a C1-C12 hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is a transition metal Is the valence of M.)
    It is obtained by copolymerizing ethylene and the C6-C8 alpha-olefin in presence of the catalyst for olefin polymerization which becomes.
    In the catalyst, the (a) organoaluminum oxy compound, (b-I) transition metal compound and (b-II) transition metal compound are preferably supported on (c) carrier.
    In addition, the ethylene copolymer composition (A ') according to another aspect of the present invention comprises (B) an ethylene-α-olefin copolymer, (C) an ethylene-α-olefin copolymer, and (E) a high pressure radical method low density polyethylene. And
    The ethylene-α-olefin copolymer (B) is a copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms and has the following characteristics:
    (B-i) density is in the range of 0.880 to 0.970 g / cm 3,
    (B-ii) Melt flow rate (MFR) at 190 ° C. and 2.16 kg load is in the range of 0.02 to 200 g / 10 minutes,
    (B-iii) when the decane soluble fraction (W) and density (d) at room temperature satisfy MFR≤10 g / 10 min,
    W <80 x exp (-100 (d-0.88)) + 0.1
    When MFR> 10g / 10 minutes is satisfied,
    W <80 x (MFR-9) 0.26 x exp (-100 (d-0.88)) + 0.1
    Satisfy the relationship represented by
    (B-iv) The temperature (Tm) and the density (d) of the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC)
    Tm <400 × d-248
    Satisfy the relationship represented by
    (B-v) Melt tension (MT) and melt flow rate (MFR) at 190
    9.0 × MFR -0.65>MT> 2.2 × MFR -0.84
    Satisfy the relationship represented by
    (B-vi) Flow activation energy ((E a ) × 10 -4 J / molK) obtained from the shift factor of time-temperature overlap of the flow curve, carbon number (C) of the α-olefin in the copolymer, and the copolymer Content rate of (alpha) -olefin in (x mol%)
    (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 −4 ≤ (0.039Ln (C-2) +0.1660) × x + 2.87
    Satisfy the relationship represented by
    (B-vii) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC is
    2.2 <Mw / Mn <3.5
    Satisfies the relationship indicated by.
    The ethylene-α-olefin copolymer (C) is a copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms and has the following characteristics:
    (C-i) density ranges from 0.880 to 0.970 g / cm 3,
    (C-ii) Melt flow rate (MFR) at 190 ° C and 2.16 kg load is in the range of 0.02 to 200 g / 10 minutes,
    (C-iii) when the decane soluble fraction (W) and density (d) at room temperature satisfy MFR≤10 g / 10 min,
    W <80 x exp (-100 (d-0.88)) + 0.1
    When MFR> 10g / 10 minutes is satisfied,
    W <80 x (MFR-9) 0.26 x exp (-100 (d-0.88)) + 0.1
    Satisfy the relationship represented by
    (C-iv) The temperature (Tm) and the density (d) of the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC)
    Tm <400 × d-248
    Satisfy the relationship represented by
    (C-v) Melt tension (MT) and melt flow rate (MFR) at 190
    MT≤ 2.2 × MFR -0.84
    Satisfies the relationship indicated by.
    The high pressure radical low density polyethylene (E) has the following properties:
    (E-i) Melt flow rate measured at 190 ° C and 2.16 kg load ranges from 0.1 to 50 g / 10 minutes,
    (E-ii) The molecular weight distribution (Mw / Mn: Mw = weight average molecular weight, Mn = number average molecular weight) and melt flow rate (MFR) measured by gel permeation chromatography
    7.5 × log (MFR) -1.2≤Mw / Mn≤7.5 × log (MFR) +12.5
    Satisfies the relationship indicated by.
    The ratio of the melt flowrate (MFR (C)) of the copolymer (C) and the melt flowrate (MFR (B)) of the copolymer (B)
    1 <(MFR (C)) / (MFR (B)) ≤20.
    Moreover, the composition which consists of the said ethylene-alpha-olefin copolymer (B) and the said ethylene-alpha-olefin copolymer (C) has substantially the same composition and usability as the said ethylene-alpha-olefin copolymer (A).
    In the ethylene copolymer composition (A '), both the ethylene-α-olefin copolymers (B) and (C) are ethylene-1-hexene copolymers, and ethylene-α-olefin copolymers (B) and (C) It is preferred that the composition has the following properties:
    (A'-i) Melt tension (MT) and melt flow rate (MFR) at 190
    9.0 × MFR -0.65>MT> 2.2 × MFR -0.84
    Satisfy the relationship represented by
    (A'-ii) of the flow activation energy ((E a ) × 10 -4 J / molK) obtained from the shift factor of the time-temperature overlap of the flow curve, and of 1-hexene in the copolymers (B) and (C) The carbon number (C) and the content (x mol%) of 1-hexene in the copolymers (B) and (C)
    (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 −4 ≤ (0.039Ln (C-2) +0.1660) × x + 2.87
    Satisfy the relationship represented by
    (A'-iii) When the composition is inflation-molded to produce a film having a thickness of 30 µm, haze of the film satisfies the following relationship.
    When the fluidity index (FI) and the melt flow rate (MFR), defined as the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 6 dyne / cm 2, satisfy FI ≧ 100 × MFR,
    Haze 〈0.45 / (1-d) × log (3 × MT 1.4 ) × (C-3) 0.1
    When the fluidity index (FI) and the melt flow rate (MFR) defined by the shear rate when the shear stress at 190 ° C reaches 2.4 × 10 6 dyne / cm 2 satisfy the FI <100 × MFR,
    Haze 〈0.25 / (1-d) × log (3 × MT 1.4 ) × (C-3) 0.1
    (Where d is density (g / cm 3), MT is melt tension (g), and C is 1-hexene carbon atom, i.e., 6).
    Further, in the ethylene copolymer composition (A '), the composition comprising the ethylene-α-olefin copolymers (B) and (C) is in addition to the requirements of the above (A'-1) to (A'-iii), More preferably, it has the following characteristics:
    (A'-iv) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC is
    2.0≤Mw / Mn≤2.5
    To satisfy.
    Further, in the ethylene copolymer composition (A) or the ethylene copolymer composition (A '),
    (a) an organoaluminum oxy compound,
    (b-III) obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst for olefin polymerization containing a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton; ,
    (D-i) density ranges from 0.850 to 0.980 g / cm3
    (D-ii) Ethylene-alpha-olefin copolymer (A) by adding the (D) ethylene-alpha-olefin copolymer whose intrinsic viscosity ((eta)) measured in 135 degreeC and decalin is 0.4-8 dl / g. ) And a composition (A) made of a high pressure radical method low density polyethylene (E), a composition of an ethylene-α-olefin copolymer (D) (ethylene copolymer composition (A ")) or an ethylene copolymer composition (A ') It can be set as the composition (ethylene-based copolymer composition (A '")) of an ethylene-alpha-olefin copolymer (D).
    However, the ethylene-α-olefin copolymer (A) and the ethylene-α-olefin copolymer (D) are not the same, and the ethylene-α-olefin copolymer (B) and (C) and the ethylene-α-olefin copolymer (D) is not the same.
    A molded article such as a single layer film or sheet, a multilayer film or sheet, an injection molded article, an extrusion molded article, a fiber, a foam molded article, a sheath for electric wire, etc. according to the present invention is formed from the ethylene copolymer composition described above.
    Best mode for carrying out the invention
    Hereinafter, the ethylenic copolymer composition and its use according to the present invention will be described.
    In the present invention, the term "polymerization" is used to include not only homopolymerization but also copolymerization, and the term "polymer" is used to mean not only homopolymer but also copolymer.
    First, the ethylene-alpha-olefin copolymer (A), the ethylene-alpha-olefin copolymer (B), the ethylene-alpha-olefin copolymer (C), and the high pressure radical method low density which form the ethylene copolymer composition which concerns on this invention. Polyethylene (E) is demonstrated.
    Ethylene-α-olefin copolymer (A)
    The ethylene-α-olefin copolymer (A) is a random copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms. As a C6-C8 alpha olefin used for copolymerization with ethylene, the linear alpha-olefin which does not have a branch is preferable, Specifically, 1-hexene, 1-heptene, 1-octene is mentioned, for example. 1-hexene is particularly preferred.
    An ethylene-alpha-olefin copolymer (A) has the characteristic shown to following (A-i)-(A-iii).
    (A-i) Melt tension (MT (g)) and melt flow rate (MFR (g / 10 min)
    9.0 × MFR -0.65>MT> 2.2 × MFR -0.84
    Preferably
    9.0 × MFR -0.65>MT> 2.3 × MFR -0.84
    More preferably
    8.5 × MFR -0.65>MT> 2.5 × MFR -0.84
    The relationship indicated by is satisfied.
    The ethylene-α-olefin copolymer having such characteristics has good moldability because of its high melt tension (MT).
    In addition, MFR is measured by 190 degreeC and 2.16 kg load conditions based on ASTMD1238-65T.
    The melt tension MT is determined by measuring the stress when the molten polymer is stretched at a constant speed. In other words, the produced polymer powder was melted and pelletized by a conventional method to obtain a sample for measurement. It carried out on condition of 2.09 mm diameter and 8 mm nozzle length. When pelletizing, 0.05 wt% of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant was previously added to the ethylene-α-olefin copolymer and n-octadecyl-3- (4 as a heat stabilizer. 0.1 wt% of '-hydroxy-3', 5'-di-t-butylphenyl) propionate and 0.05 wt% of calcium stearate were blended as a hydrochloric acid absorbent.
    (A-ii) the flow activation energy ((E a ) × 10 -4 J / molK) obtained from the shift factor of the time-temperature overlap of the flow curve, the carbon number (C) of the α-olefin in the copolymer, and the copolymer The relationship between the content rate (x mol%) of α-olefin in
    (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 −4 ≤ (0.039Ln (C-2) +0.1660) × x + 2.87
    Preferably
    (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 −4 ≤ (0.039Ln (C-2) +0.1500) × x + 2.87
    More preferably
    (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 −4 ≤ (0.039Ln (C-2) +0.1300) × x + 2.87
    The relationship indicated by is satisfied.
    In order to improve film formability, it is known that the melt tension needs to be improved, and therefore, the introduction of long chain branching is effective. E a of the ethylene-α-olefin copolymer without long chain branching is represented by E a × 10 −4 = (0.039Ln (C-2) +0.0096) × x + 2.87. If a long chain branch is present, E a becomes large, so E a × 10 −4 > (0.039Ln (C-2) +0.0096) × x + 2.87
    In the case of, it is assumed that long chain branching exists, and film formability and transparency are improved. The E a × 10 -4> (0.039Ln (C-2) +0.1660) when a × x + 2.87, excellent in formability, but it is not preferable because poor film strength and film transparency.
    Measurement of the flow activation energy (E a ) is described, for example, in "Polymer Polymer Science Vol. 9 Thermodynamic Properties I (Polymer Polymer Society Editing Committee, Public Publications, pp. 25-28)," The viscoelastic frequency dependence is measured to obtain the flow activation energy E a from the shift factor of the time-temperature overlap. If the graph of the storage modulus (vertical axis) versus the angular velocity (horizontal axis) measured at a specific reference temperature is fixed and the data measured at different measurement temperatures are moved in parallel along the horizontal axis, it overlaps with the data of the reference temperature (thermal rheology). Intellectual simplicity). 2.303R (R is a gas constant) in a gradient of a straight line obtained by plotting a shift amount log (aT) for superimposing data at each measurement temperature with data at a reference temperature with respect to the inverse 1 / T of the measured temperature (absolute temperature). ), The activation energy is obtained as an integer independent of temperature.
    Specifically, E a is measured as follows.
    The angular velocity (ω (rad / sec)) dispersion of the storage modulus (G '(dyne / cm 2)) was measured using Rheometer RDS-II manufactured by Rheometrics. The sample holder used the parallel plate of about 25 mm, and made the sample thickness about 2 mm. The measurement temperature was 130,170,200,230 ° C, and G 'was measured in the range of 0.04≤w≤400 at each temperature. In the case of measuring at 130 degreeC, in order to melt | dissolve a crystal | crystallization completely, after heating up to 150 degreeC, it measured by cooling to 130 degreeC. The amount of deformation was appropriately selected in the range of 2 to 25% so that the torque could be detected in the measurement range and the torque was not overpowered. To 130 ℃ as the reference temperature after the measurement by the flow curve by overlapping of the four temperature conditions, the E a was calculated from the Arrhenius type print the lot of the shift factor. Calculations were performed using the analysis software RHIOS, which was attached to RDS-II.
    (A-iii) When a film having a thickness of 30 µm is produced by inflation molding the ethylene-α-olefin copolymer, the haze of the film satisfies the following relationship.
    The fluidity index (FI) and melt flow rate (MFR), defined as the shear rate when the shear stress at 190 ° C reaches 2.4x10 6 dyne / cm 2,
    If FI≥100 × MFR
    If carbon number (C) of an alpha olefin is 6,
    Haze 〈0.45 / (1-d) × log (3 × MT 1.4 ) × (C-3) 0.1
    If the carbon number (C) of the α-olefin is 7 or 8,
    Haze 〈0.50 / (1-d) × log (3 × MT 1.4 )
    The fluidity index (FI) and melt flow rate (MFR), defined as the shear rate when the shear stress at 190 ° C reaches 2.4x10 6 dyne / cm 2,
    If FI <100 × MFR
    If carbon number (C) of an alpha olefin is 6,
    Haze 〈0.25 / (1-d) × log (3 × MT 1.4 ) × (C-3) 0.1
    If the carbon number (C) of the α-olefin is 7 or 8,
    Haze <0.50 / (1-d) × log (3 × MT 1.4 )
    (Where d is density (g / cm 3) and MT is surface tension (g))
    The ethylene-alpha-olefin copolymer which satisfy | fills these requirements is excellent in moldability and the transparency of the film obtained.
    The flow index FI is determined by extruding the resin from the capillary while varying the shear rate and measuring the stress at that time. That is, using the same sample as the MT measurement, using a TSP and capillary flow characteristics tester, the resin temperature was 190 ° C and the shear stress was measured at a range of 5 × 10 4 to 3 × 10 6 dyne / cm 2. do.
    In addition, the diameter of a nozzle is changed simply as follows according to MFR (g / 10min) of resin to measure.
    0.5 mm for MFR〉 20
    1.0 mm for 20 ≥ MFR> 3
    2.0 mm for 3 ≥ MFR> 0.8
    3.0 mm for 0.8 ≥ MFR
    In addition, the density (d) was measured at a density gradient pipe after heat treatment at 120 ° C. for 1 hour, and slowly cooling the strand obtained at the time of melt flow rate (MFR) measurement at a load of 2.16 kg at 190 ° C. to room temperature over 1 hour. do.
    It is preferable that an ethylene-alpha-olefin copolymer (A) satisfy | fills the following requirements in addition to the said requirements.
    In the ethylene-α-olefin copolymer (A), the structural unit derived from ethylene is 50 to 60% by weight, preferably 55 to 99% by weight, more preferably 65 to 98% by weight, most preferably 70 to It is present in an amount of 96% by weight, and the structural unit derived from an α-olefin having 6 to 8 carbon atoms is 0 to 50% by weight, preferably 1 to 45% by weight, more preferably 2 to 35% by weight, particularly preferably Is preferably present in an amount of 4 to 30% by weight.
    The composition of the ethylene-α-olefin copolymer is a 13 C-NMR spectrum of a sample in which approximately 200 mg of the copolymer is uniformly dissolved in 1 ml of hexachlorobutadiene in a 10 mm ψ test tube, and the measurement temperature is 120 ° C., and the measurement frequency is 25.05 MHz. It is determined by measurement under the measurement conditions of spectral width 1500 Hz, pulse repetition time 4.2 sec and pulse width 6 Hz.
    The density (d) of the ethylene-α-olefin copolymer (A) is 0.880 to 0970 g / cm 3, preferably 0.880 to 0960 g / cm 3, more preferably 0.890 to 0.935 g / cm 3, most preferably 0.905 to The range is preferably 0.930 g / cm 3.
    The melt flow rate (MFR) of the ethylene-α-olefin copolymer (A) is in the range of 0.02 to 200 g / 10 minutes, preferably 0.05 to 50 g / 10 minutes, more preferably 0.1 to 10 g / 10 minutes. It is good to be.
    N-decane soluble component fraction (W (% by weight)) and density (d (g / cm 3)) of the ethylene-α-olefin copolymer (A) at 23 ° C.
    For MFR≤10g / 10min
    W <80 × exp (-100 (d-0.88)) + 0.1
    Preferably, W <60 × exp (-100 (d-0.88)) + 0.1
    More preferably, W <40 × exp (-100 (d-0.88)) + 0.1
    In the case of MFR> 10g / 10 minutes
    W <80 × (MFR-9) 0.26 × exp (-100 (d-0.88)) + 0.1
    It is good to satisfy the relationship indicated by.
    In addition, the measurement of the n-decane soluble component fraction (W) of an ethylene-alpha-olefin copolymer (the smaller the soluble component fraction is, the narrower the composition distribution) adds about 3 g of a copolymer to 450 ml of n-decanes, and it is 145 degreeC It is performed by cooling to 23 degreeC after melt | dissolution, removing an n-decane insoluble part by filtration, and recovering an n-decane soluble part from a filtrate.
    The temperature (Tm (° C.)) and the density (d (g / cm 3)) of the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) of the ethylene-α-olefin copolymer (A)
    Tm <400 × d-248
    Preferably Tm <450 × d-296
    More preferably, Tm <500 × d-343
    Especially preferably, Tm <550 × d-392
    It is good to satisfy the relationship indicated by.
    In addition, the temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) was placed in an aluminum pan of about 5 mg of sample, and the temperature was raised to 200 ° C. at a rate of 10 ° C./min, followed by 5 minutes at 200 ° C. After hold | maintaining, it cools to room temperature at 10 degree-C / min speed | rate, and is calculated | required from the endothermic curve at the time of heating up at 10 degree-C / min rate. The measurement uses a DSC-7 device manufactured by PerkinElmer.
    The relationship between the temperature (Tm) and the density (d) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC), and the n-decane soluble component fraction (W) and the density (d) The ethylene-alpha-olefin copolymer which has is narrow in composition distribution.
    Said ethylene-alpha-olefin copolymer (A) can also use 2 or more types together.
    Ethylene-α-olefin copolymer (A) is, for example
    (a) an organoaluminum oxy compound,
    (b-I) at least one transition metal compound selected from the transition metal compounds represented by the general formula (I),
    (b-II) Ethylene and C6-C8 alpha -olefins in the presence of an olefin polymerization catalyst (Cat-1) comprising at least one transition metal compound selected from the transition metal compounds represented by the general formula (II). It is obtained by copolymerizing.
    At least one transition metal compound selected from (a) the organoaluminum oxy compound, (bI) the transition metal compound represented by the general formula (I), and (b-II) the transition represented by the general formula (II). The at least one transition metal compound selected from the metal compounds may be supported on the carrier (c) (hereinafter, such a supported catalyst may be abbreviated as Cat-2).
    Next, each catalyst component which forms the catalyst for olefin polymerization (Cat-1) and (Cat-2) is demonstrated.
    (a) organoaluminum oxy compound
    The organoaluminum oxy compound (a) (hereinafter sometimes referred to as "component (a)") may be a conventionally known benzene-soluble aluminoxane, and is a benzene-insoluble organic disclosed in Japanese Patent Laid-Open No. 2-276807. An aluminum oxy compound may be sufficient.
    Said aluminoxane can be manufactured, for example by the following method, and is normally obtained as a solution of a hydrocarbon.
    (1) Compounds containing adsorbed water or salts containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, and cerium chloride hydrate, such as trialkylaluminum A method of reacting by adding an organoaluminum compound.
    (2) A method in which water, ice, or steam are directly applied to organoaluminum compounds such as trialkylaluminum in media such as benzene, toluene, ethyl ether, and tetrahydrofuran.
    (3) A method in which organotin oxides such as dimethyltin oxide and dibutyltin oxide are reacted with organoaluminum compounds such as trialkylaluminum in a medium such as decane, benzene, or toluene.
    This aluminoxane may also contain trace amounts of organometallic components. The solvent or unreacted organoaluminum compound may be distilled off and removed from the recovered solution of aluminoxane, followed by redissolution in the solvent.
    Specific examples of the organoaluminum compounds used when preparing aluminoxanes include
    Trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-aluminium, tri-tert-aluminum, tripentylaluminum, trihexylaluminum, tri Trialkyl aluminums such as octyl aluminum and tridecyl aluminum;
    Tricycloalkyl aluminums such as tricyclohexyl aluminum and tricyclooctyl aluminum;
    Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride;
    Dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride;
    Dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide; And
    Dialkyl aluminum aryl oxides, such as diethyl aluminum phenoxide, are mentioned.
    Of these, trialkylaluminum and tricycloalkylaluminum are particularly preferred.
    Moreover, as this organoaluminum compound, the following general formula
    (iC 4 H 9 ) x Al y (C 5 H 10 ) z
    (x, y, z is an integer, z≥2x)
    Isoprenyl aluminum represented by is also used.
    Said organoaluminum compounds are used individually or in combination. Examples of the solvent used in the preparation of the aluminoxane are
    Aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene;
    Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane;
    Alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane;
    Petroleum oils such as gasoline, kerosene and gas oil; And
    And halides of aromatic, aliphatic and alicyclic hydrocarbons such as chlorinated or bromide thereof. In addition, ethers, such as ethyl ether and tetrahydrofuran, can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.
    In addition, the benzene-insoluble organoaluminum oxy compound is 10% or less, preferably 5% or less, particularly preferably 2% or less, in terms of Al component dissolved in 60 ° C. benzene, insoluble or poorly soluble in benzene. to be.
    The solubility in benzene of such an organoaluminum oxy compound was suspended in 100 ml of benzene in the organoaluminum oxy compound corresponding to 100 mg · atm of Al, followed by mixing at 60 ° C. for 6 hours under stirring, followed by a jacket After heat filtration at 60 ° C. using a G-5 glass filter and washing the solid portion separated on the filter four times with 50 ml of benzene at 60 ° C., the amount of Al atoms present in the total filtrate (x mmol) to obtain (x%).
    (b-I) transition metal compounds and (b-II) transition metal compounds
    The transition metal compound (b-I) is a transition metal compound represented by the following general formula (I), and the transition metal compound (b-II) is a transition metal compound represented by the following general formula (II).
    ML 1 x ----- (I)
    (Wherein M is a transition metal atom selected from Group 4 of the periodic table; L 1 is a ligand that coordinates to transition metal atom M, and at least two ligands L 1 of these are at least one selected from hydrocarbons having 3 to 10 carbon atoms) X is a substituted cyclopentadienyl group having a group of and a ligand L 1 other than the substituted cyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom; Is the valence of the transition metal M)
    ML 2 x ----- (II)
    (Wherein M is a transition metal atom selected from Group 4 of the periodic table; L 2 is a ligand that coordinates to transition metal atom M, and at least two of them, L 2, is a methylcyclopentadienyl group or an ethylcyclopentadienyl group) And ligands L 2 other than the methylcyclopentadienyl group or the ethylcyclopentadienyl group are a C1-C12 hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom; X is a transition metal Valence of M)
    The transition metal compound represented by the general formula (I) or (II) will be described in more detail.
    In the general formula (I), M is a transition metal atom selected from Group 4 of the periodic table, specifically zirconium, titanium, or hafnium, preferably zirconium.
    L 1 is a ligand that coordinates to the transition metal atom M, at least two of them L 1 is a substituted cyclopentadienyl group having at least one group selected from hydrocarbons having 3 to 10 carbon atoms, and these ligands L 1 are each the same Or you may differ.
    The substituted cyclopentadienyl group may have two or more substituents, and two or more substituents may be the same or different, respectively. When a substituted cyclopentadienyl group has 2 or more substituents, at least 1 substituent may be a C3-C10 hydrocarbon group, and another substituent is a methyl group, an ethyl group, or a C3-C10 hydrocarbon group.
    As a C3-C10 hydrocarbon group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, etc. can be illustrated. Specific examples include alkyl groups such as n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, 2-ethylhexyl and decyl; Cycloalkyl groups such as cyclopentyl and cyclohexyl; Aryl groups such as phenyl and tolyl; And aralkyl groups such as benzyl and neofill.
    Of these, alkyl groups are preferred, and more preferred are n-propyl and n-butyl. In this invention, as a substituted cyclopentadienyl group which coordinates to a transition metal, a 2-substituted cyclopentadienyl group is preferable and a 1, 3-substituted cyclopentadienyl group is especially preferable.
    In the above general formula (I), the ligand L 1 other than the substituted cyclopentadienyl group coordinated to the transition metal atom M is a C1-C12 hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or It is a hydrogen atom.
    As a C1-C12 hydrocarbon group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, etc. can be illustrated, More specifically, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group alkyl groups such as sec-butyl, tert-butyl, pentyl, octyl, 2-ethylhexyl and decyl; Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; Aryl groups, such as a phenyl group and a tolyl group; Aralkyl groups, such as a benzyl group and a neofill group, can be illustrated.
    Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentoxy group, hexoxy group and octoxy group can do.
    A phenoxy group etc. can be illustrated as an aryloxy group.
    Examples of the trialkylsilyl group include trimethylsilyl group, triethylsilyl group, triphenylsilyl group and the like.
    Halogen atoms are fluorine, chlorine, bromine and iodine.
    Examples of the transition metal compound represented by General Formula (I) include
    Bis (n-propylcyclopentadienyl) zirconium dichloride,
    Bis (n-butylcyclopentadienyl) zirconium dichloride,
    Bis (n-hexylcyclopentadienyl) zirconium dichloride,
    Bis (methyl-n-propylcyclopentadienyl) zirconium dichloride,
    Bis (methyl-n-butylcyclopentadienyl) zirconium dichloride,
    Bis (dimethyl-n-butylcyclopentadienyl) zirconium dichloride,
    Bis (n-butylcyclopentadienyl) zirconium dibromide,
    Bis (n-butylcyclopentadienyl) zirconium methoxychloride,
    Bis (n-butylcyclopentadienyl) zirconium ethoxychloride,
    Bis (n-butylcyclopentadienyl) zirconium butoxychloride,
    Bis (n-butylcyclopentadienyl) zirconium diethoxide,
    Bis (n-butylcyclopentadienyl) zirconium methyl chloride,
    Bis (n-butylcyclopentadienyl) zirconium dimethyl,
    Bis (n-butylcyclopentadienyl) zirconium benzyl chloride,
    Bis (n-butylcyclopentadienyl) zirconiumdibenzyl,
    Bis (n-butylcyclopentadienyl) zirconiumphenyl chloride,
    Bis (n-butylcyclopentadienyl) zirconium hydride chloride
    Can be mentioned.
    In the above example, two substituents of the cyclopentadienyl ring include 1,2- and 1,3- substituents, and three substituents include 1,2,3- and 1,2,4-substituents.
    In the present invention, in the above zirconium compound, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal can be used.
    Among the transition metal compounds represented by general formula (I), bis (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3- Particular preference is given to n-propylcyclopentadienyl) zirconium dichloride and bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride.
    In Formula (II), M is a transition metal atom selected from Group 4 of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium.
    L 2 is a ligand that coordinates to the transition metal atom M, at least two of them, L 2, is a methylcyclopentadienyl group or an ethylcyclopentadienyl group, and each may be the same or different.
    In the above general formula (II), the ligand L 2 other than the methylcyclopentadienyl group or the ethylcyclopentadienyl group coordinated to the transition metal atom M is a hydrocarbon having 1 to 12 carbon atoms such as L 1 in the general formula (I). Group, alkoxy group, aryloxy group, trialkylsilyl group, halogen atom or hydrogen atom.
    Examples of the transition metal compound represented by General Formula (II)
    Bis (methylcyclopentadienyl) zirconium dichloride,
    Bis (ethylcyclopentadienyl) zirconium dichloride,
    Bis (methylcyclopentadienyl) zirconium dibromide,
    Bis (ethylcyclopentadienyl) zirconium dibromide,
    Bis (methylcyclopentadienyl) zirconium methoxychloride,
    Bis (ethylcyclopentadienyl) zirconium methoxychloride,
    Bis (methylcyclopentadienyl) zirconium ethoxychloride,
    Bis (ethylcyclopentadienyl) zirconium ethoxychloride,
    Bis (methylcyclopentadienyl) zirconium diethoxide,
    Bis (ethylcyclopentadienyl) zirconium diethoxide,
    Bis (methylcyclopentadienyl) zirconium methyl chloride,
    Bis (ethylcyclopentadienyl) zirconium methyl chloride,
    Bis (methylcyclopentadienyl) zirconium dimethyl,
    Bis (ethylcyclopentadienyl) zirconium dimethyl,
    Bis (methylcyclopentadienyl) zirconium benzyl chloride,
    Bis (ethylcyclopentadienyl) zirconium benzyl chloride,
    Bis (methylcyclopentadienyl) zirconiumdibenzyl,
    Bis (ethylcyclopentadienyl) zirconiumdibenzyl,
    Bis (methylcyclopentadienyl) zirconiumphenyl chloride,
    Bis (ethylcyclopentadienyl) zirconiumphenyl chloride,
    Bis (methylcyclopentadienyl) zirconium hydride chloride,
    And bis (ethylcyclopentadienyl) zirconium hydride chloride.
    In the present invention, in the above zirconium compound, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal can be used.
    Among the transition metal compounds represented by these general formulas (II), bis (methylcyclopentadienyl) zirconium dichloride and bis (ethylcyclopentadienyl) zirconium dichloride are particularly preferable.
    In the present invention, at least one transition metal compound selected from the transition metal compound represented by the general formula (I) as the transition metal compound and the transition metal compound represented by the general formula (II) Metal compounds are used in combination. As a combination method, under the same polymerization conditions, MFR (MFR (I)) and a transition metal compound component of an olefin polymer obtained from a catalyst component containing only the transition metal compound represented by the general formula (I) as a transition metal compound component As a combination of catalysts in which the ratio of MFR (MFR (II)) of the olefin polymer obtained from the catalyst component containing only the transition metal compound represented by the above general formula (II) is MFR (I) / MFR (II) ≦ 20 It is preferable.
    Specifically, bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride and bis (methylcyclopentadienyl) zirconium dichloride are combined and bis (1,3-n-propylmethylcyclopentadienyl ) Zirconium dichloride and bis (methylcyclopentadienyl) zirconium dichloride are preferably combined, and bis (n-butylcyclopentadienyl) zirconium dichloride and bis (methylcyclopentadienyl) zirconium dichloride are preferably combined.
    At least one transition metal compound (bI) selected from the transition metal compounds represented by the general formula (I) and at least one transition metal compound (b-) selected from the transition metal compounds represented by the general formula (II). II) has a molar ratio (bI / b-II) of 99/1 to 40/60, preferably 95/5 to 45/55, more preferably 90/10 to 50/50, most preferably 85/15 It is recommended to use the amount in the range of ~ 55/45.
    The transition metal compound containing at least one selected from the transition metal compounds (bI) represented by the general formula (I) below and at least one selected from the transition metal compounds (b-II) represented by the general formula (II). The catalyst component may be described as "component (b)".
    The catalyst for olefin polymerization (Cat-1) is formed of the organoaluminum oxy compound (a), the transition metal compound (bI) and the transition metal compound (b-II). The oxy compound (a), the transition metal compound (bI) and the transition metal compound (b-II) may be supported and used as a catalyst (Cat-2).
    (c) carrier
    The carrier (c) to be used as necessary is an inorganic or organic compound, and granular or particulate solids having a particle diameter of 10 to 300 µm, preferably 20 to 200 µm are used. Among the inorganic compounds, a porous oxide is preferable, and specifically, SiO 2 , Al 2 O 3 , MgO, ZrO 2 , TiO 2 , B 2 O 3 , CaO, ZnO, BaO, ThO 2 , or the like, or a mixture containing them. For example, SiO 2 -MgO, SiO 2 -Al 2 O 3 , SiO 2 -TiO 2 , SiO 2 -V 2 O 5 , SiO 2 -Cr 2 O 3 , SiO 2 -TiO 2 -MgO and the like will be exemplified. Can be.
    Of these, it is preferable that a main component at least one kind of component selected from the group as SiO 2 and Al 2 O 3.
    In addition, the inorganic oxide contains a small amount of Na 2 CO 3 , K 2 CO 3 , CaCO 3 , MgCO 3 , Na 2 SO 4 , Al 2 (SO 4 ) 3 , BaSO 4 , KNO 3 , Mg (NO 3 ) 2 , Al (nO 3) 3, also there is no hindrance to contain the carbonate, sulfate, nitrate and oxide components such as Na 2 O, K 2 O, Li 2 O.
    Such carrier (c) has different properties depending on the type and production method, but the carrier used preferably has a specific surface area of 50 to 1000 m 2 / g, preferably 100 to 700 m 2 / g, and a pore volume of 0.3 to 2.5. It is preferable that it is cm <3> / g. The carrier is used by firing at 100 to 1000 ° C, preferably 150 to 700 ° C, if necessary.
    In such a carrier (c), the amount of adsorbed water is preferably less than 1.0% by weight, preferably less than 0.5% by weight, and the surface hydroxyl value is 1.0% by weight or more, preferably 1.5 to 4.0% by weight, particularly preferably 2.0 to 3.5% by weight. It is good to be%.
    The amount of adsorbed water (% by weight) and the amount of surface hydroxyl groups (% by weight) of the carrier (c) are determined as follows.
    (Amount of adsorption)
    At 200 ° C., the percentage of the reduced weight when dried for 4 hours under normal pressure and nitrogen flow as the weight before drying is taken as the adsorption water amount.
    (Surface fishery)
    The weight of the carrier obtained by drying at 200 ° C. for 4 hours under normal pressure and nitrogen flow was X (g), and the weight of the fired product obtained by calcining the carrier at 1000 ° C. for 20 hours was Y (g). It calculates by the following formula.
    Surface hydroxyl level (wt%) = ((X-Y) / X) × 100
    Moreover, as a carrier (c) which can be used for this invention, the granular or particulate solid of an organic compound whose particle diameter is the range of 10-300 micrometers is mentioned. These organic compounds include a (co) polymer or vinylcyclohexane, styrene produced by using a C2-C14 α-olefin such as ethylene, propylene, 1-butene, or 4-methyl-1-pentene as a main component. The produced polymer or copolymer can be illustrated.
    Moreover, as an ingredient which forms the catalyst for olefin polymerization (Cat-1) and (Cat-2), the following organoaluminum compound (d) can be used as needed.
    (d) organoaluminum compounds
    Examples of the organoaluminum compound (d) (hereinafter sometimes referred to as "component (d)") to be used if necessary include an organoaluminum compound represented by the following general formula (i).
    R 1 n AlX 3-n ------- (i)
    (Wherein R 1 is a hydrocarbon group of 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, n is 1 to 3)
    In general formula (i), R 1 is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, n-propyl group, isopropyl group, isobutyl group, pen And a methyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.
    Specific examples of such organoaluminum compound (d) include the following compounds.
    Trialkyl aluminum, such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum and tri-2-ethylhexyl aluminum;
    Alkenyl aluminum, such as isoprenyl aluminum;
    Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide;
    Alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide;
    Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride and ethylaluminum dibromide;
    Alkyl aluminum hydrides, such as diethyl aluminum hydride and diisobutyl aluminum hydride.
    Moreover, the compound represented by the following general formula (ii) can also be used as an organoaluminum compound (d).
    R 1 n AlY 3-n ----- (ii)
    (Wherein R 1 is the same as above, Y is —OR 2 group, —OSiR 3 3 group, —OAlR 4 2 group, —NR 5 2 group, —SiR 6 3 group or —N (R 7 ) AlR 8 2 group, n is 1-2, R 2 , R 3 , R 4 and R 8 are methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl group, phenyl group and the like, R 5 is a hydrogen atom, Methyl group, ethyl group, isopropyl group, phenyl group, trimethylsilyl group, and the like, and R 6 and R 7 are methyl group, ethyl group and the like.) Examples of such organoaluminum compounds include the following compounds.
    (1) a compound represented by R 1 n Al (OR 2 ) 3-n , for example, dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide and the like;
    (2) a compound represented by R 1 n Al (OSiR 3 3 ) 3-n , for example Et 2 Al (OSiMe 3 ), (iso-Bu) 2 Al (OSiMe 3 ), (iso-Bu) 2 Al (OSiEt 3 ) and the like;
    (3) a compound represented by R 1 n Al (OAlR 4 2 ) 3-n , for example Et 2 AlOAlEt 2 , (iso-Bu) 2 AlOAl (iso-Bu) 2, and the like;
    (4) a compound represented by R 1 n Al (NR 5 2 ) 3-n , for example Me 2 AlNEt 2 , Et 2 AlHNMe, Me 2 AlNHEt, Et 2 AlN (SiMe 3 ) 2 , (iso-Bu) 2 AlN (SiMe 3 ) 2 and the like;
    (5) a compound represented by R 1 n Al (SiR 6 3 ) 3-n , such as (iso-Bu) 2 AlSiMe 3 and the like;
    (6) a compound represented by R 1 n Al (N (R 7 ) AlR 8 2 ) 3-n , for example Et 2 AlN (Me) AlEt 2 , (iso-Bu) 2 AlN (Et) Al (iso -Bu) 2 and the like.
    Among the organoaluminum compounds represented by the general formulas (i) and (ii), R 1 3 Al, R 1 n Al (OR 2 ) 3-n , R 1 n Al (OAlR 4 2 ) 3-n The compound represented is preferable, and the compound whose R <1> is an isoalkyl group and n = 2 is especially preferable.
    The olefin polymerization catalyst (Cat-1) is formed of the above-mentioned component (a) and component (b) and the component (d) as needed, and the olefin polymerization catalyst (Cat-2) (solid catalyst (Cat- 2)) is formed of the solid catalyst (component) in which the above components (a) and (b) are supported on the carrier (c) and, if necessary, the component (d).
    The catalyst for olefin polymerization (Cat-1) can be produced by mixing and contacting each catalyst component in the polymerization reactor or outside the polymerization reactor. However, after the component (a) is made into a solid component, the solid phase catalyst is mixed and brought into contact with the component (b). After forming or contact-mixing component (a) and component (b) in advance, the solid catalyst may be added to the polymerization system.
    The catalyst for olefin polymerization (Cat-1) can be formed by mixing and contacting component (a), component (b) and component (d) as necessary in an inert hydrocarbon solvent. Although the contact order of each component is arbitrarily selected, in the case of mixing and contacting component (a) and component (b), it is preferable to add component (b) to the suspension of component (a). Moreover, it is preferable that component (b) mix-contacts with another component, after mixing two or more types of transition metal compounds (component (b-I) and (b-II)) which form the said component (b) beforehand.
    Specific examples of the inert hydrocarbon solvent used in the preparation of the catalyst for olefin polymerization (Cat-1) include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and the like, and mixtures thereof.
    When the component (a) and the component (b) and the component (d) are mixed and contacted as necessary, the concentration of the component (a) is converted into aluminum in the component (a) and is about 0.1 to 5 mol / liter (solvent). Preferably it is 0.3-3 mol / liter (solvent) range. The atomic ratio (Al / transition metal) of aluminum (Al) in the component (a) and the transition metal in the component (b) is usually 10 to 500, preferably 20 to 200. The atomic ratio (Al-d / Al-a) of the aluminum atom (Al-d) in the component (d) to be used as necessary and the aluminum atom (Al-a) in the component (a) is usually 0.02 to 3, preferably Is in the range of 0.05 to 1.5. The mixing temperature at the time of mixing and contacting component (a), component (b), and component (d) as needed is normally -50-150 degreeC, Preferably it is -20-120 degreeC, and a contact time is 1 minute-50 The time is preferably 10 minutes to 25 hours.
    In the olefin polymerization catalyst (Cat-1) prepared as described above, the component (b) per 1 g of the catalyst is converted into a transition metal atom so that 5 × 10 −6 to 5 × 10 −4 moles, preferably 10 −5 to 2 x 10 -4 moles, and 10 -2 to 2.5 x 10 -2 moles, preferably 1.5 x 10 -2 to 2 x 10 -2 , in terms of component (a) and component (d) in terms of aluminum atoms It is good to be.
    The solid catalyst (Cat-2) can be produced by supporting the above components (a) and (b) and, if necessary, the component (d) on the carrier (c).
    The order of contacting of the component (a), the component (b), the carrier (c) and the component (d) when preparing the solid catalyst (Cat-2) is arbitrarily selected, but preferably the component (a) and the carrier (c) are preferred. ) And the mixed contact with component (b), followed by mixed contact with component (d) as necessary. In addition, the component (b) is preferably mixed with other components after mixing two or more kinds of the transition metal compounds, the components (b-I) and (b-II) forming the component (b) in advance.
    The contacting of the component (a), component (b), carrier (c) and component (d) can be carried out in an inert hydrocarbon solvent, and the catalyst for olefin polymerization specifically described above as an inert hydrocarbon solvent used in the preparation of the catalyst. The inert hydrocarbon solvent used at the time of manufacture of (Cat-1) is mentioned.
    When a component (a), a component (b) and a carrier (c) and, if necessary, the component (d) are mixed in contact, the component (b) is converted into 5 x 10 -6 to 5 x 10 in terms of transition metal atoms per gram of the carrier. -4 moles, preferably 10 -5 to 2 x 10 -4 moles are used, and the concentration of component (b) is about 10 -4 to 2 x 10 -2 moles / liter (solvent), preferably 2 x 10 -4 to 10 -2 mol / liter (solvent). The atomic ratio (Al / transition metal) of aluminum (Al) in the component (a) and the transition metal in the component (b) is usually 10 to 500, preferably 20 to 200. The atomic ratio (Al-d / Al-a) of the aluminum atom (Al-d) in the component (d) to be used as necessary and the aluminum atom (Al-a) in the component (a) is usually 0.02 to 3, preferably Is in the range of 0.05 to 1.5. The mixing temperature at the time of the mixed contact between the component (a), the component (b) and the carrier (c) and, if necessary, the component (d) is usually -50 to 150 ° C, preferably -20 to 120 ° C, and the contact time. Is 1 minute to 50 hours, preferably 10 minutes to 25 hours.
    The catalyst for olefin polymerization (Cat-2) prepared as described above has 5 x 10 -6 to 5 x 10 -4 moles, preferably 10 -of component (b) per 1 g of the carrier (c) in terms of transition metal atoms. 5 ~ 2 × 10 -4 mol to be supported, and the support (c) component per 1g (a) and the component (d) to the aluminum atom in terms of ~ 5 × 10 -2 mol -3 10, preferably from 2 × 10 - It is better to carry 3 to 2 × 10 -2 .
    The olefin polymerization catalyst (Cat-2) may be a prepolymerization catalyst in which olefins are prepolymerized.
    The prepolymerization catalyst can be produced by introducing olefins into an inert hydrocarbon solvent in the presence of the above components (a), (b) and carrier (c) to perform prepolymerization. In addition, the solid catalyst component (Cat-2) is preferably formed from the component (a), the component (b) and the carrier (c). In this case, component (a) and / or component (d) may further be added to the solid catalyst component (Cat-2).
    The prepolymerization catalyst may be introduced into the suspension of the above-mentioned solid catalyst (Cat-2) (solid catalyst component), or may be produced after the solid catalyst (Cat-2) is produced. ) May be separated from the suspension, and then the solid catalyst (Cat-2) may be suspended again with an inert hydrocarbon, and olefin may be introduced therein.
    When preparing the prepolymerization catalyst, the component (b) is usually converted into a transition metal atom in the component (b) in the range of 10 −6 to 2 × 10 −2 mol / liter (solvent), preferably 5 × 10 −5 to 10 -2 mol / l (solvent) is used, the component (b) is usually 5 × 10 -6 ~ 5 × 10 -4 mol, preferably 10 -5 ~ 2 × 10, in terms of transition metal atom per carrier 1g - 4 moles are used. The atomic ratio (Al / transition metal) of aluminum in component (a) and transition metal in component (b) is usually 10 to 500, preferably 20 to 200. The atomic ratio (Al-d / Al-a) of the aluminum atom (Al-d) in the component (d) to be used as necessary and the aluminum atom (Al-a) in the component (a) is usually 0.02 to 3, preferably Is in the range of 0.05 to 1.5.
    The solid catalyst component is usually 10 −6 to 2 × 10 −2 mol / liter (solvent), preferably 5 × 10 −5 to 10 −2 mol / liter (solvent) as the transition metal in the transition metal compound.
    Prepolymerization temperature is -20-80 degreeC, Preferably it is 0-60 degreeC, and prepolymerization time is 0.5-100 hours, Preferably it is about 1-50 hours.
    The olefins used in the prepolymerization include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1 -Decene, 1-dodecene, 1-tetradecene and the like can be exemplified. Of these, ethylene or a combination of ethylene and an α-olefin used in polymerization is particularly preferable.
    The prepolymerization catalyst is prepared, for example, as follows. In other words, the carrier is suspended in an inert hydrocarbon. Subsequently, an organoaluminum oxy compound (component (a)) is added to this suspension and made to react for predetermined time. The supernatant is then removed and the solid component obtained is resuspended with inert hydrocarbon. After adding a transition metal compound (component (b)) to this system and making it react for a predetermined time, supernatant liquid is removed and a solid catalyst component is obtained. Subsequently, the above-mentioned solid catalyst component is added to the inert hydrocarbon containing an organoaluminum compound (component (d)), and an olefin is introduce | transduced here and a prepolymerization catalyst is obtained.
    In the preliminary polymerization, the resulting olefin polymer is preferably 0.1 to 500 g, preferably 0.2 to 300 g, more preferably 0.5 to 200 g per 1 g of the carrier (c).
    In the prepolymerization catalyst, the component (b) per 1 g of the carrier is supported by about 5 x 10 -6 to 5 x 10 -4 moles, preferably 10 -5 to 2 x 10 -4 moles, in terms of transition metal atoms. The aluminum atom (Al) in a) and component (b) may be supported in a molar ratio (Al / M) to transition metal atom (M) in component (b) in the range of 5 to 200, preferably in the range of 10 to 150. .
    The preliminary polymerization can be carried out either batchwise or continuously, and can be carried out either under reduced pressure, atmospheric pressure or pressure. In prepolymerization, it is preferable to produce a prepolymer having hydrogen in the presence of at least 0.2 to 7 dl / g, preferably 0.5 to 5 dl / g, which has an intrinsic viscosity (η) measured in at least 135 ° C decalin solution.
    Copolymerization of ethylene and alpha -olefin is carried out in a gaseous phase or a slurry liquid phase in the presence of the catalyst for olefin polymerization as described above, preferably in a gaseous phase. In slurry polymerization, an inert hydrocarbon may be used as a solvent, and olefin itself may be used as a solvent.
    Specific examples of the inert hydrocarbon solvent used for slurry polymerization include aliphatic hydrocarbons such as propane, butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane and octadecane; Alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane and cyclooctane; Aromatic hydrocarbons such as benzene, toluene and xylene; Petroleum fractions such as gasoline, kerosene and diesel. Among these inert hydrocarbon solvents, aliphatic hydrocarbons, alicyclic hydrocarbons, petroleum fractions and the like are preferable.
    In the case of the slurry polymerization method or the gas phase polymerization method, the catalyst is usually 10 -8 to 10 -3 moles / liter, preferably 10 -7 to 10 -4 moles / liter as the concentration of the transition metal atom in the polymerization reaction system. It is good to use.
    In the catalyst for olefin polymerization formed from the component (a) and the component (b) and the component (d) as needed, the transition in the aluminum atom (Al) and the transition metal compound (b) in the component (d) used as needed The atomic ratio (Al / M) of the metal atoms (M) is in the range of 5 to 300, preferably 10 to 200, more preferably 15 to 150.
    In the catalyst for olefin polymerization formed from component (a), component (b) and carrier (c) and, if necessary, component (d), at the time of polymerization, to the organoaluminum oxy compound (component (a)) supported on the carrier The organic aluminum oxy compound which is not supported may be further added and used. In this case, the atomic ratio (Al / M) of the aluminum atom (Al) in the unsupported organoaluminum oxy compound and the transition metal atom (M) in the transition metal compound (b) is 5 to 300, preferably 10 to 200 More preferably, it is the range of 15-150. The component (d) used as needed may be supported by the support (c), and may be added at the time of superposition | polymerization. At this time, the component (d) supported on the carrier and the component (d) added during polymerization may be the same or different. The atomic ratio (Al / M) of the aluminum atom (Al) in the component (d) to be used as necessary and the transition metal atom (M) in the transition metal compound (b) is 5 to 300, preferably 10 to 200, more Preferably it is the range of 15-150.
    When the slurry polymerization method is carried out, the polymerization temperature is usually -50 to 100 ° C, preferably 0 to 90 ° C, and when the vapor phase polymerization method is carried out, the polymerization temperature is usually 0 to 120 ° C, preferably 20 to 100 ° C. ℃.
    The polymerization pressure is usually at normal pressure to 100 kg / cm 2, preferably 2 to 50 kg / cm 2, and the polymerization can be carried out by any of batch, semi-continuous and continuous methods.
    Moreover, superposition | polymerization can be performed in two or more steps from which reaction conditions differ. The olefin polymerization catalyst may contain other components useful for olefin polymerization in addition to the above components.
    As the olefin which can be polymerized by such an olefin polymerization catalyst, in addition to ethylene and an α-olefin having 6 to 8 carbon atoms, for example, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-decene Α-olefins such as 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; Cyclic olefins having 3 to 20 carbon atoms, for example cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-di Metano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like. Styrene, vinylcyclohexane, diene, etc. can also be used.
    In the ethylene-α-olefin copolymer obtained by the olefin polymerization method, the structural unit derived from ethylene is 50 to 100% by weight, preferably 55 to 99% by weight, more preferably 65 to 98% by weight, most preferably Is present in the range of 70 to 96% by weight, and the structural unit derived from the C6-C8 α-olefin is 0 to 50% by weight, preferably 1 to 45% by weight, more preferably 2 to 35% by weight, most preferably Preferably 4 to 30% by weight.
    The ethylene-α-olefin copolymer thus obtained preferably has the properties shown in the above-mentioned (A-i) to (A-iii), and is excellent in moldability and can produce a film excellent in transparency and mechanical strength.
    Ethylene-α-olefin copolymer (B)
    The ethylene-α-olefin copolymer (B) is a random copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms. As a C6-C8 alpha olefin, the same thing as the above is mentioned.
    The ethylene-α-olefin copolymer (B) has 50 to 100% by weight of structural units derived from ethylene, preferably 55 to 99% by weight, more preferably 65 to 98% by weight, most preferably 70 to 96 The structural unit is present in a weight percent, derived from a C6-8 α-olefin 0 to 50% by weight, preferably 1 to 45% by weight, more preferably 2 to 35% by weight, particularly preferably 4 to 30% by weight is preferably present.
    It is preferable that an ethylene-alpha-olefin copolymer (B) has the characteristics of following (B-i)-(B-vii), and it is especially preferable to have the characteristics of following (B-i)-(B-viii).
    (B-i) The density d is in the range of 0880 to 0.970 g / cm 3, preferably 0.880 to 0960 g / cm 3, more preferably 0.890 to 0.935 g / cm 3 and most preferably 0.905 to 9930 g / cm 3.
    (B-ii) Melt flow rate (MFR) is 0.02-200g / 10min, Preferably it is 0.05-50g / l0min, More preferably, it is the range of 0.01-10g / 10min.
    (B-iii) n-decane soluble fraction (W (% by weight)) and density (d (g / cm 3)) at 23 ° C.
    For MFR≤10g / 10min,
    W <80 × exp (-l00 (d-0.88)) + 0.l
    Preferably W <60 × exp (−l00 (d-0.88)) + 0.l
    More preferably, W <40 x exp (-100 (d-0.88)) + 0.l
    In the case of MFR> 10g / 10 minutes
    W <80 x (MFR-9) 0.26 x exp (-100 (d-0.88)) + 0.1
    Satisfies the relationship indicated by.
    (B-iv) The temperature [Tm (° C.)] and the density [d (g / cm 3)] of the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC)
    Tm <400 × d-248
    Preferably Tm <450 × d-296
    More preferably, Tm <500 × d-343
    Especially preferably, Tm <550 × d-392
    Satisfies the relationship indicated by.
    The relationship between the temperature (Tm) and the density (d) of the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC), and the n-decane soluble fraction (W) and the density (d) have the above relationship The ethylene-α-olefin copolymer (B) has a narrow compositional distribution.
    (B-v) melt tension (MT (g)) and melt flow rate [MFR (g / l0 min)]
    9.0 × MFR -0.65>MT> 2.2 × MFR -0.84
    Preferably 9.0 × MFR -0.65>MT> 2.3 × MFR -0.84
    More preferably 8.5 × MFR -0.65>MT> 2.5 × MFR -0.84
    It satisfies the relationship indicated by.
    Since the ethylene-α-olefin copolymer having such a property has high melt tension (MT), moldability is good.
    (B-vi) Flow activation energy ((Ea) 10 -4 J / molK) obtained from the shift factor of the time-temperature overlap of the flow curve, carbon number (C) of the α-olefin in the copolymer, and α in the copolymer The relationship between the content of olefins (x mol%),
    (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 −4 ≤ (0.039Ln (C-2) +0.1660) × x + 2.87
    Preferably,
    (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 −4 ≤ (0.039Ln (C-2) +0.1500) × x + 2.87
    More preferably
    (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 −4 ≤ (0.039Ln (C-2) +0.1300) × x + 2.87
    Satisfies the relationship indicated by.
    (B-vii) The molecular weight distribution (Mw / Mn, Mw: weight average molecular weight, Mn: number average molecular weight) measured by GPC is 2.2 &lt; Mw / Mn &lt; 3.5,
    Preferably it is 2.4 <Mw / Mn <3.0.
    Moreover, molecular weight distribution (Mw / Mn) was measured as follows using GPC-150C by Mirpoa Co., Ltd.
    Separation column is TSK GNH HT, column size is 72mm in diameter, 600mm in length, column temperature is 140 ° C, 0.025% by weight of o-dichlorobenzene (Wako Pure Chemical Industries Co.) and BHT (Taketa Chemical) as antioxidant Differential refractometer was used at 0.1 ml / min, sample concentration was 0.1 wt%, sample injection amount was 500 microliters, and a differential refractometer was used as a detector. The standard polystyrene used the Tosoh Corporation for molecular weight Mw <1000 and Mw> 4x10 < 6 >, and the Fresha Chemical company for 1000 <Mw <4x10 <6> .
    The number of unsaturated bonds present in the molecule (B-viii) is 0.5 or less per 10,000 carbon atoms, and less than 1 per molecule of polymer.
    In addition, the quantification of the unsaturated bonds is performed by using 13 C-NMR, integrating the area intensity of signals belonging to the double bonds, i.e., the range of 10 to 50 ppm, and signals belonging to the double bonds, i.e., the signal of 105 to 150 ppm. Is determined from the ratio.
    The ethylene-α-olefin copolymer (B) is, for example, in the presence of a catalyst for olefin polymerization containing (a) an organic aluminum oxy compound and (b-II) a transition metal compound represented by the general formula (II). Obtained by copolymerizing ethylene and the C6-C8 alpha-olefin.
    The (a) organoaluminum oxy compound and (b-II) transition metal compound are the same as those described in the manufacturing method of the said ethylene-alpha-olefin copolymer (A). As in the case described above, the carrier (c) and the organoaluminum compound (d) may be used or prepolymerized. The usage-amount of each component, prepolymerization conditions, and this polymerization condition are also the same as the case of the said ethylene-alpha-olefin copolymer (A) manufacture.
    Ethylene-α-olefin copolymer (C)
    The ethylene-α-olefin copolymer (C) is a random copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms. The same thing as the above is mentioned as a C6-C8 alpha olefin.
    In the ethylene-α-olefin copolymer (C), the structural unit derived from ethylene is 50 to 100% by weight, preferably 55 to 99% by weight, more preferably 65 to 98% by weight, most preferably 70 to 96 wt% is present, and the structural unit derived from an α-olefin having 6 to 8 carbon atoms is 0 to 50 wt%, preferably l to 45 wt%, more preferably 2-35 wt%, particularly preferably 4 It is preferred to be present at -30% by weight.
    It is preferable that an ethylene-alpha-olefin copolymer (C) has the characteristic shown to following (C-i)-(C-v), and it is especially preferable to have the characteristic shown to following (C-i)-(C-vi).
    (C-i) The density d is in the range of 0880 to 0.970 g / cm 3, preferably 0.880 to 0,960 g / cm 3, more preferably 0.890 to 0.935 g / cm 3 and most preferably 0.905 to 0.930 g / cm 3.
    (C-iii) Melt Flow Rate (MFR) is in the range of 0.02 to 200 g / l0 minutes, preferably 0.05 to 50 g / 10 minutes, more preferably 0.1 to 10 g / 10 minutes.
    (C-iii) n-decane soluble fraction (W (% by weight)) and density (d (g / cm 3)) at 23 ° C.,
    For MFR≤10g / 10min,
    W <80 x exp (-l00 (d-0.88)) + 0.1
    Preferably W <60 × exp (−l00 (d-0.88)) + 0.l
    More preferably, W <40 x exp (-100 (d-0.88)) + 0.l
    In the case of MFR> l0g / 10min,
    W <80 × (MFR-9) 0.26 × exp (-100 (d-0.88)) + 0.l
    Satisfies the relationship indicated by.
    (C-iv) The temperature (Tm (° C.)) and the density (d (g / cm 3)) of the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC)
    Tm <400 × d-248
    Preferably Tm <450 × d-296
    More preferably, Tm <500 × d-343
    Especially preferably, Tm <550 × d-392
    Satisfies the relationship indicated by
    The relationship between the temperature (Tm) and the density (d) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC), and the relationship between the n-decane soluble fraction (W) and the density (d) as described above. The ethylene-α-olefin copolymer having a narrow compositional distribution.
    (C-v) melt tension (MT (g)) and melt flow rate (MFR (g / 10 min))
    MT≤2.2 × MFR -0.84
    Satisfy the relationship.
    The number of unsaturated bonds present in the (C-vi) molecule is 0.5 or less per 10,000 carbon atoms, and less than 1 per molecule of polymer.
    Such ethylene-α-olefin copolymer (C) is, for example, in the presence of a catalyst for olefin polymerization containing (a) an organoaluminum oxy compound and (BI) a transition metal compound represented by the general formula (I). It is obtained by copolymerizing C6-C8 olefin. The (a) organic aluminum oxy compound and the (b-I) transition metal compound are the same as described in the manufacturing method of the said ethylene-alpha-olefin copolymer (A). As in the case described above, the carrier (c) and the organoaluminum compound (d) may be used or prepolymerized. The usage-amount of each component, prepolymerization conditions, and this polymerization condition are also the same as the case of the said ethylene-alpha-olefin copolymer (A) manufacture.
    (E) high pressure radical method low density polyethylene
    High Pressure Radical Low Density Polyethylene is a branched polyethylene with long chain branching produced by so-called high pressure radical polymerization, and the MFR measured under conditions of 190 ° C and 2.16 kg load in accordance with ASTM D1238-65T ranges from 0.l to 50 g / 10 minutes, Preferably it is the range of 0.2-10 g / l0 minutes, More preferably, it is the range of 0.2-8 g / l0 minutes.
    The high pressure radical low density polyethylene has an index (Mw / Mn: Mw = weight average molecular weight, Mn = number average molecular weight) and a melt flow rate (MFR) of molecular weight distribution measured using gel permeation chromatography (GPC).
    7.5 × log (MFR) -1.2≤Mw / Mn≤7.5 × log (MFR) +12.5
    Preferably 7.5 × log (MFR) −0.5 ≦ Mw / Mn ≦ 7.5 × log (MFR) +12.0
    More preferably 7.5 × log (MFR) ≦ Mw / Mn ≦ 7.5 × log (MFR) +12.0
    Satisfies the relationship indicated by
    Moreover, the measuring method of the molecular weight distribution of a high pressure radical method low density polyethylene is the same as the above.
    In addition, the high pressure radical method low density polyethylene preferably has a density in the range of 0.910 to 0.930 g / cm 3.
    Density is measured in a density gradient tube after heat-treating the strand obtained at the time of melt flowrate measurement at the load of 2.16 kg at 190 degreeC at 120 degreeC for 1 hour, and slowly cooling to room temperature over 1 hour.
    In addition, the high pressure radical low density polyethylene was extruded at a extrusion speed of 10 mm / min from a nozzle having an inner diameter (D) of 2.0 mm and a length of 15 mm under conditions of 190 ° C. using a swell ratio, that is, a capillary flow characteristic tester indicating the degree of long chain branching. It is preferable that ratio (Ds / D) of the diameter Ds of one strand and the nozzle inner diameter D is l.3 or more.
    In addition, as long as the high pressure radical method low density polyethylene does not impair the objective of this invention, it may be a copolymer with polymerizable monomers, such as another alpha olefin, vinyl acetate, and acrylate ester.
    Ethylene Copolymer Composition
    The ethylene-based copolymer composition (A) according to the present invention comprises the ethylene-α-olefin copolymer (A) and the high pressure radical method low density polyethylene (E).
    Although the composition ratio of the ethylene copolymer composition (A) which consists of an ethylene-alpha-olefin copolymer (A) and a high pressure radical method low density polyethylene (E) is not restrict | limited especially, (A) Ethylene-alpha-olefin copolymer (A ) Is usually contained in a proportion of 99 to 60% by weight, preferably 99 to 80% by weight, more preferably 99 to 90% by weight, and the high pressure radical method low density polyethylene (E) is usually 1 to 40% by weight, preferably Is preferably contained in an amount of 1 to 20% by weight, more preferably 1 to 10% by weight.
    Such an ethylene copolymer composition (A) can be manufactured using a well-known method, for example, can be manufactured by the following method.
    (l) A method of mechanically blending an ethylene-α-olefin copolymer (A) and a high pressure radical method low density polyethylene (E) and other components to be added, if necessary, using an extruder, a kneader or the like.
    (2) Ethylene-α-olefin copolymer (A) and high pressure radical method low density polyethylene (E), and other components to be added, if necessary, in a suitable good solvent (for example; hexane, heptane, decane, cyclohexane, benzene , Hydrocarbon solvents such as toluene and xylene), and then the solvent is removed.
    (3) preparing a solution in which an ethylene-α-olefin copolymer (A) and a high pressure radical method low density polyethylene (E), and other components added as needed, were separately dissolved in a suitable good solvent, respectively, and then mixed. How to remove the solvent in.
    (4) A method performed by combining the methods of (l) to (3) above.
    The ethylene-based copolymer composition (A ') according to another aspect of the present invention is the ethylene-α-olefin copolymer (B), the ethylene-α-olefin copolymer (C) and the high pressure radical method low density polyethylene (E). do.
    The ethylene-based copolymer composition (A ') made of an ethylene-α-olefin copolymer (B), an ethylene-α-olefin copolymer (C) and a high pressure radical method low density polyethylene (E) is not particularly limited in its composition ratio. The ethylene-α-olefin copolymers (B) and (C) are contained in a total amount of usually 99-60% by weight, preferably 99-80% by weight, more preferably 99-90% by weight, ( E) High Pressure Radical Method Low density polyethylene is usually contained in an amount of 1 to 40% by weight, preferably 1 to 20% by weight, more preferably 1 to 10% by weight.
    In addition, ethylene-alpha-olefin copolymer (B) and (C) make 100 weight% of total amounts of said (B) and (C), and the ethylene-alpha-olefin copolymer (B) is 1-90 weight% Preferably, it is 2 to 80 wt%, and the ethylene-α-olefin copolymer (C) is 10 to 99 wt%, preferably 20 to 98 wt%.
    Such an ethylene copolymer composition (A ') can be manufactured using a well-known method, for example, can be manufactured by the following method.
    (l) A method of mechanically blending an ethylene-α-olefin copolymer (B) and (C), a high pressure radical method low density polyethylene (E), and other components to be added, if necessary, using an extruder, a kneader or the like.
    (2) an ethylene-α-olefin copolymer (B) and (C), a high pressure radical method low density polyethylene (E), and other components to be added, if necessary, in a suitable good solvent (for example, hexane, butane, decane, Hydrocarbon solvents such as cyclohexane, benzene, toluene and xylene) and then remove the solvent.
    (3) After preparing the solution which melt | dissolved the ethylene-alpha-olefin copolymer (B) and (C), the high pressure radical method low density polyethylene (E), and the other component added as needed separately in a suitable good solvent, respectively, Then, the solvent is removed.
    (4) A method performed by combining the methods of (l) to (3) above.
    In the present invention, the composition (F) is formed from the ethylene-α-olefin copolymers (B) and (C), and then the known composition described above from the composition (F) and the high pressure radical method low density polyethylene (E). An ethylene copolymer composition (A ') can also be manufactured by the method.
    The composition (F) consisting of the ethylene-α-olefin copolymer (B) and the ethylene-α-olefin copolymer (C) is composed of a melt flow rate (MFR (B)) of the ethylene-α-olefin copolymer (B). Ratio of the melt flow rate (MFR (C)) of the ethylene-α-olefin copolymer (C),
    l <(MFR (C)) / (MFR (B)) ≤20
    It is preferable to be.
    Especially in this invention, it is preferable that all the said ethylene-alpha-olefin copolymers (B) and (C) are ethylene 1-hexene copolymers. In this case, the composition (F) made of the ethylene-α-olefin copolymer (B) and (C) preferably has substantially the same physical properties as the ethylene-α-olefin copolymer (A), as shown below. The same usefulness is expected.
    (A'-i) melt tension (MT (g)) and melt flow rate (MFR (g / 10min))
    9.0 × MFR -0.65>MT> 2.2 × MFR -0.84
    Preferably
    9.0 × MFR -0.65>MT> 2.3 × MFR -0.84
    More preferably
    8.5 × MFR -0.65>MT> 2.5 × MFR -0.84
    Satisfies the relationship indicated by.
    Since the composition (F) having such a characteristic has a high melt tension (MT), the moldability is good.
    (A'-ii) Flow activation energy ((E a ) × 10 -4 J.molK) obtained from the shift factor of time-temperature overlap of the flow curve, and hexene-1 in copolymers (B) and (C) The relationship between the carbon number (C) and the total content (x mol%) of 1-hexene in the copolymer (B) and (C)
    (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 −4 ≤ (0.039Ln (C-2) +0.1660) × x + 2.87
    Preferably,
    (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 −4 ≤ (0.039Ln (C-2) +0.1500) × x + 2.87
    More preferably
    (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 −4 ≤ (0.039Ln (C-2) +0.1300) × x + 2.87
    Satisfies the relationship indicated by.
    (A'-iii) When the composition (F) is produced with a film having a thickness of 30 µm by inflation molding, the haze of the film satisfies the following relationship.
    The fluidity index (FI) and melt flow rate (MFR), defined as the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 6 dyne / cm 2,
    For FI ≥100 × MFR
    Haze <0.45 / (ld) × log (3 × MT 1.4 ) × (C-3) 0.1
    The fluidity index (FI) and melt flow rate (MFR), defined as the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 6 dyne / cm 2,
    For FI <100 × MFR
    Haze <0.25 / (ld) × log (3 × MT 1.4 ) × (C-3) 0.1
    (Wherein d represents density (g / cm 3), MT represents melt tension (g), and C represents 1-hexene carbon number, that is, '6'.
    The composition (F) which consists of an ethylene-alpha-olefin copolymer (B) and (C) which satisfy | fills these requirements is excellent in moldability and the transparency of the film obtained.
    Moreover, it is preferable that the composition (F) which consists of an ethylene-alpha-olefin copolymer (B) and (C) satisfy | fills the following requirements in addition to the said requirements.
    (A'-iv) The molecular weight distribution (Mw / Mn, Mw: weight average molecular weight, Mn: number average molecular weight) measured by GPC is
    2.0 ≤ Mw / Mn ≤ 2.5
    Preferably, the range is 2.0 ≦ Mw / Mn ≦ 2.4.
    In the composition (F), the structural unit derived from ethylene is present in 50 to 100% by weight, preferably 55 to 99% by weight, more preferably 65 to 98% by weight, most preferably 70 to 96% by weight, The structural unit derived from an α-olefin having 6 to 8 carbon atoms, preferably 1-hexene, is 0 to 50% by weight, preferably 1 to 45% by weight, more preferably 2 to 35% by weight, particularly preferably 4-30% by weight is preferably present.
    The density (d) of the composition (F) is in the range of 0.880 to 0.970 g / cm 3, preferably 0.880 to 0.960 g / cm 3, more preferably 0.890 to 0.935 g / cm 3 and most preferably 0.905 to 0.930 g / cm 3 It is good.
    The melt flow rate (MFR) of the composition (F) is preferably 0.05 to 200 g / 10 minutes, preferably 0,08-50 g / 10 minutes, more preferably 0.1 to 10 g / 10 minutes.
    N-decane soluble fraction (W (% by weight)) and density (d (g / cm 3)) at 23 ° C. of the composition (F)
    For MFR≤10g / 10min,
    W <80 × exp (-100 (d-0.88)) + 0.l
    Preferably W <60 × exp (-100 (d-0.88)) + 0.l
    More preferably, W <40xexp (-l00 (d-0.88)) + 0.l
    In the case of MFR> 10g / 10 minutes
    W <80 x (MFR-9) 0.26 x exp (-100 (d-0.88)) + 0.1
    It is good to satisfy the relationship indicated by.
    The temperature (Tm (° C.)) and density (d (g / cm 3)) of the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) of the composition (F)
    Tm <400 × d-248
    Preferably Tm <450 × d-296
    More preferably, Tm <500 × d-343
    Especially preferably, Tm <550 × d-392
    It is good to satisfy the relationship indicated by.
    The relationship between the temperature (Tm) and the density (d) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC), and the n-decane soluble fraction (W) and the density (d) The composition (F) which has is narrow compositional distribution.
    The composition (F) which consists of an ethylene-alpha-olefin copolymer (B) and an ethylene-alpha-olefin copolymer (C) can be manufactured using a well-known method, For example, it can be manufactured by the following method. have.
    (l) Mechanically blending or melt-mixing the ethylene-α-olefin copolymer (B), the ethylene-α-olefin copolymer (C), and other components to be added, if necessary, using a turner, an extruder, a kneader, or the like. Way.
    (2) Ethylene-α-olefin copolymer (B), ethylene-α-olefin copolymer (C), and other components to be added, if necessary, in a suitable good solvent (e.g., hexene, heptane, decane, cyclohexane , Hydrocarbon solvents such as benzene, toluene and xylene), and then the solvent is removed.
    (3) After mixing the ethylene-alpha-olefin copolymer (B), the ethylene-alpha-olefin copolymer (C), and the other component added as needed in a suitable good solvent separately, respectively, mixing, Then, how to remove the solvent.
    (4) The method performed by combining the method of said (l)-(3).
    As described above, the ethylene copolymer composition (A) and the ethylene copolymer composition (A ') according to the present invention are both excellent in moldability and can produce a film excellent in transparency and mechanical strength. Further, in combination with other polymers, preferably an ethylene-α-olefin copolymer, for example, an ethylene-based copolymer composition (A) and a composition of another ethylene-α-olefin copolymer (ethylene-based copolymer composition (A ″) ), And an ethylene copolymer composition (A ') and a composition (ethylene copolymer composition (A "')) of another ethylene-alpha-olefin copolymer, etc. can be used. As such another ethylene-alpha-olefin copolymer, the ethylene-alpha-olefin copolymer (D) demonstrated below is especially used preferably.
    The ethylene-alpha-olefin copolymer (D) used for this invention is a random copolymer of ethylene and the C3-C20 alpha-olefin. Examples of α-olefins having 3 to 20 carbon atoms for copolymerization with ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, l-decene and 1-dode Sen, 1-tetradecene, l-hexadecene, 1-octadecene, 1-eicosene, etc. are mentioned.
    In the ethylene-α-olefin copolymer (D), the structural unit derived from ethylene is 50 to 100% by weight, preferably 55 to 99% by weight, more preferably 65 to 98% by weight, most preferably 70 to 96 The constituent units present in the wt% and derived from α-olefins having 3 to 20 carbon atoms are 0 to 50 wt%, preferably l to 45 wt%, more preferably 2 to 35 wt%, most preferably 4 It is preferred to be present at -30 wt%.
    It is preferable that such an ethylene-alpha-olefin copolymer (D) has the characteristic shown to following (Di) and (D-ii), and it is more preferable to have the characteristic shown to following (Di)-(D-iv). Do.
    (D-i) Density (d) is in the range of 0850 to 0.980 g / cm 3, preferably 0.910 to 0.960 g / cm 3, more preferably 0.915 to 0.955 g / cm 3 and most preferably 0.920 to 0.950 g / cm 3.
    (D-ii) Intrinsic viscosity ((eta)) measured in 135 degreeC and decalin is 0.4-8 dl / g, Preferably it is 0.4-1.25 dl / g, More preferably, it is the range of 0.5-1.23 dl / g.
    (D-iii) The temperature (Tm (° C.)) and the density (d (g / cm 3)) of the maximum peak position in the endothermic curve measured by a differential scanning calorimeter (DSC)
    Tm <400 * d-250
    Preferably Tm <450 × d-297
    More preferably, Tm <500 × d-344
    Especially preferably, Tm <550 × d-391
    It is good to satisfy the relationship indicated by.
    (D-iv) n-decane soluble fraction (W (% by weight)) and density (d (g / cm 3)) at room temperature
    For MFR≤10g / 10min,
    W <80 × exp (-100 (d-0.88)) + 0.l
    Preferably W <60 × exp (-100 (d-0.88)) + 0.1
    More preferably, W <40 x exp (-100 (d-0.88)) + 0.l
    For MFR> l0g / l0 minutes,
    W <80 × (MFR-9) 0.26 × exp (-100 (d-0.88)) + 0.l
    Satisfies the relationship indicated by.
    Thus, the relationship between the temperature (Tm) and the density (d) of the maximum peak position in the endothermic curve measured by a differential scanning calorimeter (DSC), and the n-decane soluble fraction (W) and the density (d) are The ethylene-α-olefin copolymer (D) having a relationship of has a narrow compositional distribution.
    However, the ethylene-α-olefin copolymer (A) and the ethylene-α-olefin copolymer (D) are not the same, and the ethylene-α-olefin copolymer (B) and (C) and the ethylene-α-olefin air Union D is not the same. Specifically, the ethylene-α-olefin copolymer (D) and the ethylene-α-olefin copolymer (A) to (C) can be distinguished by the following characteristics.
    That is, the ethylene-α-olefin copolymer (D) is a copolymer that does not satisfy at least one of the requirements (A-i) to (A-iii) for defining the copolymer (A).
    The ethylene-α-olefin copolymer (D) is a copolymer that does not satisfy at least one of the requirements (B-iii) to (B-vii) that define the copolymer (B).
    The ethylene-α-olefin copolymer (D) is a copolymer that does not satisfy at least one of the requirements (C-iii) to (C-v) that define the copolymer (C).
    Moreover, as an ethylene-alpha-olefin copolymer (D), it is one of the preferable aspects that the intrinsic viscosity ((eta)) measured in 135 degreeC and decalin is smaller than ethylene-alpha-olefin copolymer (A), and its density is low. Moreover, as an ethylene-alpha-olefin copolymer (D), it is also preferable that the intrinsic viscosity ((eta)) measured in 135 degreeC and decalin is smaller than ethylene-alpha-olefin copolymer (B) and (C), and its density is low. Is one of.
    Such ethylene-α-olefin copolymer (D) is, for example, in the presence of a catalyst for olefin polymerization containing (a) an organic aluminum oxy compound and (b-III) a transition metal compound represented by the following general formula (III). It is obtained by copolymerizing ethylene and olefins of 3 to 20 carbon atoms. The organic aluminum oxy compound (a) is the same as that described in the manufacturing method of the said ethylene-alpha-olefin copolymer (A). As in the case described above, the carrier (c) and the organoaluminum compound (d) may be used or prepolymerized. The usage-amount of each component, prepolymerization conditions, and this polymerization condition are also the same as the case of manufacture of the said ethylene-alpha-olefin copolymer (A).
    Hereinafter, the transition metal compound (b-III) will be described.
    (b-III) Transition Metal Compounds
    Transition metal compound of Group 4 of the periodic table containing a ligand having a (b-III) cyclopentadienyl skeleton used in the preparation of the ethylene-α-olefin copolymer (D) (hereinafter referred to as "component (b-III) Is not particularly limited as long as it is a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton, but a transition metal compound represented by the following general formula (III) is preferable.
    ML 3 x ------- (III)
    Wherein M is a transition metal atom selected from Group 4 of the periodic table, specifically zirconium, titanium or hafnium, with zirconium being preferred.
    X is the valence of the transition metal.
    L 3 is a ligand that coordinates to the transition metal atom M, at least one of L 3 is a ligand having a cyclopentadienyl skeleton, and a ligand having a cyclopentadienyl skeleton is, for example, a cyclopentadienyl group or methylcyclo Pentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methyl Alkyl-substituted cyclopentadienyl groups or indenyl groups, such as propylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclopentadienyl group, and hexylcyclopentadienyl group, 4,5,6,7-tetrahydroindenyl group, Fluorenyl group etc. can be illustrated. These groups may be substituted with halogen atoms, trialkylsilyl groups and the like.
    Among the ligands having these cyclopentadienyl skeletons, alkyl substituted cyclopentadienyl groups are particularly preferred.
    When the compound represented by the said general formula (III) contains two or more ligands which have a cyclopentadienyl frame | skeleton, the ligands which have two cyclopentadienyl frame | skeleton among these are alkylene groups, such as ethylene and propylene, and iso You may couple | bond via substituted alkylene groups, such as propylidene and diphenylmethylene, a silylene group, or substituted silylene groups, such as a dimethylsilylene group, a diphenylsilylene group, and a methylphenylsilylene group.
    In General Formula (III), L 3 other than a ligand having a cyclopentadienyl skeleton is a C 1-12 hydrocarbon group, an alkoxy group, an aryloxy group, the same as L 1 in General Formula (I), A trialkylsilyl group, a halogen atom, a hydrogen atom, or a SO 3 R group (wherein R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen). Examples of the ligand represented by SO 3 R include p-toluenesulfonato group, methanesulfonato group, trifluoromethanesulfonato group and the like.
    The transition metal compound represented by such general formula (III) is more specifically represented by the following general formula (III ') when the valence of the transition metal is 4, for example.
    R 2 k R 3 l R 4 m R 5 n M --------- (III ')
    (Wherein M is the transition metal atom, R 2 is a group having a cyclopentadienyl skeleton (ligand), and R 3 , R 4 and R 5 are a group having an cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group) , Aryl group, aralkyl group, alkoxy group, aryloxy group, trialkylsilyl group, SO 3 R group, halogen atom or hydrogen atom, k is an integer of 1 or more, k + l + m + n = 4)
    In the present invention, in the above general formula, a metallocene compound in which one of R 3 , R 4, and R 5 is a group having a cyclopentadienyl skeleton, for example, R 2 and R 3 is a cyclopentadienyl skeleton. The metallocene compound which is a group (ligand) which has is used preferably. Groups having these cyclopentadienyl skeletons include alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene, silylene groups or substituted silyls such as dimethylsilylene, diphenylsilylene and methylphenylsilylene It may be combined via a Len group or the like. In this case, other ligands (for example, R 4 and R 5 ) may be a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a trialkylsilyl group, or SO. R 3, is a halogen atom or a hydrogen atom.
    Such transition metal compounds represented by general formula (III) include bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato), bis (4 , 5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis Nil) dimethyl zirconium, ethylene bis (indenyl) diphenyl zirconium, ethylene bis (indenyl) methyl zirconium monochloride, ethylene bis (indenyl) zirconium bis (methanesulfonato), ethylene bis (indenyl) zirconium bis (p Toluenesulfonato), ethylenebis (indenyl) zirconiumbis (trifluoromethanesulfonato), ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadie) on -Fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopenta Dienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethyl Silylenebis (indenyl) zirconiumbis (trifluoromethanesulfonato), dimethylsilylenebis (4.5,6.7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium Dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, methylphenylsilylenebis (indenyl) zirconium dichloride, Bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methyl zircomnium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclo Pentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis (cyclopentadienyl) benzylzirconium monochloride, bis (cyclopentadienyl) zirconium monochloride monohydride, bis ( Cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) Zirconium methoxychloride, bis (cyclopentadienyl) zirconium ethoxychloride, bis (cyclopentadien Nile) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopenta) Dienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxychloride, bis (methylcyclopentadienyl) zirconium bis (fluoromethanesulfonato), Bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, Bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclophene Tadienyl) zirconium bis (methanesulfonato), bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, Bis (hexyl cyclopentadienyl) zirconium dichloride, bis (trimethylsilyl cyclopentadienyl) zirconium dichloride, etc. are mentioned.
    Also in the above examples, the disubstituents of the cyclopentadienyl ring include 1,2- and l, 3- substituents, and the trisubstituents include l, 2,3- and l, 2,4-substituents. Moreover, alkyl groups, such as propyl and butyl, contain isomers, such as n-, I-, sec-, and tert-.
    Moreover, in said zirconium compound, the compound which substituted zirconium by titanium or hafnium can also be used.
    The transition metal compound represented by the general formula (III) includes the transition metal compound (bI) represented by the general formula (I) and the transition metal compound (b-II) represented by the general formula (II). .
    The ethylene-α-olefin copolymer (D) is produced by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of the catalyst for olefin polymerization so that the density of the resulting copolymer becomes 0.850 to 0.980 g / cm 3. Can be.
    The ethylene-α-olefin copolymer (D) is preferably 99 to 60 parts by weight, more preferably to 100 parts by weight of the ethylene copolymer composition (A) or ethylene copolymer composition (A ') described above. It is used in the ratio of 95-160 weight part.
    The composition of the ethylene-α-olefin copolymer (D) and the ethylene copolymer composition (A) or the ethylene copolymer composition (A ') described above can be produced using a known method described above.
    The molded article according to the present invention is formed from the ethylene copolymer composition (A), (A '), (A ") or (A"').
    The molded article includes a single layer film, a multilayer film, an injection molded article, an extruded molded article, a fiber, a foam, an electric wire sheath, and more specifically, an agricultural film (single layer, multilayer), a waterproof sheet, a multilayer film, a packaging film (multilayer). Film, stretch film, film for high load packaging), multilayer barrier film, sealant for laminated film, heavy packaging film, grain bag, fluid packaging pouch, patch packaging package, pack-in box inner container, medical container, heat-resistant container, fiber , Foamed molded articles, gaskets, extruded products, pipes, various injection molded articles, electric wire sheaths, and the like.
    Below, the molded object formed from the said ethylene-based copolymer composition (A), (A '), (A ") or (A"') is demonstrated in more detail.
    Agricultural Film (Single Layer):
    Agricultural film is the ethylene-based copolymer composition (A), (A '), (A ") or (A"'), and if necessary, a conventionally known antioxidant, ultraviolet absorber, lubricant, slip agent, anti blocking agent, Additives such as a oil-repellent agent, an antistatic agent, a colorant, carbon black, a medium density polyethylene vinyl acetate copolymer, and an ethylene-α-olefin copolymer rubber.
    The agricultural film which concerns on this invention is 3-30 micrometers in thickness, Preferably it is the range of 7-20 micrometers.
    An agricultural film can be manufactured from the said ethylene-based copolymer composition (A), (A '), (A ") or (A"'), for example by film molding by the inflation method and the T-die method. . Film molding by the inflation method is performed by extruding the composition (A), (A '), (A ") or (A"') through a slit die and expanding with a predetermined air flow.
    Such agricultural films are excellent in adhesion to soil, that is, flexibility, and excellent in various properties such as weather resistance, tensile properties, tearing properties, impact resistance, and rigidity, and are mainly multi-films requiring geothermal synergistic effects. It is effectively used for house semi-thickness cultivation, processing non-cultivation cultivation, and early cultivation.
    Agricultural Multilayer Film:
    The agricultural multilayer film which concerns on this invention is a 3-layer laminated film which consists of an outer layer, an intermediate | middle layer, and an inner layer.
    (Outer floor)
    The outer layer constituting the multilayered agricultural film according to the present invention comprises the above-mentioned ethylene copolymer composition (A), (A '), (A ") or (A"'), an inorganic compound and a weathering stabilizer and an antifogging agent as needed. It forms from the composition containing it.
    Since the outer layer of this composition (A), (A '), (A ") or (A"') has a very small decrease in the light transmittance over time, an agricultural multilayer film having such an outer layer can be used over a long period of time. have.
    Moreover, when the composition (A), (A '), (A ") or (A"') is used, the outer layer of a multilayer film can be thinned, and weight reduction of a multilayer film can be aimed at.
    (Inorganic compound)
    The inorganic compound used at the time of forming the outer layer of the multilayer film is an inorganic oxide, an inorganic hydroxide, hydrotalcites or the like containing at least one atom of Mg, Ca, Al and Si effective as a heat insulating agent.
    Specifically, SiO 2, Al 2 O 3, MgO, inorganic oxides such as CaO; Inorganic hydroxides such as Al (OH) 3 , Mg (OH) 2 and Ca (OH) 2 ;
    Formula M 2+ lx Al x (OH) 2 (A n- ) x / nmH 2 O
    ( Wherein M 2+ is a divalent metal ion of Mg, Ca or Zn, A n- is Cl − , Br − , I − , NO 3 − , ClO 4- , SO 4 2- , CO 2 2- , Anions such as SiO 3 2- , HPO 4 2- , HBO 3 2- , PO 4 2- ,
    x is a number that satisfies the condition of 0 <x <0.5,
    m is a number satisfying the condition of 0≤m≤2)
    Hydrotalcite, such as the inorganic composite compound represented by these, and the baking material, etc. are mentioned. Among these, hydrotalcites are preferable, and the calcined product of the inorganic composite compound represented by the above formula is particularly preferable.
    Said inorganic compound can be used individually or in combination of 2 or more types.
    The average particle diameter of an inorganic compound is 10 micrometers or less, Preferably it is 5 micrometers or less, More preferably, it is 3 micrometers or less.
    If the average particle diameter of an inorganic compound is within the said range, a multilayer film with favorable transparency can be obtained.
    In the present invention, the inorganic compound is 1 to 20 parts by weight, preferably 1 to 18 parts by weight, more preferably based on 100 parts by weight of the composition (A), (A '), (A ") or (A"'). Is used in the proportion of 2 to 15 parts by weight.
    When forming an outer layer of a multilayer film, when an inorganic compound is used at said ratio, the multilayer film excellent in heat insulation can be obtained.
    (Weather stabilizer)
    The weather stabilizer used as needed when forming the outer layer of the multilayer film is roughly classified into an ultraviolet absorber and a light stabilizer. However, the light stabilizer is effective for thin agricultural films and has a large effect of improving weather stability.
    As the light stabilizer, conventionally known light stabilizers can be used, and among them, hindered amine light stabilizers (HALS; Hindered Amine Light Stabilizers) are preferably used. Specifically, the following compounds are used as the hindered amine stabilizer.
    (l) bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate,
    (2) dimethyl dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate,
    (3) tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane tetracarboxylate,
    (4) 2,2,6,6-tetramethyl-4-piperidinylbenzoate,
    (5) Bis (1,2,6,6-tetramethyl-4-piperidinyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate ,
    (6) bis (N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate,
    (7) 1,1 '-(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone),
    (8) (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate,
    (9) (mixed l, 2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -l, 2,3,4-butane tetracarboxylate,
    (10) Mixed 2,2,6,6-tetramethyl-4-piperidyl / β, β, β ', β'-tetramethyl-3-9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl-l, 2,3,4-butanedetracarboxylate,
    (11) Mixed 1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ', β'-tetramethyl-3-9- [2,4,8,10-tetra Oxaspiro (5,5) undecane] diethyl-1,2,3,4-butanedetracarboxylate,
    (12) N, N'-bis (3-aminopropyl) ethylenediamine-2-4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) Amino] -6-chloro-l, 3.5-triazine condensate,
    (13) a condensate of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethyleneamine with 1.2-diburomoethane,
    (14) [N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) No] propionamide, etc.
    These hindered amine light stabilizers can be used individually or in combination of 2 or more types.
    Such light stabilizer is 0.005 to 5 parts by weight, preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight based on 100 parts by weight of the composition (A), (A '), (A ") or (A"'). It is used in the ratio of 1 weight part.
    Specific examples of the ultraviolet absorber include salicylic acid ultraviolet absorbers such as phenyl salicylate, p-tert-butylphenyl salicylate and p-octylphenyl salicylate;
    2.4-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyl oxy benzophenone, 2,2'-di Benzophenone ultraviolet rays such as hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and 2-hydroxy-4-methoxy-5-sulfobenzophenone Absorbents;
    2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ' , 5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy- Benzotria, such as 3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-3', 5'-di-tert-amylphenyl) benzotriazole Sol-based ultraviolet absorbers;
    And cyanoacrylate ultraviolet absorbers such as 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate and ethyl-2-cyano-3,3'-diphenyl acrylate. .
    The ultraviolet absorber is 0.005 to 5 parts by weight, preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight based on 100 parts by weight of the composition (A), (A '), (A ") or (A"'). Used in parts by weight.
    (Other ingredients)
    In the composition (A), (A '), (A ") or (A"'), additives, such as a conventionally well-known antifog additive, an antistatic agent, and a heat stabilizer, are mix | blended in the range which does not impair the objective of this invention. can do. As the antifogging agent, an antifogging agent whose main component is a partial ester of polyhydric alcohol and higher fatty acid having 12 to 24 carbon atoms (including hydroxy fatty acid) is preferably used.
    (Middle floor)
    The intermediate layer constituting the agricultural multilayer film according to the present invention is formed of a composition containing an ethylene-vinyl acetate copolymer, an inorganic compound and, if necessary, an ethylene-α-olefin copolymer (A-1), a weathering stabilizer, and an antifogging agent. have.
    (Ethylene vinyl acetate copolymer)
    The ethylene-vinyl acetate copolymer used for this invention has a vinyl acetate content of 2.0-30 weight%, Preferably it is 3.0-25 weight%, More preferably, it is the range of 5.0-20 weight%.
    When an intermediate | middle layer is formed with this ethylene vinyl acetate copolymer, the multilayer film excellent in heat retention can be obtained. Here, the term "heat insulation" refers to the ability to absorb the sun's heat during the day to absorb and reflect the radiation emitted at night from the ground where the temperature rises to maintain the internal temperature (temperature and geothermal) of the house and the tunnel.
    (Inorganic compound)
    The inorganic compound used at the time of forming the intermediate layer of the multilayer film is the same as the inorganic compound used at the time of forming the outer layer.
    In the present invention, the inorganic compound is 1 to 20 parts by weight, preferably 1 to 18 parts by weight, based on 100 parts by weight of the total amount of the ethylene-vinyl acetate copolymer and the ethylene-α-olefin copolymer (A-1) to be described later. More preferably, it is used in the ratio of 2-15 weight part. However, since component (A-1) is an arbitrary component, it may become 0 weight part.
    When forming an intermediate | middle layer of a multilayer film, when an inorganic compound is used at the said ratio, the multilayer film excellent in heat retention can be obtained.
    (Ethylene-α-olefin copolymer (A-1))
    The ethylene-α-olefin copolymer (A-1) used as necessary in forming the intermediate layer of the multilayer film has a density of 0.925 g / cm 3 or less, preferably in the ethylene-α-olefin copolymer (A) described above. It is an ethylene-alpha-olefin copolymer of 0.880-0.920 g / cm <3>.
    In the present invention, the weight ratio [(A-1) / (C)] of the ethylene-α-olefin copolymer (A-1) and the ethylene-vinyl acetate copolymer (C) is 99 / l to 1/99, preferably 90/10-10/90, More preferably, it is the range of 80/20-20/80.
    At the time of formation of the intermediate layer of the multilayer film, the intermediate layer can be thinned by using the ethylene-α-olefin copolymer (A-1) in the above weight ratio with respect to the ethylene-vinyl acetate copolymer.
    (Weather stabilizer)
    The weathering stabilizer used as needed at the time of intermediate | middle layer formation of a multilayer film is a ultraviolet absorber and a light stabilizer used at the time of outer-layer formation mentioned above.
    The light stabilizer is 0.005 to 5 parts by weight, preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight based on 100 parts by weight of the total amount of the ethylene-α-olefin copolymer (A-1) and the ethylene-vinyl acetate copolymer. It is used in the ratio of 1 weight part. However, since component (A-1) is an arbitrary component, it may become 0 weight part.
    The ultraviolet absorber is 0.005 to 5 parts by weight, preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight based on 100 parts by weight of the total amount of the ethylene-α-olefin copolymer (A-1) and the ethylene-vinyl acetate copolymer. 1 part by weight is used. However, since component (A-1) is an arbitrary component, it may become 0 weight part.
    (Other ingredients)
    The ethylene-vinyl acetate copolymer for intermediate | middle layer formation can be mix | blended with additives, such as a conventionally well-known antifog additive, an antifog additive, an antistatic agent, and a heat stabilizer, in the range which does not impair the objective of this invention.
    As the antifogging agent, an antifogging agent whose main component is a partial esterified product of the above-mentioned polyhydric alcohol and C12-24 higher fatty acid (including hydroxy fatty acid) is preferably used. The antifogging agent is 0.05 to 5 parts by weight, preferably 0.1 to 4 parts by weight, more preferably based on 100 parts by weight of the total amount of the ethylene-α-olefin copolymer (A-1) and the ethylene-vinyl acetate copolymer. Is used in the ratio of 0.5 to 3 parts by weight. However, since component (A-1) is an arbitrary component, it may become 0 weight part.
    (Inner layer)
    The inner layer which comprises the agricultural multilayer film which concerns on this invention is formed from composition (A), (A '), (A ") or (A"'). An inorganic compound, a weathering stabilizer, and an antifog additive can be mix | blended with this composition (A), (A '), (A ") or (A"').
    In this invention, an inorganic compound is used in the ratio of 1-3 weight part with respect to 100 weight part of total amounts of a composition (A), (A '), (A ") or (A"').
    When an inorganic compound (B) is used in the said ratio at the time of inner layer formation of a multilayer film, the multilayer film excellent in heat retention can be obtained.
    (Weather stabilizer)
    The weathering stabilizer used as needed at the time of internal layer formation of a multilayer film is the ultraviolet absorber and light stabilizer mentioned above.
    The light stabilizer is 0.005 to 5 parts by weight, preferably 0.005 to 2 parts by weight, and more preferably 0.01 to 1 part by weight based on 100 parts by weight of the composition (A), (A '), (A ") or (A"'). Parts by weight are used.
    The ultraviolet absorber is 0.005 to 5 parts by weight, preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part, based on 100 parts by weight of the composition (A), (A '), (A ") or (A"'). Parts by weight are used.
    (Other ingredients)
    To the composition (A), (A '), (A ") or (A"') used for inner layer formation of a multilayer film, additives, such as a conventionally well-known antifog additive, an antistatic agent, a heat stabilizer, are made into the objective of this invention. It can mix | blend in the range which does not harm.
    As the antifogging agent, an antifogging agent whose main component is a partial esterified product of the above-mentioned polyhydric alcohol and C12-24 higher fatty acid (including hydroxy fatty acid) is preferably used.
    The antifogging agent is 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, more preferably based on 100 parts by weight of the composition (A), (A '), (A ") or (A"'). Is used in a ratio of 0.5 to 2 parts by weight.
    (Multilayer film)
    The agricultural multilayer film according to the present invention comprising the above-mentioned outer layer, middle layer and inner layer has a thickness of the outer layer, usually 3 to 100 µm, preferably 10 to 80 µm, more preferably 20 to 70 µm, and the thickness of the intermediate layer. 10-150 micrometers, Preferably it is 20-120 micrometers, More preferably, it is the range of 30-100 micrometers, The thickness of an inner layer is 3-100 micrometers, Preferably it is 10-80 micrometers, More preferably, it is 20-70 micrometers The thickness of the whole layer is 30-200 micrometers, Preferably it is 50-180 micrometers, More preferably, it is the range of 70-150 micrometers.
    The agricultural multilayer film according to the present invention has the following physical properties and properties.
    (i) Elmandorf tear strength is at least 90 kg / cm in the MD direction, preferably at least l00 kg / cm and at least 90 kg / cm in the TD direction, preferably at least 100 kg / cm.
    (ii) The dart impact strength in thickness of 100 micrometers is 900 g or more, Preferably it is 1,000 g or more.
    (iii) The tensile breaking strength is at least 350 kg / cm 2 in the MD direction, preferably at least 370 kg / cm 2, and at least 350 kg / cm 2 in the TD direction, preferably at least 370 kg / cm 2.
    (iv) The initial light transmittance at a thickness of 100 µm is 90% or more, preferably 92% or more, and the light transmittance after 120 days of outdoor exposure is 85% or more, preferably 87% or more.
    Elmendorf tear strength is obtained by performing a tear strength test in the MD direction and the TD direction of the multilayer film in accordance with JIS Z 1702. The dart impact strength is obtained by performing an impact test in accordance with JIS Z 1707 (38 mm in diameter at the tip of the dart). Tensile breaking strength is a value obtained by performing a tensile test using a crosshead moving speed constant tension tester (manufactured by Instron Co., Ltd.) in the MD direction and the TD direction of a multilayer film in accordance with JIS K 6781 under the following conditions. .
    Moreover, the glossiness of the 50-micrometer-thick agricultural multilayer film which concerns on this invention is 60% or more normally, and haze is 15% or less normally.
    In addition, the glossiness of the film was measured at the incident angle (60 degree) based on ASTMD523. In addition, the haze of the film was measured according to ASTMD1003-61.
    (Manufacture of a multilayer film)
    The agricultural multilayer film which concerns on said this invention mixes components, such as the polyethylene-type resin used in each layer of a multilayer film, the above-mentioned additives, etc., melt-mixes with a chestnut mixer, a roll mill, etc., and then co-extrudes inflation method Or it can manufacture by laminating | stacking an outer layer, an intermediate | middle layer, and an inner layer by co-extrusion T-die method.
    Such an agricultural multilayer film is excellent in heat retention, dustproofness, and toughness, and is extended to agricultural horticultural facilities such as houses and tunnels, and can be used for a long time for the cultivation of useful crops.
    Waterproof sheet:
    The waterproof sheet includes the ethylene copolymer composition (A), (A '), (A ") or (A"'), and carbon black, a heat stabilizer, a weather stabilizer, a pigment, and a filler (except carbon black as needed). ), A lubricant, an antistatic agent, a flame retardant, a foaming agent, etc., are formed with well-known additives. The waterproof sheet may be a multi-layered body in which the layer of the composition (A), (A '), (A ") or (A"') is made into an inner layer or an outer layer in combination with another base material, a reinforcement material, a drain material, etc.
    The waterproof sheet has an elongation at break (JIS A 6008, graph method, speed of 200 mm / min) at a thickness of 0.5 mm or more, 80% or more, and an elongation at break of 5 mm or more at a thickness of 1.5 mm, and is used in the field. When heat-sealing on condition of set temperature 500 degreeC and sealing speed 5m / min using the heat sealer to make, it is preferable that peeling strength (JIS K 6328, speed 50mm / min) in a fusion | melting part is 10 kg / 20mm or more.
    Since the waterproof sheet may collide with an uneven object, especially a sharp object, the elongation at the time of tearing and the elongation at the time of stabbing are important factors for maintaining the performance of the waterproof sheet.
    In addition, as a heat sealer for field use, the hot air sheet welding machine 10E type | mold made by Leystar is used. In addition, the peeling test was carried out by fusing two sheets under conditions of a set temperature of 500 ° C. and a speed of 5 m / min using a hot air sheet welding machine type 10E manufactured by Leystar, and after adjusting the conditions at 23 ° C. for 48 hours or more, according to JlS K6328, a speed of 50 mm The peeling strength test was done on condition of / min, and peeling strength was measured and it was set as the index of fusion characteristic. The stab test uses an Instron universal testing machine to fix the waterproof sheet to a jig of 5 cm in diameter, and to measure the breaking strength when a needle having a flat tip of 0.7 mm in diameter is stabbed at a speed of 50 mm / min. Strength / sheet thickness (kg / mm) and elongation at break were determined.
    The waterproof sheet according to the present invention is very preferable in practical use because heat sealing can be performed easily and with high strength by the sheet sealer actually used in the field.
    Such a waterproof sheet is excellent in mechanical strength, flexibility, and adhesion such as tensile strength, tear strength, elongation at tearing, puncture strength, elongation at stabbing, and the like.
    Multilayer film:
    The multilayer film is formed from a base film layer and a layer made of the ethylene copolymer composition (A), (A '), (A ") or (A"').
    The material for forming the base film is not particularly limited as long as it has a film forming ability, but any polymer or paper, aluminum foil, cellophane, or the like can be used. Such polymers include, for example, high density polyethylene, medium density polyethylene, low density polyethylene, ethylene / vinyl acetate copolymers, ethylene / acrylic acid ester copolymers, ionomers, polypropylene, poly-butene, poly-4-methyl-1 Olefin polymers such as pentene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylates, vinyl polymers such as polyacrylonitrile, nylon 6, nylon 66, nylon l0, nylon 11, nylon 12, nylon 610 , Polyamide-based polymers such as polymethylene adadiamide, ester-based polymers such as polyethylene terephthalate, polyethylene terephthalate / isophthalate, polybutylene terephthalate, vinyl alcohol, ethylene-vinyl alcohol copolymer, polycarbonate air Coalescence, etc. are mentioned.
    Moreover, when a base film turns into a polymer, this polymer film may be non-oriented and may be extended | stretched uniaxially or biaxially.
    These base materials can be suitably selected according to the use of a multilayer film. For example, in the case of a composite film for packaging, the substrate can be appropriately selected according to the packaged object. For example, when the package is a food which is easily corroded, a resin having excellent transparency, rigidity, and gas permeation resistance, such as polyamide, polyvinylidene chloride, ethylene / vinyl alcohol copolymer, polyvinyl alcohol, polyester, or the like can be used. . In the case where the packaged object is a confectionery or a textile package, it is preferable to use polypropylene having good transparency, rigidity and water permeation resistance.
    When extrusion coating the ethylene copolymer composition (A), (A '), (A ") or (A"') on said base material, the composition (A), (A '), ( A ") or (A" ') may be extrusion-coated and a method well-known in advance to a base material in order to raise the adhesive force of a base material and a composition (A), (A'), (A ") or (A" '). For example, after applying a coating agent such as an organic titanium-based, polyethyleneimine-based or isocyanate-based, or preparing a hinged resin layer such as an adhesive polyolefin or a high-pressure polyethylene, the composition (A), (A '), (A ") Or (A" ') may be extrusion-coded.
    Moreover, in order to ensure the adhesiveness between the base material and the resin (the lap resin or the composition (A), (A '), (A ") or (A"')) in contact with the base material, ozone is applied to the molten film of the extruded resin. It is also possible to force the oxidation of the surface of the membrane by blowing.
    Such multilayer films include various packaging bags such as liquid soups, pickled foods, wet food packaging bags such as fine vermicelli, fast food packaging bags such as miso and jam, powder packaging bags such as sugar, flour, and fish powder, and pharmaceutical tablets. It is suitable for the granule packaging bag use, and serves as a sealant layer for this use.
    Packaging Multilayer Film:
    The multilayer film for packaging consists of a film of at least three layer structure of an outer layer, one or two or more intermediate layers, and an inner layer. The resin composition used for an outer layer and an inner layer differs from the resin composition which comprises an intermediate | middle layer.
    The outer layer and the inner layer are formed of the ethylene copolymer composition (A), (A '), (A ") or (A"'). Moreover, composition (A), (A '), (A ") or (A"') which forms an outer layer and an inner layer may be the same, and may differ from each other.
    Although the intermediate | middle layer is arbitrarily selected from the resin composition used as a raw material of the said base film, What is formed of the resin or resin composition which consists of a 1-butene type (co) polymer and an ethylene propylene 1-butene random copolymer as needed desirable.
    The 1-butene-based (co) polymer is a 1-butene homopolymer or a 1-butene propylene copolymer having 75 to 85 mol% of 1-butene content and 15 to 25 mol% propylene content.
    This l-butene-based (co) polymer has an MFR of 0.1 to 5 g / l 0 minutes, preferably 0.5 to 2 g / 10 minutes, and a density of 0.890 to 0.925 g / cm 3, preferably 0.895 to 0.920 g / cm 3 to be. This 1-butene-based (co) polymer can be prepared using a conventional Ziegler-Natta catalyst.
    In the present invention, the 1-butene-based (co) polymer is 40-100% by weight, preferably 50-90 with respect to 100% by weight of the total amount of the 1-butene-based (co) polymer and the ethylene propylene-1-butene random copolymer. It is used in the ratio of 55% by weight, more preferably 55 to 95% by weight.
    The ethylene propylene 1-butene random copolymer preferably has a propylene content in the range of 50 to 98 mol%, preferably 70 to 97 mol%.
    The ethylene propylene 1-butene random copolymer has an MFR of 0.1 to 100 g / 10 minutes, preferably 1 to 30 g / 10 minutes, and a density of 0.890 to 0.910 g / cm 3.
    This ethylene propylene 1-butene random copolymer can be manufactured using a normal Ziegler-Natta catalyst.
    In the present invention, the ethylene propylene 1-butene random copolymer is 0 to 60% by weight, preferably 0 to 100% by weight of the total amount of the 1-butene system (co) polymer and the ethylene propylene 1-butene random copolymer. 50 to 50% by weight, more preferably 5 to 45% by weight.
    When the ratio of the 1-butene system (co) polymer and the ethylene propylene 1-butene random copolymer is in the range of the blending ratio, a multilayer film having excellent cutability by an automatic packaging machine is obtained.
    In the present invention, in addition to the 1-butene-based (co) polymer and the ethylene propylene-1-butene random copolymer in the resin or resin composition constituting the intermediate layer, similarly to the resin or resin composition constituting the outer layer and the inner layer described above, Various stabilizers, compounding agents, fillers and the like can be added within a range not impairing the object of the present invention. In particular, an antifogging agent, an antistatic agent, or the like may be added to improve the appearance of the contents, or a sunscreen may be added to protect the contents, and an antioxidant and a lubricant may be added.
    The intermediate layer may be composed of one to two layers or more in which the 1-butene-based (co) polymer and the ethylene-propylene-butene random copolymer are blended in the amounts in the above ranges.
    The multilayer film for packaging which concerns on this invention is shape | molded normally with the thickness of 10-20 micrometers, The intermediate | middle layer is 1-5 micrometers, and outer layer and inner layer are adjusted to the thickness of 2-8 micrometers, respectively. Moreover, depending on a use, you may form another resin layer in the outer side of an inner layer and / or an outer layer.
    The packaging multilayer film is mixed with each component forming each layer using various blenders, and then used in a conventional molding method, that is, an inflation film molding machine having a plurality of die lips in an extruder, or a T-die molding machine. Manufactured by supply.
    The multilayer film for packaging preferably has a ratio of the Elmandorf tearing strength in the longitudinal direction and the transverse direction (lateral direction / vertical direction) of 9.l or less, and can be used as an excellent packaging film in this case. In particular, when the film is applied to an automatic packaging machine, since the film is cut by a knife running in the transverse direction, the cutting property is good and bad can be evaluated by the ratio of the Elmandorf tear strength in the longitudinal direction and the transverse direction. When the ratio of the Elmandorf tear strength is 9.l or less, it is judged that the cutting property by the automatic packaging machine is good.
    In the multilayer film for packaging according to the present invention, the Elmandorf tearing strength ratio is 9.1 or less, so that cutting is easy by an automatic packaging machine and continuous packaging can be performed at high speed. Elmandorf tear strength is measured by a method in accordance with JIS Z 1702.
    Moreover, the multilayer film for packaging which concerns on this invention is excellent in transparency, and haze value is 2.0% or less normally.
    Moreover, the multilayer film for packaging which concerns on this invention is excellent in acupressure resilience, initial stage recovery rate is 70% or more, and residual distortion is 5.5 mm or less.
    Moreover, the multilayer film for packaging which concerns on this invention is excellent in low temperature sealing property, and the sealing strength of the film heat-sealed at 90 degreeC is 100 kg / cm <2> or more.
    Such a multilayer film for packaging is excellent in mechanical strength properties, transparency and low temperature heat sealing property, and even after pressing, for example, by pressing with a finger on the contents side, the subsequent film has good recoverability and is suitable for packaging foodstuffs and daily necessities.
    Stretch Wrap Film:
    Stretch packaging film is the ethylene-based copolymer composition (A), (A '), (A ") or (A"'), and other resin components, for example, density 0.880-0.895 g / cm <3> as needed. It is formed from an ethylene propylene random copolymer, an ethylene butene random copolymer having a density of 0.880 to 0.895 g / cm 3 and a high pressure ethylene vinyl acetate random copolymer having a density of 0.910 to 0.924 g / cm 3.
    Such other resin components are used at 0-40 weight part with respect to 100 weight part of said compositions (A), (A '), (A ") or (A"').
    Moreover, in this invention, resin composition different from the said composition (A), (A '), (A ") or (A"') or composition (A), (A '), (A ") or (A"'). Various additives, such as a slip agent, an anti blocking agent, an antifog additive, an antistatic agent, and a sunscreen, etc. can be mix | blended with the composition which does not impair the objective of this invention.
    As the slip agent, for example, higher fatty acid amides such as oleic acid amide, stearic acid amide, and elca acid amide are preferably used.
    Moreover, as an anti blocking agent, inorganic substances, such as a silica and a talc, are used preferably, for example.
    As antistatic agents, for example, glycerin fatty acid esters and sorbitol fatty acid esters are preferably used.
    The film of the composition (A), (A '), (A ") or (A"') has the proper adhesiveness required, but when more adhesiveness is required, linear low density polyethylene, liquid polybutadiene, poly What is necessary is just to mix isobutylene etc. about 2 to 10 weight%.
    The stretch packaging film concerning this invention contains the film of the above-mentioned composition (A), (A '), (A ") or (A"').
    The film for stretch packaging which concerns on this invention is 10-50 micrometers in thickness normally. The stretch packaging film may have a single layer structure or a multilayered structure.
    The stretch packaging film of a single | mono layer structure can be manufactured by normal film forming methods, such as an inflation method and a T-die method.
    The stretch packaging film of a multilayer structure can be manufactured using a conventionally well-known shaping | molding method, for example, a shaping | molding apparatus, such as an inflation film molding machine or a T-die molding machine provided with a some die leaf in an extruder.
    Stretch packaging film has a tensile tensile stress at break (JIS Zl702) of 400k g / cm 2 or more, a tensile tensile strength at break (JIS Z1702) of 500% or more, and an impact strength (ASTM D3420) of 2,500 kg. Cm / cm or more, longitudinal tear strength (JlS Zl 720) is 50 kg / cm or more, adhesive force (20 kg, 50 ° C × l day) is 3 to 25 g / cm, elongated 300% and elapsed for 1 hour It is preferable that the after-force is 150-300g / 15mm, and the maximum extending | stretching limit is 300% or more.
    The stretch packaging film according to the present invention has a higher tensile fracture elongation than a film of a conventional low density polyethylene or ethylene / vinyl acetate copolymer, and can be stretched at 300 to 600%. Suitable for stretch packaging of 2 or more objects.
    Moreover, compared with the film of the conventional low density polyethylene or the ethylene-vinyl acetate copolymer, the stretch packaging film which concerns on this invention has a small stress applied after packaging, does not deform a to-be-packed object, and the film strength after packaging is strong, The film appearance is good.
    The film for stretch packaging which concerns on this invention may be a film which consists of said composition (A), (A '), (A "), or (A"') of 1 sheet, and this composition (A), (A '), In addition to the film layer consisting of (A ″) or (A ″ ′), a film having a multilayer structure having one or two or more film layers may be used.
    The multi-layered stretch packaging film, for example, the multi-layered film in which the non-adhesive side and the adhesive side are shared in the stretch-packaging film may be formed of the composition (A), (A '), (A ") or (A"'). The film layer serves as an intermediate layer, and on one surface of the intermediate layer, as a non-adhesive layer, a film layer made of high density linear low density polyethylene is formed at a thickness of about 5 to 30% of the total thickness of the stretch packaging film, and the other 2 to 10% by weight of a liquid polyisobutylene, a liquid polybutadiene, or the like in the above composition (A), (A '), (A' ') or (A' '') as an adhesive layer It can obtain by the method of forming a film layer in thickness of about 5 to 30% with respect to the total thickness of the film for stretch packaging.
    Since such stretch packaging film is highly stretchable and has proper adhesiveness, excessive stress is not applied to the packaged product after packaging, and the strength characteristics and appearance after packaging are excellent, and the film has no excessive adhesiveness, thus productivity, packaging It is excellent in sex and handleability.
    Packing film:
    Packaging films are improved packaging or wrapping films, and more particularly shrink, skin, stretch, hot, exhibiting improved transparency, toughness, extrusion processability and irradiation crosslinking efficiency. Hot tack and vacuum wrap films. These films are equipped with at least 1 layer of at least 1 type of ethylenic copolymer composition (A), (A '), (A "), or (A"'), and may be biaxially oriented, or may be multilayer. It may be configured to have good and / or barrier properties.
    This ethylene-based copolymer composition (A), (A '), (A ") or (A"') may contain additives, for example antioxidants (e.g., Hindered phenolic (e.g., Irganox® 1010 manufactured by Chiba Geigy Corp), phosphites (e.g. Irgafos® 168, etc.), cling additives (e.g. Polyisobutylene (PlB) and the like), PEPQ (trademark of Sando Chemical, its main material is considered biphenylphosphonite), pigments, colorants, fillers and the like. The film produced may also contain additives which enhance its antiblocking and coefficient of friction characteristics, including, but not limited to, untreated and treated silicon dioxide, talc, calcium carbonate and clay, etc. And primary and secondary fatty acid amides, silicone coatings and the like. As described, for example, in US Pat. No. 4,486,552 to Niemann et al., Other additives may be added that enhance the antifogging properties exhibited by this film. In addition, in order to improve the antistatic properties of the film, another additional additive, such as quaternary ammonium compound, which enables the packaging of electronic sensitive objects, alone or in combination with EAA or other functional polymers, It is also possible to add.
    Ethylene-based copolymer compositions (A), (A '), (A ") or (A"') used in the preparation of the packaging and lapping olefin films of the present invention have a single or multi-layer structure. It can be used as only one polymer component of this film. By blending other polymers together with this ethylene copolymer composition (A), (A '), (A ") or (A"'), processability, film strength, heat sealability or adhesiveness of the film can be improved. Can be. Packaging and wrapping films produced by appropriate blending of this ethylene copolymer composition (A), (A '), (A ") or (A"') with other polymer components maintain improved performance and As a case, an improved combination of properties is given. Some suitable materials for blending with this ethylenic copolymer composition (A), (A '), (A ") or (A"') include, but are not limited to, high pressure low density polyethylene (LDPE), for example. ), Ethylene vinyl acetate copolymer (EVA), ethylene carboxylic acid copolymers and their ionomers, polybutylene (PB) and α-olefin polymers such as high density polyethylene, medium density polyethylene, polypropylene, Ethylene propylene copolymers, linear low density polyethylene (LLDPE) and ultra low density polyethylene, graft modified polymers and blends thereof, and the like, and those having a combination of density, MWD and / or comonomers, For example, US Pat. No. 5,032,463 to Smith, which is incorporated by reference, and the like, are also included. However, this ethylenic copolymer composition (A), (A '), (A ") or (A"') is preferably at least 50% of this blend composition, more preferably at least 80% of this blend composition. Consists of. However, in the case of a multilayer film structure, very preferably the outer film layer (called "surface layer" or "surface layer" in the art) and the sealant layer are the ethylene-based copolymer compositions (A), (A Essentially '', (A ") or (A" ').
    The oriented and unoriented film structures of the present invention can be manufactured using conventional simple hot flow bubble, cast extrusion or extrusion coating techniques, while in the case of oriented films in particular, more demanding techniques such as "tenter framing" (tenter framing) or "double bubble" or "trapped bubble" method or the like.
    While the present technology and the specification use "stretched" and "oriented" interchangeably, the orientation is practically such as, for example, internal air pressure in a tube or tenter fleming that presses the edge of the film. This occurs as a result of the film being stretched.
    A simple hot flow bubble film method is described, for example, in "The encyclopedia of Chemical Technology", Kirk-0thmer) 3rd Edition, John Wiley & Sons, New York) 1981, Vol. 16, pp. 416-417 and 18, 191-192. Page, etc. are described. Suitable methods for producing biaxially oriented films, such as the "double bubble" method described in US Pat. No. 3,456,044 (Pahlke), and other methods suitable for the production of biaxially oriented or oriented films are described. U.S. Patent 4,865,902 (Golike et al.), U.S. Patent 4,352,849 (Mueller), U.S. Patent 4,820,557 (Warren), U.S. Patent 4,927,708 (Herra et al.), U.S. Patent 4,963,419 (Lustig et al.) And U.S. Patents 4,952,451 to Mueller et al.
    As described by Pahlke in U.S. Patent No. 3,456,044, as a comparison of the simple bubble method, processing of "double bubble" or "trap bubble" film greatly increases the orientation of the film in both machine and transverse directions. can do. As the orientation increases in this manner, the free shrinkage value when the film is subsequently heated becomes higher. In addition, Pahlke in U.S. Patent No. 3,456,044 and Lustig et al. In U.S. Patent No. 5,059,481, when the low density polyethylene and the ultra low density polyethylene materials are prepared by the simple bubble method, show their shrinkage characteristics in the machine and transverse directions, respectively. For example, it is disclosed that the free shrinkage drops by about 3% in both directions. However, in contrast to known film materials, in particular, in contrast to the film materials disclosed by Lustig in U.S. Pat.Nos. 5,059,481, 4,976.898 and 4,863,796, U.S. Pat. In contrast to the film material that Smith discloses, the ethylene-based copolymer composition (A), (A '), (A ") or (A"') of the present invention is a simple bubble method, with machine direction and transverse Very improved shrinkage in both directions. It is also possible to use a simple bubble method at a high blow up ratio, for example blow up ratio equal to or greater than 2.5: 1, or more suitably to Pahlke disclosed in U.S. Patent No. 3,456,044, When the ethylene copolymer composition (A), (A '), (A ") or (A"') is prepared using the "double bubble" method disclosed by Lustig in 4,976,898, machine direction and transverse Good shrinkage in the direction can be achieved, and the film obtained therefrom is suitable for shrink wrap packaging purposes.
    Equation: BUR = diameter of bubble ÷ die diameter, to calculate the blow up ratio expressed in the abbreviation as "BUR" herein.
    The olefin film for packaging and lapping of the present invention may be a single layer or a multilayer film. In a form in which the film structure is a monolayer, the monolayer is at least 10% by weight, preferably at least one ethylene copolymer composition (A), (A '), (A ") or (A"'). It may contain at least 30% by weight and may also contain 100% by weight of at least one ethylene copolymer composition (A), (A '), (A' ') or (A' '').
    The ethylene copolymer composition (A), (A '), (A ") or (A"') used for forming a single layer film depends on the required characteristic of this film. When two or more kinds of ethylenic copolymer compositions (A), (A '), (A ") or (A"') are used in the single layer film structure, the compatibility with one another is partially based on processing and use conditions. As the above, the polymers are selected. Likewise, at least one ethylenic copolymer composition (A), (A '), (A ") or (A"') and at least one conventional ethylene polymer (eg described in U.S. Patent No. 3,645,992). Conventional homogeneously branched linear ethylene-α-olefin copolymers prepared as if, or blends of conventional heterogeneous branched ethylene-α-olefin copolymers prepared by the Ziegler method described in US Pat. No. 4,076,698). In this case, the ethylene polymer is selected based in part on the compatibility with respect to this ethylene copolymer composition (A), (A '), (A ") or (A"').
    Depending on the various properties indicated by these monolayers, any of these monolayers can be used in any of the various five kinds of packaging methods, but in practice, a single layer film is most suitable for use in a stretch overlap and a skin packaging method. As required for stretch overlapping, monolayer films made from the ethylene-based copolymer compositions (A), (A '), (A ") or (A"') of the present invention have surprisingly good oxygen transmission rates. Indicates.
    Oxygen permeation is particularly important when stretching and wrapping individual slices of red meat (ie, in an "instore" package where food vendors / butchers actually cut the original meat into smaller slices for individual sales purposes). It is advantageous and can make bright red desired for fresh red meat by permeation of oxygen. Films effective for packaging individual red meat slices usually exhibit minimal shrinkage and at the same time good drawability. The film exhibits suitable oxygen permeability and exhibits good elastic recovery so that consumers can inspect the meat without permanently deforming the film and making the meat unattractive. A pending US application filed April 28, 1993, under the names of Pak-Wing Steve Chum and Nicole F. Whiteman, packs food containing these individual pieces of red meat. A method is disclosed. However, even if shrinkage is not used in the present technology, a film used when packaging individual red meat portions can be produced as a heat shrinkable film.
    One monolayer which is particularly preferred for use in the stretch overlap method is an ethylene-based copolymer composition (A), (A '), (A ") or (A"') and an ethylene / α, β-unsaturated carbonyl copolymer , Blends such as (eg EVA, EAA) ethylene / methacrylic acid / (EMAA), and alkali metal salts (ionomers), esters and other derivatives thereof.
    In the case of coextruded or laminated multilayer film structures (for example, three and five layer film structures), the ethylene-based copolymer compositions (A), (A '), (A ") or (A") described herein. ') Can be used as the core layer, outer surface layer, intermediate layer and / or inner sealant layer of this structure. Especially in the hot tag film of this invention, this film structure is equipped with at least 1 sort (s) of the ethylene-type copolymer composition (A), (A '), (A ") or (A"') described in this specification. It is used as a heat-sealable outer layer of at least 1 layer which is made. The heat-sealable outer layer may be coextruded with another layer (stream), or the heat-sealable outer layer may be laminated on the other layer (stream) by a second operation, for example, Wilmer A. Jenkins. And WJSchrernk and CR, as described in "Packaging Foods With Plastics" (1991) by James P. Harrington, or "Society of Plastics Engineers RETEC Proceedings", June 15-17 (1981), 211-229. It can be implemented as described in Finch "Coextrusion For Barrier Packaging".
    In a multilayer film structure, generally, the ethylene-based copolymer compositions (A), (A '), (A ") or (A"') described herein comprise at least 10% of all of this multilayer film structure. have. Other layers of this multilayer structure include, but are not limited to, barrier layers and / or tie layers and / or structural layers. Various materials may be used as these layers, and some of them may be used. Dogs may be used as two or more layers in such film structures. Some examples of these materials are foil, nylon, ethylene / vinyl alcohol (EVOH) copolymers, polyvinylidene chloride (PVDC), polyethylene terephthalate (PET), oriented polypropylene (OPP), ethylene / vinyl acetate (EVA) copolymerization Retention, ethylene / acrylic acid (EAA) copolymers, ethylene / methacrylic acid (EMAA) copolymers, ULDPE, LLDPE, HDPE, MDPE, LMDPE, LDPE, ionomas, graft modified polymers (e.g., maleic anhydride graft) Oxidized polyethylene, etc.) and paper. Generally, this multilayer film structure contains 2 to 7 layers.
    The multilayer film structures of one aspect disclosed herein comprise at least three layers (eg, “A / B / A” structures, etc.), wherein each outer layer is at least one ethylenic copolymer composition (A), (A '), (A ") or (A"'), and at least one core layer or hidden layer is low density polyethylene (LDPE) manufactured by the high pressure method. Such multilayer film structures exhibit surprisingly good optical properties while maintaining good overall film strength properties. In general, the ratio of the layers included in the film structure is a percentage of the structure as a whole, in which the core layer is the main part of the film structure. This core layer should be at least 33% of the total film structure (eg in a three layer film structure each “A” outer layer constitutes 33% by weight of the total film structure, while the core layer of LDPE (layer B) 33 wt% of the total film structure). In the three-layer film structure, the core layer of the LDPE preferably constitutes at least 70% of the total film structure. Moreover, you may insert the hidden additional layer in this film structure as long as it does not deteriorate this optical characteristic. For example, ethylene / vinyl acetate copolymers, ethyleneacrylic acid copolymers or anhydride graft modified polyethylenes, or the like, for example, using a bond or an intermediate layer, or for example vinylidene chloride / vinyl chloride copolymers or ethylene. The barrier layer which consists of vinyl alcohol copolymers, etc. can be used. More suitable three-layer film structures include each "A" outer layer having at least one ethylene copolymer composition (A), (A '), (A ") or (A"') 15 weight of the entire film structure. And the “B” core layer contains 70% by weight of the LDPE in the entire film structure. By carrying out the orientation and / or irradiation (in any order) of the multilayer film structure, it is possible to produce a shrunk film structure that becomes a multilayer or an outer package exhibiting controlled linear tearabiliy. LDPEs suitable for multilayer film structures exhibiting improved optical clarity disclosed herein generally have a density of 0.915 g / cm 3 to 0.935 g / cm 3, melt index from 0.1 g / 10 min to 10 g / 10 min, and at least 1 g of melt. Indicates tension. In order to improve optical transparency, the ethylenic copolymer composition (A), (A '), (A ") or (A"') generally has a density of 0.85 g / cm 3 to 0.96 g / cm 3, preferably 0.9 g / Cm <3> -0.92g / cm <3>, melt index (I2) 0.2g / 10min-10g / l0min, Preferably 0.5g / l0min-2g / 10min are shown.
    These multilayer film structures are also described in this film as (A) in the structure of the ethylene copolymer composition (A), (A '), (A ") or (A"') (the structure of the following film structures). When used alone or in combination with other oxygen permeable film layers, such as ethylene / vinyl acetate (EVA) and / or ethylene / acrylic acid (EAA), oxygen permeability can be exhibited. Of particular interest are, for example, (A) / EAA / (A), (A) / VLDPE / (A) and LLDPE / (A) / LLDPE film structures, which are substitutes for conventional films such as PVC At the same time, a variety of fresh foods, such as red meat, fish, poultry, vegetables, fruits, cheeses, etc., cut into sleeves, and other food products that are benefited from retail labeled and oxygen in the surroundings or need to be properly breathed It is suitable for outer packaging. Preferably, wholesalers are prepared by making their films from non-shrinkable films (eg, not having biaxial orientation induced by double bubble processing) that exhibit good oxygen permeability, stretchability, elastic recovery and heat sealability. And allowing retailers to use them in any of the usual forms, for example, in the form of stockrolls, and at the same time, in a conventional packaging device.
    In another aspect, these multilayer film structures are oxygen barrier films (eg SARAN®, a film made of polyvinylidene chloride polymer manufactured by Dow Chemical Company, or a subsidiary of Kuraray of America, Inc.). EVAL (trademark) resin which is an ethylene / vinyl alcohol copolymer manufactured by Eval Company of America (the subsidiary which Kuraray Ltd. owns in its entirety) may be included. Oxygen barrier properties are important for film applications when packaging original meat slices (ie large meat slices that are shipped to special stores for recutting for specific consumer consumption). As described by Davis in US Pat. No. 4,886,690, the oxygen barrier layer can also be designed to be "peelable" so that the first section of this package can be removed upon arrival at the butcher / food vendor. This peelable structure or design is particularly effective for the individual part of the "case-ready" vacuum envelope package, thereby eliminating the need to repack it in an oxygen permeable package for the purpose of adding a bright red color.
    A film prepared from any of the known methods, for example, an extrusion molding method or the like and prepared from the ethylene-based copolymer composition (A), (A '), (A' ') or (A' '') described herein. The structure may be molded in advance according to the shape and contour of the product to be packaged. The advantages of using preformed film structures are that they can be supplemented or avoided given individual packaging operations, such as increased stretchability, thinner film thickness for a given stretch requirement, shorter heat up and cycle times, and the like. do.
    The thickness of these single or multilayer film structures can be varied. However, the thicknesses of both single and multilayer film structures described herein typically range from 0. lmil (2.5 μm) to 50 mil (1270 μm), preferably 0.4 mil (10 μm) to 15 mil (381 μm), in particular 0.6 mils (15 micrometers) to 4 mils (10 micrometers).
    The film structures prepared from the ethylene-based copolymer compositions (A), (A '), (A ") or (A"') described herein are surprisingly used in conventional Ziegler polymerized linear ethylene / a-olefin polymers. Compared with irradiation efficiency which is more efficient compared with the above. In one aspect of the present invention, by utilizing the advantages of irradiation efficiency exhibited by these polymers, it is possible to produce a film structure provided with a film layer that is crosslinked either selectively or selectively. In order to further utilize the advantages of this finding, a specific film layer material containing this ethylenic copolymer composition (A), (A '), (A ") or (A"') is produced by a pro-rad agent. pro-rad agents, for example triarylcyanurate described by Warrern in US Pat. No. 4,957,790 and / or crosslinking inhibitors, such as butylation described by Ever in US Pat. No. 5,055,328. Combinations with hydroxytoluene and the like.
    Moreover, the crosslinking by irradiation is also effective in the case where it is going to raise the shrinkage temperature range and hot sealing range of these film structures. For example, US Pat. No. 5,089,321 discloses a multilayer film structure having at least one heat sealable outer layer and at least one core layer exhibiting good radiation crosslinking performance. Among the irradiation crosslinking techniques, beta irradiation with an electron beam source and gamma irradiation with a radioactive element of cobalt 60 are the most common methods for causing crosslinking of the film material.
    As an irradiation crosslinking method, after manufacturing a thermoplastic film by the blast film method, it exposes to the irradiation source (beta or gamma) of 20 Mrad or less irradiation dose, and produces crosslinking of this polymer film. When the alignment film is desired, irradiation crosslinking may be induced before or after the final film alignment, for example in the case of shrinkage and shell packaging, but preferably irradiation crosslinking is performed before the final alignment. Induce. When the heat-shrinkable film or outer packaging film is manufactured by a method of irradiating pellets or films before final film orientation, these films are uniform, and thus exhibit higher shrinkage tension so that the bending of the package and the bending of the cardboard can be There exists a tendency to become high, and conversely, if it oriented before irradiation, the shrinkage tension of the film obtained will become lower. Unlike shrinkage tension, the free shrinkage properties exhibited by the ethylene-based copolymer compositions (A), (A '), (A ") or (A"') of the present invention depend on whether the irradiation is performed before or after the final film orientation. Nevertheless, it is essentially unaffected.
    Irradiation techniques effective for carrying out the treatment of the film structures described herein include techniques known to those skilled in the art. Preferably, this irradiation is achieved using an electron beam (beta) irradiation apparatus at dose levels of 0.5 Megarad (Mrad) to 20 Mrad. Shrink film structures prepared from the ethylenic copolymer compositions (A), (A '), (A ") or (A"') described herein have a lower degree of chain breakage as a result of irradiation treatment. It is expected to exhibit improved physical properties as a cause.
    Hot-tak films of the invention are oriented or unoriented single layer or multilayer structures, which show utility in back-in-box and form-fill-seal operations. Examples of using the film of the present invention for foam, thread and yarn operations are described in Wilmer A. Jenkins and James P. Harrington, "Packaging Foods With Plastics" (1991), 32-83. C.G.Davis, "Packaging Machinery 0perations: No. 8, Form-Fill-Sealig, A Self-Instructional Course" by Packaging Machinery Manufacturers lnstitute (April 1982); "The Wiley Encyclopedia of Packaging Technology" by M. Bakker (Editor), John Wiley & Sons (1986) (334, 364-369); and by S. Sacharow and ALBrody, "Packaging: An lntroduction", Harcourt Packages can also be prepared using vertical or horizontal foam / fill / sealing and hot foam / fill / sealing, as described in Brace Javanovich Publications, Inc. (1987), pp. 332-326. Particularly effective devices for foam / fill / thread operations are the vertical foam / fill / thread machines of Hayssen Ultima Super CMB., Which are used to package typical products such as food, pharmaceuticals and hardware. Cryovac and Koch are other manufacturers of apparatus for venting by thermoforming pouches.
    Heavy Duty Packaging Films:
    The high load packaging film is a film of the above ethylene-based copolymer composition (A), (A '), (A ") or (A"'), and the film thickness is at least about l.25 mil (31 micrometers), It has a film density in the range of 0.923-0.95 g / cm 3 (g / cc) and typically exhibits at least 30% higher tear strength or impact resistance than polyethylene films currently used in industry. The film can be used for heavy-duty packaging and transportation applications and for ho-fill packaging.
    In the present specification, the term "medium modulus" is used to refer to the novel film, which means that the calculated film density is in the range of 0.923 to 0.95 g / cc. In this specification, the term "calculated film density" is used for the purpose of meaning the film density as calculated from the known weight of the constituent polymers or layers and the measured density after annealing.
    In the present specification, the reference to the novel film, the term "thick" is used for the purpose of meaning a film thickness of about l.25 mil (31 탆) or more.
    The term "variable stalk extrusion" means that the distance between the annular die for the film and the height of the stalk, i.e., the bubble expansion point, can vary from 0 inches (0 cm) to 144 inches (366 cm) or more during the manufacture of the blown film. Indicates. The term includes both well known pocket blown film extrusion and stoke blow extrusion. In this specification, the term “high stock extrusion” is used as a conventional meaning, meaning that the distance between the annular die for the film and the air ring is equal to or greater than 30 inches (76 cm).
    In the present specification, the term "heat charge" refers to the packaging or product filling operation at a product temperature of 45 ℃ or more. As used herein, the term “high load” generally refers to packaging an industrial article in bulk or with a single package weight of at least 10 pounds (4.5 kilograms).
    The tear resistance exhibited by the film of the present invention is measured according to ASTM Dl922 and reported in grams. The tear resistance is measured in both the machine direction MD and the transverse direction CD. In this specification, the term "tear strength" is used to indicate an average between the MD tear resistance value and the CD tear resistance value, which is likewise reported in grams. The impact resistance exhibited by the film of the invention is measured according to ASTM Dl709. If the relationship shows that the performance value also increases as the thickness increases, it is normalized to exactly 3 mil by increasing or decreasing the tear and impact results accordingly based on the actually measured film thickness (μm). The normalized calculations are reported and reported only when the variation in thickness is within 10%, that is, when the measurement thickness is in the range of 2.7 to 3.3 mils.
    The calculated film density of the medium modulus film of the present invention is in the range of 0.923 g / cc to 0.95 g / cc, especially 0.926 g / cc to 0.948 / cc, more preferably 0.93 g / cc to 0.945 / cc.
    Film thicknesses generally range from about l.25 mils or more, in particular in the range from l.5 mils to 8.75 mils, more preferably in the range of 2 mils to 8 mils.
    The tear strength or impact resistance exhibited by this novel film is at least 30% higher than the tear strength or impact resistance exhibited by polyethylene films of the prior art having almost the same film density, melt index and film thickness.
    This novel film can be conveniently molded into a bag, making it useful for use in thermally charged packaging applications in addition to high load packaging and transport applications, where such films exhibit good balance of properties, i.e. tear, impact and dimensional stability. There is a need for a film that is both good in strength and medium in modulus.
    This new film can be produced by variable-stalk blown extrusion. The production of films by blown film extrusion is well known. See, for example, US Pat. No. 4,632,801 to Dowd, which describes a typical method for extrusion of a blown film. In a typical method, a polymer is introduced into a screw extruder, the polymer is melted therein, and the inside of the extruder is advanced forward under pressure. The molten tube is formed by passing the molten polymer through an annular die for film and extruding it. Air is then supplied into the annular die to expand the tube to produce a "bubble" having the desired diameter. Air is held in the bubble with this annular die and nip rollers located downstream of the die, and then the bubble is pressed to produce a lay-flat film. The final thickness of the film is controlled by extrusion rate, bubble diameter and nip speed, and they are adjustable with variables such as screw speed, haul off rate and winding speed. If the bubble diameter and nip speed are constant to increase the extrusion rate, the final film thickness will be thicker.
    Typical blown extrusion methods are generally categorized as "stock" or "pocket" extrusion. In the case of a stoke extrusion, the bubble swells and expands at a considerably high point of the annular die, and the adjustment is performed. An air ring (which is usually a single granule) such that the tube is maintained at about the same diameter as the annular die for the film until the molten tube swells at least 5 inches (12.7 centimeters) above the annular die. -lip) to supply the airflow outside the tube in parallel to the machine direction. Moreover, it is also possible to cool the inside of a bubble in order to ensure the optimal stability of a bubble during manufacture, and it is also possible to use a bubble stabilization means inside likewise.
    It is known that the use of stalk extrusion improves molecular relaxation, reduces the tendency of excessive orientation in the l directions and thus obtains balanced film properties. Increasing the height of the stoke, i.e., the inflation, generally improves the transverse direction (CD) characteristics, thereby improving the average film characteristics. The high temperature polyethylene composition, such as high molecular weight high density polyethylene (HMW-HDPE) and high molecular weight low density polyethylene (HMW-LDPE), etc. (they have sufficient melt strength to ensure sufficient bubble stability) In the case of production, stock extrusion processing, in particular high stock extrusion, is very useful.
    In the case of pocket extrusion, air is supplied from an air ring placed in the immediate vicinity of the annular die so that the bubbles from the die immediately swell and expand. This air ring is typically two-neutral for the purpose of ensuring the stability exhibited by the bubbles after the air supply. Pocket extrusion is more widely used than stoke extrusion and is generally suitable for polyethylene compositions with lower molecular weights and lower melt strengths, such as linear low density polyethylene (LLDPE) and ultra low density polyethylene (ULDPE). .
    Both the single layer film and the multilayer film can be produced by stoke and pocket extrusion, and the film of the present invention may be a single layer structure or a multilayer structure. Multilayer films can be produced by any technique known in the art, which includes, for example, coextrusion, lamination or combinations thereof. However, suitable thick medium modulus polyethylene films of the present invention are single layer film structures.
    Additives such as antioxidants, phosphites, and clings to the ethylene copolymer composition (A), (A '), (A ") or (A"') used in the manufacture of the film of the present invention. ), Additives, Standostab PEPQ (trademark), pigments, colorants, fillers, and the like, may contain the improved tear and impact resistance disclosed by the applicants to such an extent that the additives and materials do not interfere. Generally, but not required, additives that improve antiblocking and coefficient of friction characteristics, including, but not limited to, untreated and treated silicon dioxide, talc, calcium carbonate and clay, as well as primary, secondary and Substituted fatty acid amides, etc.), a release agent, a silicone coating material, etc. can also be contained in the film of this invention. Further, for the purpose of improving the antistatic properties exhibited by the film of the present invention and enabling high load packaging of, for example, electron sensitive products, another additive such as a quaternary ammonium compound or the like may be used alone or in ethylene. It is also possible to add in combination with acrylic acid (EAA) copolymers or other functional polymers.
    The strength characteristics of this novel film have been improved, and the dosage typically possible when a polymer for dilution is used in addition to the reuse material and the scrap material to the film composition used for the production of this novel film is used in the polyethylene film composition of the prior art. Higher amounts can be mixed or blended and the new film can have or maintain the performance characteristics required for successful use in high load packaging and transportation applications. Suitable diluent materials include, for example, elastomers, rubbers and anhydride modified polyethylenes (e.g., LLDPE and HDPE grafted with polybutylene and maleic anhydride), for example high pressure polyethylenes such as low density polyethylene (LDPE). Ethylene / acrylic acid (EVA) copolymers, ethylene / vinyl acetate (EVA) copolymers, ethylene / methacrylate (EMA) copolymers, and the like, and combinations thereof.
    Stretched adhesive film:
    The present invention is a multilayer film comprising at least two layers and having substantial adhesiveness on one side, and suitable for use as a stretch wrap material. This novel multilayer film consists of at least one ethylenic copolymer composition (A), (A '), (A ") or (A"') having a density of at least about 0.90 g / cc or about 0.90 g / cc. A backing layer, a surface layer of at least one film-forming olefin polymer composition having a density of about 0.90 g / cc, and optionally at least one core or structure layer of at least one high strength ethylene polymer composition.
    The surface layer exhibits significantly less adhesiveness than the back layer. The core or structural layer can be varied to suit specific film strength requirements.
    According to the present invention, a film produced with one-sided adhesiveness is particularly useful for stretching lapping, stretching bundling and tension winding operations for wrapping or holding a small article or object. The single-sided adhesive film of the present invention is provided without the need for an adhesive additive or a functional polymer.
    Advantages of the present invention include reduction or disappearance of piles or accumulation of resin in the die lip and migration of low molecular weight materials. This means that the cleaning and holding time during film making and wrap operation is reduced. The problem of sticking the film to adjacent articles and packages, and the problem of contamination or retention of dust or debris on the film surface, are also reduced.
    Another aspect of the present invention provides a one-sided tacky film of polymers having similar rheological and monomeric chemical properties, thus easily achieving consistent improved melt viscosity and good polymer compatibility for recycling during coextrusion. .
    Another aspect of the present invention is to provide a single-sided tacky film in which the film exhibits markedly stretched and unstretched tack without a decrease in high tack under drawing conditions.
    The amount of adhesion is related to the density of the polymer or blend combination forming the back layer and the surface layer of the film, and it has been found that the adhesion improves as the polymer density of the back layer decreases. The back layer of the present invention is a surface layer when the density of the back layer is 0.90 g / cc or less, preferably 0.85 g / cc to 0.99 g / cc, and most preferably 0.86 g / cc to 0.98 g / cc It shows a substantial adhesion of. The density of the surface layer of the present invention is at least 0.90 g / cc, preferably in the range of 0.91 g / cc to 0.96 g / cc, more preferably in the range of 0.93 g / cc to 0.95 g / cc. More preferred 0.93 g / cc to 0.95 g / cc surface layer provides a single-sided adhesive film having comparable stretch and non-stretch adhesion.
    The density of the core layer or the structure layer included in the multilayer film of the present invention can be changed to match the overall film strength requirements according to the end use.
    Ethylene polymer having a density of less than 0.90g / cc or less than 0.90g / cc constituting the back layer of the present invention is a uniformly branched ultra low density polyethylene (VLDPE), the ethylene-based copolymer composition (A), (A '), (A ″) or (A ″ ′) and blends thereof. Preferably, a back layer becomes a composition (A), (A '), (A ") or (A"').
    The film-forming olefin polymer composition having a density greater than 0.90 g / cc constituting the surface layer of the present invention is a propylene and ethylene polymer such as polypropylene, ethylene propylene copolymer, low density polyethylene (LDPE), medium density polyethylene (MDPE) , High density polyethylene (HDPE), composition (A), (A '), (A ") or (A"'), heterogeneous or uniformly branched linear low density polyethylene (LLDPE), heterogeneous or uniformly branched ultra low density polyethylene (VLDPE) ) And blends thereof. Preference is given to the surface layer being made of polypropylene, for example MDPE and HDPE or MDPE alone and a combination of polypropylene, because of the ability to give the same stretch and non-stretch adhesion.
    Ethylene polymers constituting the core or structural layer of the present invention are low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), composition (A), (A '), (A ") or (A"). '), Heterogeneous and uniformly branched linear low density polyethylene (LLDPE), heterogeneous and uniformly branched ultra low density polyethylene (VLDPE).
    Heterogeneous branching VLDPE and LLDPE are well known to those skilled in the art of linear polyethylene. They are prepared using Ziegler-Natta solutions, slurries or gas phase polymerization and coordination metal catalysts described in Anderson, U.S. Patent 4,076,698. These Ziegler-type linear polyethylenes are not homogeneous branches and they have a low melt tension. In addition, these polymers have a low density and are substantially amorphous. This is because it inherently has a substantial high density (crystal) polymer portion. At densities of less than 0.90 g / cc, these materials are difficult to prepare using conventional Ziegler-Natta catalysts and are also very difficult to pelletize. Pellets are sticky and easy to stick together.
    Homogeneous branching VLDPE and LLDPE are also well known to those skilled in the art of linear polyethylene. See, for example, the disclosure of US Pat. No. 3,645,992 to Erston. They are prepared by solution, slurry or vapor phase using zirconium and vanadium catalyst systems. Yiwen, in US Pat. No. 4,937,299, describes a preparation method using a metallocene catalyst. These secondary linear polyethylenes are homogeneous branched polymers, but like Ziegler-type heterogeneous linear polyethylenes, they have a low melt tension. Commercial examples of these polymers include trade name "TAFMER" sold by Mitsui Chemicals, and trade name "EXACT" sold by Exxon Chemical.
    The ethylene polymer composition used for the back layer, the film-forming olefin polymer composition used for the back layer, and the high-strength ethylene polymer composition used for the core or the structural layer of the present invention are homopolymerized with ethylene or a small amount of ethylene and various monomers. Ethylene polymers produced by interpolymerization.
    Additives such as adhesive additives, pressure sensitive adhesives (eg PIB), slip and anti blocking agents, antioxidants (eg hindered phenols such as Irganox1010 or Irganox1076 supplied by Ciba-Geigy), phosphites ( Irgafos 168 for example, supplied by Ciba-Geigy, Stanstav PEPQ (supplied by Sandos), pigments, colorants, fillers, and processing aids are not necessary to achieve the desired results of the present invention, but It can be made to contain in the extending | stretching wrap material disclosed by the. Naturally, the additives may be blended to such an extent that they do not interfere with the substantial stickiness and non-tackiness found in the present invention.
    The multilayer film of the present invention can be produced from two or more film layers comprising A / B and A / B / C structures, by film lamination and / or coextrusion techniques, and by blow or cast film extrusion apparatus known in the art. have. Preferred structures are A / B / C structures produced by coextrusion techniques, more preferably by cast coextrusion techniques.
    Suitable blown film methods are described, for example, in The encyclopedia of Chemical Technology, Kirk-Othmer, 3rd edition, (John Wiley & Sons, New York), 1981, Vol. 16, pp. 416-417, and Vol. 18, pp. 191-192. It is. Suitable cast extrusion methods are described, for example, in the Mid October 1989 Encyclopedia Issue, Vol. 66, No. 11, pages 256-257. Suitable coextrusion techniques and requirements are described in Tom I. Butler "Film Extrusion Manual: Process, Materials, Properties, Coextrusion", Ch 4, pp. 31-80, TAPPI Press, (Atlanta, Ga. 1992).
    The melt index of each polymer layer of the multilayer film of the present invention is in the range of 0.4 to 20 g / 10 minutes, preferably 0.5 to 12 g / 10 minutes, more preferably 0.8 to 6 g / 10 minutes.
    The total film thickness of the multilayer film of the present invention is 0.4 to 20 mils (10 μm to 508 μm), preferably 0.6 to 10 mils (15 μm to 254 μm), more preferably 0.8 to 5 mils (20 μm to 127 μm) to be.
    The layer ratio of the A / B multilayer film of this invention is larger than A-layer / B layer of 2:98, Preferably it is 5: 95-35: 65, More preferably, it is the range of 10: 90-25: 75. The layer ratio of the multilayer film of two or more layers is maintained at the same thickness of the back layer and the surface layer of the film, the ratio of the core or structural layer is 60 to 98% by weight, preferably 65 to 95% by weight, more preferably 70 to 90 Weight percent range.
    Multilayer barrier film:
    The multilayer barrier film is an oxygen and moisture impermeable multilayer barrier film, and examples of the use thereof include ostomy bags, laminates for percutaneous delivery of drugs, and heat sealable bags. The product manufactured is mentioned.
    One aspect of the present invention provides an oxygen and moisture impermeable multilayer barrier film having a heat sealing strength of at least 1.0 lb, preferably greater than 1.5 lb, per inch of film width.
    "Oxygen impermeable" means that the film has an oxygen permeability of 90 cc / m 2 / H · atm or less. "Moisture impermeability" means that the film has a water vapor transmission rate of 5 gm / m 2 / H or less.
    In one aspect, the film includes a barrier layer having at least one heat sealable skin layer thereon. The barrier layer comprises any suitable barrier layer material that provides the desired oxygen and moisture impermeability, eg suitable as a heat sealable skin layer (monolayer or plural layers). Preferred barrier materials are copolymers of vinylidene chloride and vinyl chloride or methyl methacrylate. When the barrier layer comprises copolymers of vinylidene chloride and vinyl chloride or methyl methacrylate, the barrier layer optionally contains 0 to 6% by weight of a copolymer of ethylene and vinyl acetate, more preferably 4 to 6 as a processing aid. May contain%.
    In one aspect of the invention, the barrier layer is coextruded with at least one heat sealable skin layer. To provide the desired flexibility, the heat sealable skin layer preferably has a 2% secant modulus of less than 15,000 psi in both the machine direction (MD) and the transverse direction (TD). The skin layer which can be heat-sealed contains an ethylenic copolymer composition (A), (A '), (A ") or (A"'). In order to assist the processing of the film, the skin layer (single layer or plural layers) may contain 0 to 10% by weight of the copolymer of ethylene and vinyl acetate, more preferably 0.5 to 5% of the copolymer as a processing aid. The skin layer may also optionally contain a slip agent / anti-stick agent. Between the skin layer and the barrier layer, it is desired to co-extrude an adhesive layer of ethylene and vinyl acetate copolymer to improve the adhesion of the layer.
    In a preferred aspect of the present invention, the barrier layer is coextruded between two heat sealable skin layers. In that case, the skin layer is 70% by volume (thickness) of the film, and the barrier layer is 30% by volume (thickness) of the film. This structure can be used to fabricate reusable Ostomy bags or pouches. The barrier layer and the skin layer (single layer or plural layers) may be prepared separately, and then laminated at the same time using a suitable adhesive polymer, liquid adhesive, or hot melt adhesive. The multilayer barrier film of the present invention exhibits less than 85 dB of noise when bent at an angle of 65 ° at 0.45 Hz, preferably exhibits less than 83 dB when bent at an angle of 65 ° at 0.45 Hz, most preferably 65 at 0.45 Hz. Curved at an angle of less than 81dB of noise.
    In another aspect of the present invention, an additional layer may be added to the barrier layer to form a system for transdermal delivery of a medicament. Preferably the system comprises a backing layer of barrier film which serves as a gateway to the pharmaceutical system. The adhesive comprising the active agent is preferably attached to one side of the film. The adhesive is adjacent to a controlled release membrane that is suitable for contacting the skin of the patient and for releasing the agent under control.
    In another form of this aspect, the backing layer can form a reservoir comprising the active agent, with a controlled release membrane that controls the diffusion of the agent into the patient's skin and conceals the opening of the reservoir. Adhesives can be used around the membrane or throughout the membrane to adhere the percutaneous delivery system to the patient's skin. Preferably, the release liner is covered over the adhesive and the membrane to protect the structure prior to use.
    It is therefore a feature of the present invention to provide an oxygen and moisture impermeable multilayer barrier film that can be prepared using co-extrusion or lamination. Further features of the present invention include odor barrier properties, flexibility, and low noise. In addition, a surface capable of heat sealing for use in fabricating bags and pouches is provided.
    In one aspect, the multilayer barrier film of the present invention can be prepared using standard extrusion techniques such as, for example, feedblock coextrusion, multi-manifold die co-extrusion, or a combination of the two. The volume (thickness) of each independent layer can be adjusted at the time of extrusion. Therefore, the overall thickness of the multilayer structure can be adjusted. Alternatively, the independent layers can be made separately and laminated together using a suitable adhesive bonding layer.
    In order to protect the low noise of the film, the film is not intentionally stretched or stretched other than naturally occurring at the time of manufacture. For example, the film produced by the blow method essentially has several orientations in both the machine direction (MD) and the transverse direction (TD), and the cast film is unstretched in the transverse direction. In general, the smaller the orientation introduced into the film, the smaller the noise. The multilayer barrier film of the present invention exhibits less than 85 dB of noise when bent at an angle of 65 ° at 0.45 Hz, preferably exhibits less than 83 dB when bent at an angle of 65 ° at 0.45 Hz, most preferably 65 at 0.45 Hz. Curved at an angle of less than 81dB of noise.
    In addition, to provide the desired flexibility, the heat sealable skin layer preferably has a 2% secant modulus of less than 15,000 psi in both the machine direction (MD) and the transverse direction (TD). 2% secant modulus is a measure of the stiffness or flexibility of the film. We found that the lower the 2% split modulus of the heat-sealable skin layer, the more flexible the resulting film. It is generally desirable for the 2% secant modulus of the film to be as low as possible and still be processable by conventional apparatus. As for the entire multilayer film, the 2% secant modulus is preferably 30,000 psi or less. The resulting multilayer film has low oxygen and vapor permeability and also has the odor barrier properties, flexibility and low noise properties required for ostomy applications.
    Oxygen and moisture impermeable multilayer barrier films are copolymers of vinyl chloride (15-20 wt%) and vinylidene chloride (80-85 wt%) or vinylidene chloride (93-94 wt%) and methyl methacrylate (6 ˜7 wt.%) Copolymer. Suitable barrier materials include, for example, Saran® 469 and Saran MA, available from Dow Chemical Company. In the case of using the Saran barrier layer material, the barrier layer may contain 0 to 6% by weight, more preferably 4 to 6% by weight of a copolymer of ethylene and vinyl acetate as a processing aid. Suitable examples of ethylene / vinylacetate copolymer compositions are copolymers sold under the trademark Elvax® from E.I duPont de Nemours & Co., Inc.
    Preferably, the barrier layer is co-extruded with two heat sealable skin layers containing the ethylenic copolymer composition (A), (A '), (A ") or (A"'), or said 2 Laminate between layers.
    The barrier film is folded to overlap the film and then heat-sealed the ethylene-based copolymer composition (A), (A '), (A ") or (A"') skin layers to produce a reusable Ostomy bag or pouch. Can be used for Preferably the bag has an oxygen permeability of less than 90 cc / m 2 / H · atm (1.8 cc / 100 in 2 / H · atm). The barrier film is 35-100 micrometers in total thickness, and a barrier layer comprises 10-30% of the film total thickness. The skin layer (and adhesive layer if necessary) typically constitutes 70-90% of the overall thickness of the film.
    The multilayer barrier film of the present invention can also be produced by a lamination technique using a suitable adhesive. For example, the barrier layer and the skin layer (monolayer or plural layers) can be made separately and then laminated together using an adhesive polymer, a liquid adhesive, or a hot melt adhesive. Suitable adhesive polymers for bonding the barrier and skin layers include, but are not limited to, ethylenically unsaturated copolymers of vinyl acetate, ethyl acrylate, ethyl methacrylate, methyl acrylic acid, acrylic acid, and carbon monoxide. Other acids include ionomers of ethylene and methylacrylic acid or acrylic acid, and graft anhydride copolymers. Suitable liquid adhesives or hot melt adhesives include, but are not limited to, those based on copolymers of urethanes, copolymer esters, and amide acrylates.
    The five layers of oxygen and moisture impermeable barrier film comprise a barrier layer of a suitable barrier material as previously described. Preferably the barrier layer is coextruded with the two outer heat sealable skin layers while sandwiching the adhesive layer between the two outer heat sealable skin layers. The heat-sealable skin layer in this five-layer aspect is a substantially linear copolymer of ethylene and α-olefins as described in published PCT application NO.PCT / US92 / 08812 or eg EXACT resin. And a uniformly branched linear polyolefin resin such as a TAFMER resin. Suitable adhesives include copolymers of ethylene and vinyl acetate, which improve the mutual adhesion of the barrier layer and skin layer.
    In the simplest form in another aspect of the invention where an additional layer is included with the barrier film to form a system for delivering the drug transdermally, the barrier and skin layers of the film are backside films that are barriers to the drug system. Function as. The barrier film further comprises an adhesive layer comprising an active agent adhered to one side of the film and blended in the matrix. The adhesive chosen must be compatible with the active agent and must be permeable to the active agent. Active agents, including for example estrogen, nitroglycerin, nicotine and scopolamine, can be administered to a patient in this manner. In theory, almost any drug can be administered in this manner.
    There is a controlled release membrane on the adhesive that is suitable for bonding in contact with the skin of the patient and for releasing the controlled agent. An additional layer of adhesive, which may be applied around the membrane or on the entire surface of the membrane, may be present to secure the percutaneous delivery system to the patient's skin. Adhesives used in the practice of this aspect of the invention are medical adhesives, such as silicone adhesives, acrylic adhesives or vinyl acetate adhesives. Typically, in this aspect, the system is sealed during packaging or secured with a second barrier film and the packaging or second barrier film is removed before use.
    Another aspect of the transdermal drug delivery system according to the present invention is described. The barrier layer and skin layer form a barrier film formed therein into a reservoir for containing the active agent. The opening of the reservoir is concealed with a controlled release membrane. Adhesives that can be applied around the membrane or over the entire area of the membrane serve to secure the system to the skin layer of the patient. The adhesive selected must also be compatible with the active agent and must be permeable to the agent. Preferably the release liner or the like hides and protects the adhesive and film prior to use.
    A typical reusable Ostomy bag comprising an opening made from a multilayer barrier film can be fabricated by folding and overlapping the edges of the multilayer film and heat sealing the edges. Preferably, the film is folded and sealed so that the inner surface of the bag or pouch is provided by one heat sealable skin layer.
    The barrier film of the present invention provides the flexibility and quietness, water resistance and odor barrier properties and oxygen barrier properties required for Ostomy applications. As appreciated by those skilled in the art, the barrier films of the present invention can be used in other packaging applications where barrier to moisture and oxygen is required.
    Sealants for Laminated Films:
    The sealant for laminated films can be molded by an air-cooled inflation method using the ethylene copolymer composition (A), (A '), (A ") or (A"').
    The sealant for laminated films according to the present invention has a dart impact strength of 100 kg / cm or more, preferably 150 kg / cm or more.
    Moreover, this film has a complete sealing temperature of 130 degrees C or less, Preferably it is 110-130 degreeC.
    Moreover, as for the sealant for laminated films which concerns on this invention, blocking strength is 1.5 kg / cm or less normally, and tensile Young's modulus is 500 kg / cm <2> or more normally.
    The thickness of the sealant for laminated films according to the present invention is 10 to 150 µm, preferably 10 to 60 µm.
    When laminated with the sealant for laminated films which concerns on said this invention as a base material, a laminated film is obtained.
    As said base material, the thin film body which consists of arbitrary materials which can form a film form can be used. Such thin films include polymer films or sheets, fabrics, paper, metal foils, and cellophane.
    Such a sealant for laminated films is excellent in low temperature heat sealing property, hot tag property, impact resistance, blocking resistance, and opening property.
    Heavy Packaging Films:
    The Young's modulus measured in accordance with JIS K6781 has a Young's modulus of 4000 kg / cm 2 or more, the dart impact strength measured in accordance with ASTM A1709 method is 55 kg / cm or more, and the film thickness is 30-200 micrometers normally.
    The film for heavy packaging can manufacture the said ethylene-based copolymer composition (A), (A '), (A ") or (A"') by the inflation method and the T-die method. For example, it can also be laminated | stacked with the film of polyester and polyamide, and can also be set as a multilayer film.
    Such a heavy packaging film is excellent in mechanical strength, transparency, and smoothness of the film surface, and is suitable for packaging of food, office supplies, furniture, toys, electric appliances, mechanical parts, and the like. It can also be used as a bag for heavy packaging in a cold district.
    Grain bags:
    The grain bag for grains of this invention becomes a film of the said ethylene-type copolymer composition (A), (A '), (A ") or (A"'), and the three directions of the two films superimposed on each other are blocked. As long as an opening part is formed in one end and a bottom part is formed in the other end, you may manufacture by what kind of method. For example, one film may be folded twice to block both sides, and two synthetic resin films may be superimposed on each other and the three directions inside thereof may be blocked, or usually formed by an inflation method or the like (tube shape). You may block one direction of the film, and let another direction be an opening part.
    Moreover, when blocking one direction of a film, it is preferable to weld films, for example, but what kind of method may be used as long as the content can be sealed when blocking films.
    (Director)
    The extension end serves as a base for attaching the string to be described below, and also serves as an edge for winding the string for blocking the opening of the grain bag of the present invention.
    This extension end may adhere a separate film to one end of the opening end of the film to be wrapped, or may form a film overlapping each other so that the extension end is formed when the bag is formed.
    (String tied)
    The tie string is to block the opening of the grain bag. Although what kind of thing may be used for the material of this string to be tied, when a material like a film is used, convenience is improved when reproducing the grain bag of this invention, and it is preferable.
    (Sealing part for string)
    The string sealing portion is formed so as to load the tie string to the production end. This string sealing part is formed by folding a part of the extension end part toward the opening end side of the other film, and folding it so as to incorporate a string to be bound therein. For example, you may make it the state which inserted the string to be tied simply by sealing the folded | stretched leading ends. Alternatively, the strings that are tied together with the production ends may be sealed so that the strings do not move. For example, you may apply | coat an adhesive to the inside of a string sealing part, and the string which bonds and binds the string sealing part may not be moved.
    (Gap)
    The gap is formed between the sealing portion for the string and the opening end of the other film. If this gap is formed, the opening becomes easy to open when the grain bag is used, and this gap is preferable because it serves as an edge for winding the tie string for blocking the grain bag. The width of this gap is 5 to 100 mm, preferably 10 to 30 mm.
    (Additional components of the present invention)
    Although the grain bag of the present invention is an essential component described above, it may further include additional components described below.
    (Flap)
    The grain bag of the present invention may extend from the string sealing portion toward the opening end side to cover the opening and have a flap portion having a predetermined width. In this case, since the flap portion keeps the contents in the vicinity of the opening, even if the grain bag is placed sideways, it is preferable in that the grains do not spill inside.
    Moreover, the width | variety of a flap part is at least the width | variety of the said clearance gap, and is 30-150 mm, More preferably, it is 50-100 mm.
    (Fold portion)
    The bottom part may be provided with a pleated portion having a cross-sectional V-shape formed by folding one end of the synthetic resin film inward. In this case, when the grain is placed inside the grain bag, the bottom of the bag becomes flat and the bag stands up stably.
    At this time, if the diagonal sealing such that the two sides draw the quadrilateral of an isosceles triangle that is about the width of each corrugation part is applied to each corner of the bottom of the grain bag, the width of the bottom becomes constant regardless of the grain capacity. desirable.
    (Air hole)
    It is preferable to provide the film with a plurality of vent holes along both sides of the grain bag, so that the state of the stored grain can be properly maintained. A plurality of vents may be formed along at least one of the opening end and the lower end of the film. Moreover, each vent may be arranged in a rectangular shape integrally with a film.
    In addition, the ventilation hole may be provided only in any one of two films, and may be provided in both films.
    In addition, since the bag for grains stores heavy materials and moves frequently, it is required to be excellent in impact resistance and tear resistance.
    The grain bag according to the present invention is formed from a film formed of the composition (A), (A '), (A ") or (A"') by, for example, an inflation method, and has a strength suitable for grain bags. Since it is obtained, the thickness of the grain bag is thinner than conventional polyethylene. The film formed by the air-cooled inflation method from this composition (A), (A '), (A ") or (A"') has (I) tensile Young's modulus of 4,000 kg / cm <2> or more, (ii) dart impact strength Is 55 kg / cm or more, suitable for use as a bag for grain.
    Moreover, it is preferable that the glossiness of the said film is 50% or more, and it is preferable that the thickness of the said film is 30-200 micrometers as a grain bag.
    Moreover, since this film is excellent in low-temperature characteristics, such as low-temperature falling bag strength characteristic which can be fully utilized also in the cold region below freezing point, film thickness can be made thin and high-speed molding of a film is possible.
    According to the grain bag of the present invention, first, an opening provided at the other end of the grain bag is opened, and an appropriate amount of grain is put therein. Next, the extension end is wound appropriately on the opening end side of the other film. Finally, the two sides of the tie string are connected to each other to bind the openings. Therefore, the method of using the grain bag is the same as that of the conventional paper bag. There is no change in the working practices of the producer or trader who is working with the conventional bag of grain.
    Moreover, since the grain bag of this invention is a synthetic resin bag, it can manufacture cheaply compared with the conventional grain bag made of paper. In addition, each component mentioned above can be arbitrarily combined as much as possible.
    (Production method of grain bag)
    Next, the manufacturing method of the grain bag of this invention is comprised as follows. In other words, out of two films, a production end portion forming step of forming a production end portion in which an end portion of one film extends in the opening direction than an opening end portion of the other film, and at the production end portion, are predetermined from an opening end of the other film. A string supply step of supplying a string to be bundled along the width direction of the bag, a step of inverting and folding the lead end to the open end side of the other film so as to contain the string to be bound; And a sealing step of overlapping and welding the stretched lead ends to overlap each other in a state in which the binding string is enclosed and a gap is left between the open ends of the other film.
    Here, the grain bag for which the three directions of the film made of two synthetic resins superimposed on each other is clogged, the bottom part is formed at one end, and the opening part is formed at the other end may be formed by sealing three directions of two independent films, or one film The two directions may be formed by folding the sheet into two pieces and sealing the two directions. However, if the film is formed in advance, such as an inflation film, the two directions are blocked from the beginning, and the manufacturing process becomes easy.
    The bottom portion may further include a bottom portion folding step of folding the bottom portion inward to form a pleated portion having a V-shaped cross section. Moreover, you may further include the drilling process which equips a several ventilation hole along both sides of the said film of the other end. Further, a second drilling step of forming a plurality of vent holes along at least one of the opening end and the lower end of the other film may be further included.
    Flexible Material Packaging Pouches:
    Flowable material packaging pouches are pouches used in consumer packaging useful for packaging flowable materials (e.g. liquids such as milk), and the ethylene-based copolymer compositions (A), (A '), (A ") Or from certain film structures containing (A ″ ′).
    In the present invention, a single-layer film structure (polymer sealing layer) made of an ethylenic copolymer composition (A), (A '), (A ") or (A"') is used to package a fluid material. Prepare the pouch.
    Generally, the ethylene-based copolymer composition (A), (A '), (A ") or (A"') is used alone as a sealing layer of this film or film structure. However, it is also possible to blend the ethylene copolymer composition (A), (A '), (A ") or (A"') with other polymers used as a heat sealing layer. Generally, the ethylene copolymer composition is 10% by weight to 100% by weight of the film structure.
    In addition, additives known to those skilled in the art, such as antioxidants, phosphites, cling additives, Standsrab PERQ (trademark) supplied by Sandoz, and anti-blocking additives, are also known to those skilled in the art. It is also possible to add slip additives, UV stabilizers, pigments, processing aids and the like.
    The films and film structures disclosed herein are subject to the use of an ethylenic copolymer composition (A), (A '), (A ") or (A"') as at least one layer, preferably a sealing layer. It may be a single layer or a multilayer film structure. The thickness of the sealing layer is at least about 0.1 mil (2.5 μm) and more, preferably 0.2 mil (5 μm) to 10 mil (254 μm), more preferably 0.4 mil (10 μm) to 5 mil (127 μm). It may be.
    A surprising feature of the film structure for pouches of the present invention is that the heat sealing range of the film is wide. The heat sealing range of this film structure is 50 degreeC-160 degreeC, Preferably it is 75 degreeC-150 degreeC. It has been found that the sealing layer of the present invention has a wider heat sealing range than the polyethylene film of the prior art made from ethylene polymers which are unevenly branched even when the density is about the same. In order to further increase the flexibility in the heat sealing method of making pouches from the film structure, it is important to widen the heat sealing range. The melting point range of the composition (A), (A '), (A ") or (A"') used in the manufacture of the film structure having the above heat sealing range is generally 50 ° C to 130 ° C, preferably 55 ° C to 115 ° C.
    Another unexpected feature of the film structure for pouches of the present invention is that at low temperatures the film exhibits heat sealing strength. Generally, the film structures of the present invention are at least about 1 N / inch within about 0.3 seconds at a sealing bar temperature of about 110 ° C. when using the DTC Hot Tack Strength Method, as defined below herein. 0.4 seconds at a sealing bar temperature of about 110 ° C., when achieving a hot tag strength of (39.4 N / m) or using the DTC Heat Seal Strength Method defined below herein. A heat sealing strength of at least 11 bf / inch (175 N / m) is achieved within a while. The film structures of the invention also exhibit hot tag or heat sealing onset temperatures of less than about 110 ° C. with a force of at least about 1 N / inch (39.4 N / m). Sealings made using the sealing layer of the present invention have been found to exhibit higher strength at lower sealing temperatures than those using higher density prior art polyethylenes. It is important to give high heat sealing strength at low temperatures in order to produce pouches with low leakage by operating a conventional packaging device such as a vertically-formed filling sealer at high speed.
    When the ethylene copolymer composition (A), (A '), (A ") or (A"') is used as a sealing layer of the film structure for pouches of this invention, especially the pouch of this invention is linear low density polyethylene, linear When compared with a pouch manufactured using ultra low density polyethylene, high pressure low density polyethylene, or a combination thereof, it is considered that (1) a pouch that can be processed at high speed with a molded filling sealer is obtained, and (2) a pouch package with less leakage is obtained. .
    In one aspect of the present invention, a pouch is made from a tubular film structure and has a terminal which is heat-sealed in the transverse direction. This film structure,
    (I) 10 to 100% by weight of at least one layer comprising the ethylenic copolymer composition (A), (A '), (A ") or (A"'), and
    (II) 0 to 90% by weight of at least one polymer selected from the group consisting of non-uniformly branched linear ethylene / C 3 -C 18 α-olefin copolymers, high pressure low density polyethylene and ethylene / vinyl acetate copolymers It has at least 1 layer of film layers to make.
    Non-uniformly branched linear ethylene / C 3 -C 18 α-olefin copolymers of (II) are generally linear low density polyethylene (for example polyethylene produced using a Ziegler catalyst). These linear low density polyethylenes are again often subdivided into subsets, which are referred to as very low density polyethylene (VLDPE) or ultra low density polyethylene (ULDPE). VLDPE and ULDPE are interchangeable terms herein and those skilled in the art generally use them in this manner.
    The density of the linear low density polyethylene of (II) is generally in the range of 0.87 g / cm 3 to 0.94 g / cm 3, preferably 0.87 g / cm 3 to 0.915 g / cm 3. The heterogeneously branched linear low-density ethylene / C 3 -C 18 copolymer of (II) preferably has a melt index of 0.1 to 10 g / 10 minutes.
    The high pressure low density polyethylene of the above (II) preferably exhibits a density of 0.916 g / cm 3 to 0.93 g / cm 3 and a melt index of 0.1 to 10 g / 10 minutes.
    Preferably, the ethylene / vinyl acetate copolymer of the above (II) has a ethylene: vinyl acetate weight ratio of 2.2: 1 to 24: 1 and shows a melt index of 0.2 to 10 g / 10 minutes.
    Another aspect of the invention,
    (a) a density of 0.915 g / cm 3 or less and a melt index of 10.0 g / 10 minutes or less, wherein at least one composition (A), (A '), (A ") or (A"') is 10- 100% by weight,
    (b) at least one polymer selected from the group consisting of non-uniformly branched linear ethylene / C 3 -C 18 α-olefin copolymers, high pressure low density polyethylene and ethylene / vinyl acetate (EVA) copolymers Pouches prepared from 90% by weight blend.
    The non-uniformly branched linear ethylene / C 3 -C 18 α-olefin copolymer of (b) is generally linear low density polyethylene (eg polyethylene produced using Ziegler catalysts, etc.). This linear low density polyethylene comprises very low low density polyethylene (VLDPE) or ultra low density polyethylene (ULDPE) as described above. The density of the linear low density polyethylene of (b) is generally in the range of 0.87 g / cm 3 to 0.94 g / cm 3, preferably 0.87 g / cm 3 to 0.915 g / cm 3. The copolymer of the non-uniformly branched linear low density ethylene / C 3 -C 18 α-olefin of (II) preferably exhibits a melt index of 0.1 to 10 g / 10 minutes.
    The high pressure low density polyethylene of (b) preferably exhibits a density of 0.916 g / cm 3 to 0.93 g / cm 3 and a melt index of 0.1 to 10 g / 10 minutes.
    Preferably, the ethylene / vinyl acetate copolymer of (b) has an ethylene: vinyl acetate weight ratio of 2.2: 1 to 24: 1 and shows a melt index of 0.2 to 10 g / 10 minutes.
    The film structure for pouches of the present invention also includes a multilayer or composite film structure, and preferably the polymer sealing layer included in the structure is an inner layer of the pouch.
    As will be appreciated by those skilled in the art, the multilayer film structure for pouches of the present invention may include various film layer combinations as long as the sealing layer forms part of the final film structure. The multilayer film structure for pouches of the present invention may be a coextruded film, a coated film or a laminated film. This film structure is also used as a barrier film, for example polyester, nylon, ethylene / vinyl alcohol copolymer (EVOH), polyvinylidene dichloride (PVDC), for example Saran (trademark) by Dow Chemical Company ) And the metal coating film and the like. Depending on the final use of this pouch, the choice of other materials or types of materials used in combination with the present sealing layer film is greatly influenced. The pouch described in this specification refers to the sealing layer used at least inside of a pouch.
    One aspect of the film structure for pouches of the present invention includes a sealing layer of an ethylene-based copolymer composition (A), (A '), (A ") or (A"') and at least one polymer outer layer. . This polymeric outer layer is preferably a polyethylene film layer, more preferably "linear low density polyethylene (LLDPE)" and / or "linear ultra low density polyethylene (ULDPE)" and / or "very low low density polyethylene ( Heterogeneously branched linear polyethylene called " VLDPE) &quot;. An example of a commercially available LLDPE is DOWLEX® 2045 (a trademark of Dow chemical campany, commercially available from this company). An example of a commercially available ULDPE is ATTANE 4201 (a trademark of Dow chemical campany, commercially available from this company).
    LLDPE (including VLDPE and ULDPE) useful herein include ethylene and a small amount of an α-olefin having 3 to 18 carbon atoms, preferably an α-olefin having 4 to 10 carbon atoms (eg, 1-butene, 4-methyl). Non-uniformly branched linear copolymers made from -1-pentene, 1-hexene, 1-octene, 1-decene and the like). Generally, Ziegler catalysts are used to prepare such non-uniformly branched LLDPE (using, for example, methods described in US Pat. No. 4,076,698 (Anderson et al.)).
    The density of the LLDPE for the outer layer is generally at least 0.87 g / cm 3, more preferably 0.9 to 0.93 g / cm 3, and the melt index is generally 0.1 to 10 g / 10 minutes, preferably 0.5 to 2 g / 10 Minutes.
    The thickness of the outer layer may be any thickness as long as the sealing layer has a minimum thickness of 0.1 mil (2.5 μm).
    Another aspect of the film structure for pouches of the present invention includes a polymer layer interposed between two polymer sealing layers.
    Another embodiment of the film construction for pouches of the present invention includes at least one polymer core layer between at least one polymer outer layer and at least one polymer sealing layer. This polymer layer may be a film layer of LLDPE like the outer layer, or preferably another LLDPE, more preferably an LLDPE having a higher density than the outer layer. The thickness of the core layer may be any thickness as long as the sealing layer has a minimum thickness of 0.1 mil (2.5 μm).
    Another aspect of the pouch film structure of the present invention may be a structure comprising a sealing layer and another polyethylene film layer referred to herein as " high pressure low density polyethylene (LDPE) " Typically, this LDPE layer has a density of 0.916-0.930 g / cm 3 and exhibits a melt index of 0.1-10 g / 10 min. The thickness of the LDPE layer may be any thickness as long as the sealing layer has a minimum thickness of 0.1 mil (2.5 μm).
    Another aspect of the film structure for pouches of the present invention comprises an EVA copolymer layer having a weight ratio of sealing layer and ethylene: vinyl acetate of 2.2: 1 to 24: 1 and exhibiting a melt index of 0.2 to 20 g / 10 minutes. The structure may be. The thickness of this (EVA) layer may be any thickness as long as the sealing layer has a minimum thickness of 0.1 mil (2.5 μm).
    The thickness of the film structure used for manufacturing the pouch of the present invention is 0.5 mil (12.7 μm) to 10 mil (254 μm), preferably 1 mil (25.4 μm) to 5 mil (127 μm).
    The design of the film structure for the pouch of the present invention is flexible. Other LLDPEs (eg, VLDPE and ULDPE) may be used for the outer layer and the core layer for the purpose of optimizing certain film properties, for example the rigidity of the film. As such, the film can be optimized to suit particular applications, such as vertically molded filling sealers and the like.
    The polyethylene film structure used in the manufacture of the pouch of the present invention is prepared by using either a blown tube extrusion method or a cast extrusion method which is a method well known in the art. This blown tube extrusion method is described, for example, in Modern Plastic Mid-October 1989 Encyclopedia Issue, Vol. 66, Number 11, pages 264-266.
    Cast extrusion methods are described, for example, in Modern Plastic Mid-October 1989 Encyclopedia Issue, Vol. 66, Number 11, pages 256-257.
    The pouch of the present invention is a hermetically sealed container filled with "fluid material". "Fluid material" means a material that can flow under gravity or a pump transportable material, but the term "fluid material" does not include gaseous materials. These flowable materials include non-acid solutions (eg milk, water, juice, wine, etc.); Carbonated liquids (eg, cider, beer, water, etc.); Emulsions (eg ice cream mixes, soft margarine, etc.); Chops (eg, meat chops, peanut butter, etc.); Preserves (eg jams, Pie stuff, marmalade, etc.); jelly; Dough; Minced meat (eg sausage meat); Powder (eg, gelatin powder, detergents, etc.); Granular solids (eg nuts, candy, grains, etc.); And similar materials. The pouches of the present invention are particularly useful for packaging liquids (for example milk). This flowable material may also include an oily liquid (eg cooking oil or motor oil, etc.).
    At the time of manufacturing the film structure for pouches of the present invention, the film structure is cut to a width usable with a conventional pouch maker. Pouches of the present invention are made using so-called molded filling sealers, which are well known in the art. A pouch aspect of the present invention is a pouch, which is a tubular member having a longitudinal wrap seal and a transverse seal so that a "spaced" pouch is produced when the pouch is filled with a flowable material.
    The pouch aspect of the present invention has a pin seal around the three sides of the tubular member, that is, has a top seal and a side seal in the transverse direction, and the transverse direction is substantially as viewed from the cross section by filling the pouch with the flowable material. There is a pouch which is a tubular member having a lower portion sealed to the bottom portion of the tubular member substantially concave or "ball-shaped" so that a semicircular or "bow-shaped" lower portion occurs. This pouch is a so-called "Enviro-Pak" pouch known in the art.
    Pouches made according to the invention are preferably pouches made from so-called vertical molded filling seal (VFFS) groups which are well known in the art. Examples of commercially available VFFS groups include VFFS groups made by Hayssen or Prepac. VFFS is described in the following literature: F.C. Lewis "Form-Fill-Seal", Packaging Encyclopedia, p. 180, 1980.
    In the VFFS packaging method, the sheet of the plastic film structure described herein is fed to the VFFS machine, and in the tube forming section thereof, the sheet is formed into a continuous tube. Specifically, by sealing the longitudinal edges of the film, i.e. folding the plastic film and then sealing the film with an inner / outer seal, or by sealing the plastic film with an inner / outer seal and fin sealing, It produces the tubular member. The sealing bar is then used to seal the tube transversely to the position of one end that becomes the bottom of the "pouch", and then the material that fills the "pouch", for example milk, is put. The top end of the pouch is then sealed using a sealing bar and burned or cut through the plastic film to separate the resulting finished pouch from the tube. Methods of making pouches using this VFFS machine are generally described in US Pat. Nos. 4,503,102 and 4,521,437.
    The capacity of the pouches of the invention can be varied. Generally 5 ml-10L of fluid materials, Preferably 10 ml-8L, More preferably, 1L-1L can be put into this pouch.
    When the ethylene-based copolymer composition (A), (A '), (A ") or (A"') sealing layer is used as a two- or three-layer coextrusion film product, the pouch can be used at a higher speed by using the VFFS group. It is possible to produce a film structure, and a film structure with less leakage portion of the pouch thus produced is obtained.
    It is also possible to print on the pouch of the present invention using techniques known in the art, for example, corona treatment may be performed before printing.
    When the pouch of the present invention is subjected to a 5-foot (5.2 m) drop test (test defined herein), excellent performance results are shown. The percent breakage exhibited by this pouch in this 5-foot (1.52 m) drop test is preferably 40% or less, more preferably 20% or less, particularly preferably 10% or less.
    The use of the pouches in packaging for consumer liquids, such as milk, has the advantage over the previously used containers: glass bottles, paper cartons and jugs made of high density polyethylene. Previously used containers consume large amounts of natural resources for their manufacture, require significant space for landfilling, require large storage space, and require a lot of energy for temperature control of the product. (The heat transfer characteristic of the container is the cause).
    When the pouches of the present invention are made into thin films and used in liquid packaging, numerous advantages are obtained over containers that have been used in the past. This pouch has the following requirements: (l) low consumption of natural resources, (2) small space required for reclamation, (3) reusable, (4) easy to process, and (5) Small, (6) low energy used for storage (thermal properties of the package), (7) safe incineration, and (8) reusable (e.g. empty pouches for other uses) For example, frozen bags, sandwich bags, and general purpose storage bags).
    Batch included package:
    Batch inclusion packages are batch inclusion packages prepared from the above ethylenic copolymer composition (A), (A '), (A ") or (A"') or a composition comprising any one of these. . This package is made from a film, and powder, pellets, and a flowable material are put into the package to protect the material. The entire package (film and contents) can be added to the mixture during the manufacture of either product. For example, the package and contents can be placed simultaneously in an extruder or mixer.
    The above ethylenic copolymer composition (A), (A '), (A ") or (A"') used as the film of this batch containing package is preferably used as only one polymer component. However, by blending and / or multilayer extrusion and / or multilayer lamination of other polymers together with the ethylene copolymer composition (A), (A '), (A ") or (A"'), the processability of this film, You may give film hardness, film barrier properties, film strength, film melting properties or other desired film properties. Batch containing films made using suitable blends of the ethylene-based copolymer compositions (A), (A '), (A ") or (A"') with other polymer components also maintain improved performance. Useful polymer blend components include, for example, ethylene / vinyl acetate copolymer (EVA), ethylene / vinyl alcohol copolymer (EV0H), polybutylene (PB), linear high density polyethylene with a density of 0.94 l to 0.965 g / cm 3. (HDPE) and linear low density polyethylene (LLDPE) produced by a conventional Ziegler catalyst having a density of 0.87 to 0.94 g / cm 3, and the like. In said ethylene-based copolymer composition (A), (A '), (A ") or (A"'), preferably this blend composition is at least about 50%, more preferably this blend composition is at least about 80 Constitute%. However, very preferably the inner layer consists essentially of at least one of said ethylenic copolymer compositions (A), (A '), (A ") or (A"').
    Moreover, other additives, for example, a plasticizer and an oxidation, are added to the ethylene copolymer composition (A), (A '), (A ") or (A"') to such an extent that it does not interfere with the function of this batch containing package. Inhibitors, phosphites, cling additives, heat stabilizers, light stabilizers (e.g. Cyasorb® UV531 benzophenone from Cyanamid and Tinubin® 622 hindered amine light stabilizer from Chiba Geigy Corp. Etc.), pigments (e.g. titanium dioxide, calcium carbonate, carbon black, etc.), processing aids (e.g. polyethylene glycol, fluoropolymers, fluoro elastomers, waxes, etc.), flame retardants (e.g. Albright and Amgard® CPCl02, a phosphorus based flame retardant manufactured by Wilson Americas, lubricants (e.g., waxes, stearates, mineral oils, etc.), slip agents (e.g., eramides, oleamides, etc.) ), Anti-blocking additives (e.g. talc, silicon dioxide, etc.) , Crosslinking agents (e.g., peroxides (e.g. Booster (trade name) manufactured by DuPont), etc.), anti-fogging agents (e.g., Atmer l00 sorbitan ester, etc. manufactured by ICI) , Impact modifiers (e.g. Paxon (R) Pax Plus, a rubber modified film resin manufactured by Allied Corp.), antistatic agents (e.g. Armostat, an ethoxylated tertiary amine manufactured by Akzo Chemical.Inc. 410) and a filler (for example, talc, calcium carbonate, clay, fumed silica, etc.) may be contained. This list of additives is merely exemplary and is not intended to be exhaustive or limiting.
    Films and film structures having the novel properties described herein can be prepared using conventional hot blown film or cast film manufacturing techniques. In cooperation with this conventional manufacturing technique, a biaxial orientation method, for example, a tenter framing or a double bubble method, may be used. Conventional hot blown film methods are described, for example, in The Encyclopedia of Chemical Technology, Kirk-0thmer, 3rd Edition, John Wiley & Sons, New York, 1981, Vol. 16, pp. 416-417 and 18, 191-192. It is described in the page. Biaxially oriented film production methods, such as the "double bubble" method described in US Pat. No. 3,456,044 (Pahlke), and US Pat. No. 4,865,920 (Golike et al.), US Pat. No. 4,352,849 (Mueller), US Pat. The method described in US Pat. No. 4,820,557 (Warren), US Pat. No. 4,927,708 (Herran et al.), US Pat. No. 4,963,419 (Lustig et al.) And US Pat. No. 4,952,451 (Mueller), and the like are also described herein. New films and film structures can be prepared. Moreover, this film and a film structure can also be manufactured as described in a tenter fleming technique, for example, the technique used for orientation of polypropylene.
    Although this film may be a single | mono layer or a multilayer film, in the said ethylene-based copolymer composition (A), (A '), (A ") or (A"') in at least 1 layer, preferably an inner layer of this film structure. Use at least l. This inner layer is a layer adjacent to the material to be included in the package. As described by WJSchrenk and CRFinch in Coextrusion For Barrier Packaging on June 15-17 (1981), 211-229, "Society of Plastics Engineers RETEC Proceedings", the inner layer was replaced with another layer ( The inner layer may be laminated on another layer (stream) by co-extrusion or secondary operation.
    As described by KR0sborn and WAJenkins in "Plastic Film, Technology and Packaging Applications" (Technomic Publishing Co.lnc. (1992)), a tubular film (ie, blown film technology) or flat die (ie, cast film) It is also possible to produce a monolayer film, and optionally, to the film, an additional post-extrusion process is produced by adhering it to another layer of packaging material or by extrusion lamination to produce a multilayer structure. You may carry out. Although the film may be two or more layers of coextruded (as described by 0sborn and Jenkins), depending on other physical requirements regarding the film for final packaging, the film may be further laminated with an additional layer of packaging material. Also in D. Dumbleton's "Laminations Vs. Coextrusion" (Converting Magazine (September 1992)), the contrast between coextrusion and lamination is considered. Moreover, it is also possible to perform another post-extrusion technique, for example, biaxial orientation processing, to a single | mono layer and a coextrusion process film.
    Extrusion coating is another alternative technique for making materials for multilayer packages. Like cast films, extrusion coating is a flat die technique. The film layer may be extruded onto a substrate in the form of a monolayer or coextruded material.
    In the case of polymeric blends and / or multilayer film structures, generally at least one layer of the entire multilayer film structure, with the ethylene-based copolymer composition (A), (A '), (A ") or (A"'), Preferably, the inner layer is constituted. Other layers of this multilayer structure include, but are not limited to, barrier layers and / or bonding layers and / or structural layers. Various materials can be used for this layer, and some of them can be used as two or more layers in the same film structure. Some of these materials are ethylene / vinyl alcohol (EVOH) copolymers, polyvinylidene chloride (PVDC), polyethylene terephthalate (PET), oriented polypropylene (OPP), high density polyethylene (HDPE), ethylene / vinyl acetate (EVA) Copolymers, ethylene / acrylic acid (EAA) copolymers, ethylene / methacrylic acid (EMAA) copolymers, LLDPE, HDPE, LDPE, nylon, adhesive graft polymers (e.g. polyethylene grafted with maleic anhydride) and paper Etc. are included. This multilayer film structure generally comprises two to seven layers.
    Single layer or multilayer film structures typically have a thickness of 0.2 mil (5 μm) to 15 mil (381 μm) (total thickness), preferably lmil (25.4 μm) to 5 mil (127 μm). For coextrusion (or multi-layer extrusion), an inner layer comprising a substantially linear ethylene / α-olefin polymer is typically 0.2 mil (5 μm) to 15 mil (381 μm), preferably lmil (25.4). Μm) to 5 mil (127 µm).
    Films and film structures made from the ethylene-based copolymer compositions (A), (A '), (A ") or (A"') are processed into bags, liners or packaging materials, depending on the end use requirements. For example, tub liners can be used to sequentially blend various materials. Specifically, the contents and liner are transferred from one tub to another to be blended with another ingredient, and the blend is sent to a powerful mixer as needed. As another example, the additive used for rubber manufacture may be packaged in the bag, and the whole bag containing the content is added to the process, without opening the bag during rubber manufacture. The use and manufacturing techniques of such batch containing bags are described in the industry, as described in US Pat. No. 4,394,473, US Pat. No. 5,120,787, US Pat. No. 4,248,348, European Patent Application Publication No. 0270902 and Canadian Patent No. 2,053,051. It is well known.
    When the ethylene copolymer composition (A), (A '), (A ") or (A"') is used as a batch-containing bag and a film, a number of advantages are obtained. The ethylene copolymer composition (A), (A '), (A ") or (A"') exhibits excellent processability in the production of a blown film, and is lower than that of polyethylene produced by a conventional Ziegler catalyst. It has a melting point and a softening range. Moreover, since the said ethylene copolymer composition (A), (A '), (A ") or (A"') consists of carbon and a hydrogen atom, ethylene / acrylic acid or ethylene / methacrylic acid copolymers (European patent application) In contrast to using batch-containing films and bags made from as disclosed in Publication 0270902, or as described in ethylene / vinyl acetate copolymers (US Pat. Nos. 5,120,787 and 4,248,348). In comparison to films and bags made from), the ethylene-based copolymer compositions (A), (A '), (A ") or (A"') are compatible with a variety of elastomeric additives which are particularly useful in the rubber industry.
    The material (class) to be placed in the batch containing bag (or packaging material, coating material or liner) may be a material that exhibits free flow (ie the material flows easily under its own weight under gravity), or These may be materials which do not exhibit free flow (ie, these materials do not flow under their own weight under gravity). These materials are various but typically include materials that do not exhibit free flow, such as unvulcanized rubber, uncrosslinked elastomers, tars, and the like.
    Typical materials exhibiting free flow include clays, silicates, calcium carbonate, diethyldithiocarbamate cadmium disulfide, tetramethylthiuram, disulfide benzothiazole, substituted thioesters and amine antioxidants, aniline antiozone derivatives, diamines And / or UV pigments selected from thiourea curing agents selected from sulfur, sulfur giving compounds and peroxides, substituted benzotriazoles and substituted benzophenones, color pigments selected from iron oxides, titanium dioxide and organic dyes, Reinforcing pigments selected from carbon black, zinc oxide and hydrated silicon compounds, processing aids such as silicon dioxide, pumice, stearate and rubber processing oils, such as crosslinked elastomers, materials for unvulcanized rubber compounds, ground tires, herbicides, Antiseptic, mildew and chlorinated polyethylene (CPE); Free flowing materials effectively included in the package of the present invention include solids in addition to liquid.
    In the rubber industry, a small amount of rubber processing oil is typically used (for example 0.5 to 10% by weight) and mixed with at least one other rubber compound material. Not all of the materials that can be packaged using the novel package of the present invention are included in the above-listed materials, and are not limited thereto.
    The package of the present invention relates to a material for compounding in a bag or packaging, and also to a mixture of them and additives such as rubber processing oil and the like. In the case of unvulcanized rubber, a film is generally attached around the rubber, and in particular in the case of packaging, the rubber is tightly wrapped with a film and then the film is heat-sealed and attached under normal tension to complete the package. Although it is preferable to heat-seal this film in shaping | molding of this package, it is not necessarily required.
    The product made from this batch containing package will vary depending on the type of material contained within this package. Some examples include asphalt, animal feed and wires. For example, in the packaging of crushed tires in asphalt production, the packaging of titanium dioxide in animal feed production and the CPE packaging in wire coating production, the specific materials described above are placed in the batch containing package of the present invention. Other products include various rubbers (for example, by packing rubber or an additive for rubber in the batch-containing film described herein). It is also possible to produce energy by packaging waste materials (eg heavy tar effluent or waste plastic) and placing the entire package in an incinerator. In addition, by packaging and reusing waste plastic and other materials, other effective products such as garbage bags or park benches may be formed.
    Bag-in-box interior container:
    The interior container for a bag in box is formed from the film which consists of said ethylene-type copolymer composition (A), (A '), (A ") or (A"').
    Although the thickness of the film which forms the interior container for a bag in box changes with specific content or a manufacturing method, it is 30-1000 micrometers normally, Preferably it is 50-700 micrometers.
    The wall of the inner container for the bag in box according to the present invention,
    (i) the blocking force is less than l.0 g / cm,
    (ii) the number of pinholes in the area of 20.5 cm x 28.0 cm after the number of repeated twists of 2000 was achieved with a Gerbo flex tester;
    (iii) It is preferable that the film | membrane number of times of bending resistance measured based on JLS P-8115 consisted of 90,000 times or more. Moreover, the film whose neck-in at the time of shaping | molding is 20 cm or less on one side is preferable.
    The inner container for a bag in box may be formed from the single layer film which consists of said ethylene-type copolymer composition (A), (A '), (A ") or (A"'), and said composition (A), (A A so-called multilayer film in which a film made of ')', (A ") or (A" ') and a film made of another resin (nylon, ethylene vinyl alcohol copolymer, polyvinyl alcohol (EVOH), adhesive resin, etc.) are laminated. It may be formed.
    The inner box for the van box is, for example, almost entirely cuboidal in shape, and has a lid attached to its surface end, and when the cube is cut at an angle, a thick heat-sealing portion exists at a position corresponding to the periphery. In addition, the inner container for the bag-in box is formed to be able to be folded and inserted so that one container half body overlaps with the other container half body.
    The inner container for the bag-in box is filled with liquid, etc., and is stored and transported in a rigid outer container such as, for example, a short borus. The empty container is a container half of one container and the other half of a container. It is stored or transported in a shape that is folded so as to be overlapped with each other.
    In this way, when the bag-in box inner container is folded or inflated to form a cube or filled with the contents solution, various kinds of force are applied to the corner portion of the bag-in box inner container. As a result of excessively severe stress, pinholes are easily generated. Therefore, this interior container requires high pinhole resistance, flex resistance, blocking resistance, and the like. In addition, the interior container for a bag-in box according to the present invention satisfies the required physical properties.
    The inner container for a bag in box can be manufactured by the following method, for example.
    (i) Extrusion of molten resin into two sheets by a T-die arranged in parallel in the longitudinal direction, followed by vacuum molding using a metal mold having a shape capable of joining the peripheral portions of the surfaces facing the containers. Way.
    (ii) A method of extruding a molten resin from a circular die into a cylindrical shape (parison extrusion) and blow molding using a mold as described above.
    (iii) a method of stacking two or more resin films and heat-sealing four sides to form a bag (in this case, the film is composed of the composition (A), (A '), (A ") or (A"')). A single layer film may be used, and the film of the composition (A), (A '), (A ") or (A"') and other resins (nylon, ethylene vinyl alcohol copolymer resin (EVOH), polyvinyl alcohol, The so-called multilayer film which laminated | stacked the film of adhesive resin etc.) may be sufficient.
    Such a bag-in box is widely used as a container for accommodating various liquids such as alcoholic beverages, vinegar, photographic developer, bleach, and fungicide because of its excellent thermal stability, blocking resistance, pinhole resistance and flex resistance, and economical efficiency.
    Medical Containers:
    The medical container is a bag made of a multilayer film, a bag made of a single layer film, or a bottle made of a single layer, and the like, and at least one layer of the multilayer film, a single layer film, a single layer bottle is the ethylene copolymer composition (A), (A '), ( A ") or (A" ').
    The medical container can be produced by a water-cooled or air-cooled inflation method, a T-die method, a dry lamination method, an extrusion lamination method, a blow molding method or the like. As the molding method of the medical bag, the inflation method and the co-extrusion T-die method are preferable from the viewpoint of hygiene and economy, and the blow molding method is preferable as the molding of the medical bottle.
    The thickness of the medical container is usually in the range of 0.05 to 1,000 mm, preferably 0.1 to 0.7 mm, more preferably 0.15 to 0.3 mm. If the thickness of the container is 0.05 mm or more, the impact resistance is also good, and does not become a problem in practical use.
    Such medical containers do not lose transparency even when sterilized, and are excellent in heat resistance, and do not cause wrinkles or deformation.
    Heat resistant container:
    The heat-resistant container is a bag made of a multilayer film, a bag made of a single layer film, a multilayer bottle, a single layer bottle, and the like. At least one layer of the multilayer film, at least one layer of the multilayer bottle, and the single layer bottle are the ethylene copolymer composition (A ), (A '), (A ") or (A"').
    There is no restriction | limiting in particular about layers other than composition (A), (A '), (A ") or (A"') when a heat resistant container is a multilayer, Polypropylene, nylon, polyester, polyvinyl alcohol, etc. This may be used. The heat resistant container can be produced by a water-cooled or air-cooled inflation method, a T-die method, a dry lamination method, an extrusion lamination method, a blow molding method or the like.
    In the case where the heat-resistant container is bag-shaped, the inflation method and the co-extrusion T-die method are preferable in terms of hygiene and economy, and when the heat-resistant container is a bottle shape, the blow molding method is preferable.
    The thickness of the heat resistant container is in the range of 0.05 to 1.0 mm, preferably 0.1 to 0.7 mm, more preferably 0.15 to 0.3 mm. If the thickness of the container is 0.05 mm or more, the impact resistance is also good and does not become a problem in practical use.
    The heat resistant container of this invention is 30% or less of haze (ASTM D-1003-61) after heat sterilization process, Preferably it is 20 to 0%.
    Moreover, the heat distortion start temperature of a heat resistant container is 115 degreeC or more, and the thickness of a retorto food container is 0.05-1.00 mm normally.
    In addition, heat distortion start temperature is measured as follows. That is, a sample of a bag or a bottle made of a molded film is subjected to hot water sterilization at a sterilization temperature x 30 minutes in a RK-4016 small heat-resistant high-pressure steam sterilizer manufactured by Alps, and visually observes the sample taken out of the sterilizer to evaluate the change. Starting with a sterilization temperature of 110 ° C., the sterilization temperature is raised by 1 ° C. after every 1 sterilization is completed. When this deformation | transformation is confirmed for the first time to the sample taken out from the sterilizer by repeating this operation, the sterilization temperature is made into a strain start temperature.
    Such a heat resistant container, for example, a retort food container, is excellent in heat resistance and impact resistance without losing transparency even when sterilized.
    Elastic fiber:
    Elastic fibers are fibers that exhibit a recovery rate of at least 50% at 100% strain and become an ethylene-based copolymer composition (A), (A '), (A ") or (A"').
    Fibers are typically classified according to their diameter. Monofilament fibers are generally defined as having individual fiber diameters of at least about l5 denia per l filament, usually at least about 30 denia. Fine denier fibers are generally applied to fibers having a diameter of less than about 15 denier per l filament. Microdenia fibers are generally defined as fibers less than 100 μm in diameter. Fibers can also be classified by methods of making them, for example monofilaments, continuous wound fine filaments, staple or short cut fibers, spun bonds and melt blown fibers And the like can be classified.
    The melt index of the ethylene-based copolymer composition (A), (A '), (A ") or (A"') used in the manufacture of the elastic fibers used herein is monofilament (generally 15 denier / filament or more). Fibres), typically 0.01 g / 10 min to 1000 g / 10 min, preferably 0.lg / l0 to 5 g / l 0 min, and sodenia's fibers (diameter generally equal to or equal to 15 denia / filament or Or less), preferably 5 g / l 0 to 250 g / 10 min.
    The ethylene-based copolymer compositions (A), (A '), (A ") or (A"') used in the preparation of this elastic fiber do not interfere with the improved fiber and fabric properties found by the applicants, Additives such as antioxidants, phosphites, cling additives, anti blocking additives, pigments and the like may also be contained.
    Various homofil fibers can be produced using this ethylene copolymer composition (A), (A '), (A ") or (A"'). Homophile fibers are fibers that have a single region (domain) and do not have other polymer regions (such as those of bicomponent fibers). Such homofill fibers include staple fibers, spunbond fibers or meltblown fibers (eg, US Pat. No. 4,340,563 (Appel et al.), US Pat. No. 4,663,220 (Wisneski et al.), US Pat. No. 4,668,566 (Braun) or USA). And systems such as those disclosed in US Pat. No. 4,413, ll0 (Kavesh et al.). Staple fibers can be melt spun (ie they can be directly extruded to the final fiber diameter without additional drawing), or they can be melt spun to form fibers with large diameters and then heated using conventional fiber stretching techniques. Stretching or cooling stretching can be carried out to a desired diameter. The novel elastic staple fibers disclosed herein can also be used as bonding fibers, in particular where the novel elastic fibers have a lower melting point than the matrix fibers surrounding them. A typical use of bonding fibers is to blend the bonding fibers together with other matrix fibers and then heat the entire structure to join the matrix fibers that the bonding fibers melt and surround. Typical matrix fibers that benefit from using this novel elastic fibers include, but are not limited to, poly (ethylene terephthalate) fibers, cotton fibers, nylon fibers, polypropylene fibers, non-uniformly branched polyethylene fibers, and linear polyethylene. Homopolymer fibers and the like. The diameter of this matrix fiber can be varied depending on the end use application.
    Surprisingly, the recovery rate exhibited by the molten spun fiber made from this ethylenic copolymer composition (A), (A '), (A ") or (A"') is two or three times the diameter of the melt spun fiber. It is almost equal to the recovery rate of the fiber which melt-spun the fiber as much as possible and then cold-stretches the fiber to the same diameter as that of the fiber. Since elasticity here does not lose the effect of orientation by heat treatment, a product having the ability to maintain its elastic performance even after thermal exposure can be obtained.
    In the case of the novel elastic fibers disclosed herein, the ethylene copolymer composition (A), (A '), (A ") or (A"', while surprisingly small in influence on the elasticity of this fiber. You can change the melt index of) widely. As a result, the strength and shrinkage force of the fiber and the fabric can be changed independently from its elasticity, thereby increasing the flexibility regarding the design of the fabric and the final product. For example, by changing the melt index of the polymer rather than the diameter of the fiber, it is possible to change the shrinking force of the fiber (a lower melt index results in a higher shrinkage) and thus the elastic / strength performance required for the fabric. It is possible to better optimize the feel (ie the feel) of the fabric while having it.
    Moreover, a bicomponent fiber can also be manufactured using this ethylene copolymer composition (A), (A '), (A ") or (A"'). At least one part of the said bicomponent fiber is made into this ethylene-type copolymer composition (A), (A '), (A ") or (A"'). For example, in the case of a shell / core bicomponent fiber (i.e., a fiber concentrically surrounding the core), this ethylene copolymer composition (A), (A '), (A ") or (A "') may be present in either the shell or the core. In addition, other ethylenic copolymer compositions (A), (A '), (A ") or (A"') can also be used independently as a shell and a core in the same fiber, and in this case, both components are elastic It is preferable to make the melting point of the shell component lower than that of the core component. Other kinds of bicomponent fibers are likewise within the scope of the present invention, including side-by-side fibers (for example, fibers having separate polymer regions), wherein the ethylene copolymer composition And (A), (A '), (A ") or (A"') constitute at least a portion of the fiber surface).
    The shape of this fiber is not limited. For example, typical fibers have a circular cross-sectional shape, but may sometimes have other cross-sections, such as trilobal or flat (ie ribbon) shapes. The elastic fibers disclosed herein are not limited by the fiber shape.
    The diameter of the fibers can be measured and reported in various forms. Generally, the diameter of a fiber is measured in denias per fiber. Denia is a fabric term defined as the number of grams of fiber per 9000 meters of fiber length. Monofilaments are generally applied to extruded strands having at least 15 denias per filament, usually at least 30. The fibers of sodenia are generally applied to fibers having a denier of about 15 or less. Micro denier (also known as micro fiber) is generally applied to fibers having a diameter of about l00 μm or less. In the case of the novel elastic fibers disclosed in the present specification, the diameter can be varied widely with little effect on the elasticity of the fibers. However, the denier of the fiber can be adjusted to suit the function of the finished product, preferably 0.5-30 denier / filament for meltblown, 1-30 denier / filament for spunbond, and 1-2,000 denier for continuous wound filament It is filament.
    Fabrics made from the new fibers include both woven and nonwoven fabrics. Nonwoven fabrics, including spunlaced (or hydraulically entangled) fabrics, disclosed in US Pat. No. 3,485,706 (Evans) and US Pat. No. 4,939,016 (Radwanskid et al.) It is possible to manufacture by standing up a bond to heat, or by spunbonding the continuous fibers in one continuous operation, or by melt-blowning the fibers and bonding the resulting wave by calendar processing or heat. Such various nonwoven fabric manufacturing techniques are well known to those skilled in the art, and the disclosure of the present invention is not limited to any individual method. Other structures made from the fibers are also included within the scope of the present invention, including, for example, blends of these new fibers with other fibers (e.g., poly (ethylene terephthalate) (PET) or cotton, etc.) Included.
    As used in the claims of this specification, "is made essentially of" is an ethylene-based copolymer composition (A), (A '), (A ") or (A" used to make this fiber and fabric. ') Can contain additional materials that do not substantially affect the elasticity of this fiber or fabric. Such non-limiting additives include pigments, antioxidants, stabilizers, surfactants (e.g., disclosed in U.S. Pat. No. 4,486,552 (Niemann), U.S. Pat.No.4,578,414 (Sawyer et al.) Or U.S. Patent 4,835,194 (Bright et al.) Is included).
    Articles of manufacture that can be made using the novel elastic fibers and fabrics disclosed herein include composite fabric products (eg diapers, etc.) where it is desired to have a portion that exhibits elasticity. For example, a portion showing elasticity is desired, such as a waist band portion of the diaper which prevents sagging down of the diaper and a leg band portion which prevents leakage (US Patent No. 4,381,781 to Sciaraffa). )). This resilient portion often helps to better shape shape and / or shape fixation systems to desirably combine comfort and reliability. The novel elastic fibers and fabrics disclosed herein can be used to produce a structure that combines elasticity and breathability.
    The novel elastic fibers and fabrics disclosed herein can also be used in the various structures described in US Pat. No. 2,957,512 (Wade). For example, layer 50 of the structure described in US Pat. No. 2,957,512 (i.e., a component that exhibits elasticity) (especially flattened, wrinkled, creped, etc., a material that does not exhibit elasticity, etc.) To create a structure that exhibits elasticity). By melt bonding or by using an adhesive, the new elastic fibers and / or fabrics can be attached to fibers, fabrics or other structures that do not exhibit elasticity. Using this new elastic fiber and / or fabric and a non-elastic component, crimping the non-elastic component prior to attachment (described in US Pat. No. 2,957,512) and exhibiting its elasticity prior to attachment By pre-stretching or attaching the component or by heat shrinking the component exhibiting its elasticity, it is possible to produce a pleated or shearing attached elastic structure therefrom.
    The novel elastic fibers described herein may be spunlaced (or hydraulically entangled) to produce novel structures. For example, the elastic sheet 12 disclosed in US Pat. No. 4,801,482 (Goggans) can be produced using the novel elastic fibers / fabrics described herein.
    The continuous filaments exhibiting the elasticity described herein can also be used for knitting applications in which high resilience is desired.
    In addition, the toughness and shrinkage of the novel elastic fibers and fabrics disclosed herein are adjustable, and from this advantage, if necessary, the shrinkage force in the same garment as described, for example, in US Pat. No. 5,196,000 (Clear et al.) The design can be flexible.
    U.S. Patent No. 5,037,416 (Allen et al.) Describes the advantages of a shape-fit top sheet using a ribbon that exhibits elasticity (see member 19 of U.S. Patent No. 5,037,416). Can also be used in the form of a fabric in which the member 19 of U. S. Patent 5,037, 416 functions or the desired elasticity is obtained.
    Even in a composite in which linear polyethylene or copolymer polyethylene having a very high molecular weight is used, a benefit is obtained by using the novel elastic fibers disclosed herein. For example, this novel elastic fiber has a low melting point (the melting point of this polymer and the polymer density are in a linear relationship in nature) and as a result, very high, as described in US Pat. No. 4,584,347 to Harpell et al. In the case of a blend of polyethylene fibers having a molecular weight (e.g., Spectra® fiber manufactured by Allied Chemlical) with this novel elastic fiber, this low melting point elastic fiber can be used without melting high molecular weight polyethylene fibers. Since it plays a role of bonding the molecular weight fibers, the high strength and integrity exhibited by the high molecular weight fibers are maintained.
    In US Pat. No. 4,981,747 (Morman), the elastic sheet 122 forming a composite elastic material comprising a reversibly necked material is to be replaced with the novel elastic fibers and / or fabrics disclosed herein. Can be.
    This novel elastic fiber may also be used as an elastic component of meltblown processing described in reference numeral 6 in the drawing of US Pat. No. 4,879,170 (Radwanski). This U.S. Patent No. 4,879,170 generally describes a co-molded material and a method of manufacturing that exhibit elasticity.
    The novel elastic fibers and fabrics disclosed herein may be used to make elastic panels, which are described, for example, in members 18, 20 and 14 of Van Gompel. ) And / or (26) and the like. The novel elastic fibers and fabrics described herein can also be used and used as elastic components of composite side panels (eg, layer 86 of US Pat. No. 4,940,464).
    Foam molded body:
    The foamed molded article can be molded into various shapes including a rod shape, a tube shape, a tape shape, a sheet shape, and the like, and is used as a buffer, a heat insulating material, a base of a foaming agent, and the like.
    The foamed molded product is mixed with the above-mentioned ethylenic copolymer composition (A), (A '), (A ") or (A"') and a blowing agent, heated or reduced pressure, and foamed by gasification of the blowing agent or decomposition gas, It produces by making a bubble in a resin molding.
    As a manufacturing method of a foamed molded object, the following manufacturing method is mentioned, for example.
    ① Extrusion foaming method
    When the said ethylene-based copolymer composition (A), (A '), (A ") or (A"') is put into the hopper of an extruder, and is extruded at the temperature near melting | fusing point of resin, from the indentation hole provided in the middle of an extruder. A method of continuously obtaining a foam by injecting a physical foaming agent and extruding it from an outlet of a desired shape.
    Examples of the physical blowing agent include volatile blowing agents such as freon, butane, pentane, hexane, and cyclohexane, and inorganic gas blowing agents such as nitrogen, air, water, and carbon dioxide. In addition, at the time of extrusion foaming, bubble core forming agents such as calcium carbonate, talc, clay, and magnesium oxide may be added.
    The blending ratio of the physical blowing agent is usually 5 to 60 parts by weight, preferably 10 to 50 parts by weight based on 100 parts by weight of the composition (A), (A '), (A ") or (A"'). .
    If the blending ratio of the physical foaming agent is too small, the foamability of the foam decreases, and if too large, the strength of the foam lowers.
    (2) Shorten the organic thermal decomposition type blowing agent such as the ethylene copolymer composition (A), (A '), (A ") or (A"'), azodicarbonamide, and other additives or thermoplastic resins as necessary Using a kneading apparatus such as a twin screw extruder, a half-barrier mixer, a kneader mixer, a roller, or the like, to melt-kneading at a temperature below the decomposition temperature of the thermally decomposable foaming agent to prepare a foamable resin composition in a sheet form, and then A method of obtaining a foam by heating a sheet above the decomposition temperature of the blowing agent to foam.
    The blending ratio of the organic pyrolytic blowing agent is usually 1 to 50 parts by weight, preferably 4 to 25 parts by weight based on 100 parts by weight of the composition (A), (A '), (A ") or (A"'). to be. If the blending ratio of the organic pyrolytic foaming agent is too small, the foamability of the foam decreases, and if too large, the strength of the foam decreases.
    ③ Foaming method in pressure vessel
    The ethylene copolymer composition (A), (A '), (A ") or (A"') is shape | molded in the shape of a sheet form, a block shape, etc. with a press machine or an extruder, and then the said molded object is A method of obtaining a foaming agent by putting in a pressure vessel, dissolving a physical type foaming agent sufficiently in resin, and then depressurizing it. In addition, the pressure vessel into which the molded product is introduced may be filled with a physical foam at normal temperature and then pressurized, taken out after decompression, and heated in an oil bath, an oven or the like to foam.
    Moreover, when the said ethylene copolymer composition (A), (A '), (A ") or (A"') is bridge | crosslinked previously, a crosslinked foam can also be obtained.
    In general, the crosslinking method includes a method of thermally decomposing and crosslinking a peroxide radical generator mixed in a resin, crosslinking by ionizing radiation, crosslinking by ionizing radiation in the presence of a polyfunctional monomer, and silane crosslinking. Can be.
    In order to obtain a crosslinked foam by such a method, a composition (A), (A '), (A ") or (A"'), an organic pyrolytic foaming agent, a polyfunctional monomer and another compounding agent as a crosslinking aid may be used. Melt kneading is carried out at a temperature below the decomposition temperature to form a sheet. After quantitatively irradiating the obtained expandable resin composition with ionizing radiation to crosslink the composition (A), (A '), (A ") or (A"'), the crosslinked sheet is heated to a temperature higher than the decomposition temperature of the blowing agent and foamed. . Examples of ionizing radiation include α-rays, β-rays, γ-rays, and electron beams. Moreover, peroxide bridge | crosslinking and silane bridge | crosslinking can be performed instead of irradiation bridge | crosslinking by ionizing radiation.
    In the present invention, weathering stabilizers, heat stabilizers, anti-slip agents, anti-blocking agents, and antifogging agents are provided in the composition (A), (A '), (A ") or (A"') in the range which does not impair the objective of this invention. You may mix | blend additives, such as a lubricant, a pigment, dye, a nucleating agent, a plasticizer, an antioxidant, a hydrochloric acid absorber, antioxidant, as needed. In addition, small amounts of other polymers can be blended without departing from the spirit of the present invention.
    Such foams are excellent in flexibility and toughness.
    Foam structure:
    The foam structure is composed of an ethylenic copolymer composition (A), (A '), (A ") or (A"').
    Blends of ethylene-based copolymer compositions (A), (A '), (A ") or (A"') and other suitable ethylene-based polymers or other natural or synthetic polymers can be used. Suitable other ethylene-based polymers include low density polyethylene (LDPE), medium density polyethylene (MDPE) and high density polyethylene (HDPE) (e.g., made using Ziegler catalysts described in US Pat. No. 4,076,698), ethylene / vinylacetate airborne Copolymers, copolymers of ethylene and ethylenically unsaturated carboxylic acids, homo- and copolymers of -Ethylenes, and the like. Other suitable polymers include polystyrene (including impact resistant polystyrene), styrenebutadiene block copolymers, polyisoprene, and other rubbers. Blends comprising a high melting point resin in a major proportion are preferred. Compositions (A), (A '), (A ") or (A"') or blends comprising them are called ethylene-based polymer materials.
    Regardless of the composition, the ethylene-based polymer material preferably contains at least 50% by weight, more preferably at least 70% by weight of ethylene monomer units. The ethylene polymer material may be completely or wholly of the ethylene monomer. Preferred blends are ethylene-based copolymer compositions (A), (A '), (A ") or (A"') and other conventional ethylene-based polymers, such as LDPE, HDPE, ethylene / acrylic acid copolymers (EAA). ) And LLDPE.
    Additives such as antioxidants (e.g., hindered phenols (Irganox® l010), phosphites (e.g. Irgafos® 168), pigments, etc.) to an extent that do not interfere with the improved properties found by the applicant It may be included in the system copolymer composition (A), (A '), (A ") or (A"').
    The method of manufacturing the foam structure and processing it is described in Handbook of Polymer Foams and Technology, Hanser Publishers, Munich, Viena, New York, Barcelona, CPPark's "Polyolefin Foam" Chapter 9, edited by D. Klempner and KCFrisch. (1991).
    This foam structure can be produced by a conventional extrusion foaming method. This structure can generally be prepared by heating an ethylene-based polymer material to form a plasticized or molten polymer material, adding a blowing agent therein to form a foamable gel, and extruding the gel through a die to form a foam product. have. Prior to mixing with the blowing agent, the polymeric material is heated to its glass transition temperature or above its melting point. The blowing agent may be added and mixed in the molten polymer material by all means of the prior art such as an extruder, a mixer, a blender. The blowing agent is mixed with the molten polymer material at a high pressure sufficient to inhibit substantial foaming of the molten polymer material and to disperse the blowing agent approximately homogeneously. If desired, the nucleating agent may be blended into the polymer melt or dry mixed with the polymer material prior to plasticization or melting. Effervescent gels are typically cooled at lower temperatures in order to optimize the properties of the foam structure. The gel is then extruded or transported through a die of the desired shape into a reduced pressure or lower pressure zone to form a foam structure. The zone of lower pressure is a pressure lower than the pressure maintained before the expandable gel is extruded through the die. The lower pressure may be above or below atmospheric pressure (vacuum), but preferred is the atmospheric pressure level.
    The structure may be processed into a strand state in which the structure is agglomerated by extrusion of an ethylene polymer material through a multi-orifice die. The orifices are arranged so that contact between adjacent streams of the molten extrudate occurs between foaming processes and the surfaces in contact with each other have sufficient adhesion to form an integral foam structure. The stream of molten extrudate from the die takes the form of strands or profiles, which preferably foam, agglomerate, and adhere to each other to form an integral structure. Preferably, the individual strands or profiles that have been agglomerated should be in an integral structure so that the strands are not separated by the stresses applied during foam manufacture, shaping and use. Methods and apparatus for producing foam structures in the form of aggregated strands are shown in US Pat. Nos. 3,573,152 and 4,824,720.
    This foam structure may also be formed by a cumulative extrusion method, as shown in US Pat. No. 4,323,528. In this method, a low density foam structure having a large side cross-sectional area is produced by the following method.
    l) under pressure to form a gel of ethylene-based polymeric material and blowing agent. The gel is formed at a temperature that has sufficient viscosity to keep the blowing agent during foaming. 2) Extrude the gel into a holding zone maintained at a temperature and pressure that does not foam the gel. The holding zone has an outlet die surrounding the orifice opening into the lower pressure zone, which foams the gel, and an openable gate closing the die orifice. 3) The gate is opened periodically. 4) A mechanical ram is applied at the same time by a ram that is movable to the gel, and the gel is passed through the die orifice from the holding zone and discharged into the zone of lower pressure. Emission is carried out at a rate greater than the rate at which substantial foaming occurs in the die orifice and at a rate lower than the rate at which substantial irregularities in the cross-sectional area or shape occur. 5) A foamed structure is produced by foaming the released gel without constraining in at least one direction to produce a foamed structure.
    This foam structure can be processed into uncrosslinked foam beads suitable for molding products. To prepare foam beads, the separated resin particles such as particulate resin pellets are suspended in a liquid medium in which the resin such as water is substantially insoluble; Impregnating the resin particles with a blowing agent by introducing the blowing agent at high temperature and high pressure in a liquid medium in an autoclave or other pressure vessel; Rapidly discharge into the atmosphere or reduced pressure zone to form foam beads. This method is fully described in US Pat. Nos. 4,379,859 and 4,464,484.
    As a derivative of the above method, the suspended pellet may be impregnated in the styrene monomer so as to form a graft copolymer with the ethylene polymer material before impregnation of the blowing agent. The polyethylene / polystyrene copolymer beads are cooled and discharged from the vessel without substantially foaming. Thereafter, the beads are foamed and molded according to a conventional foamed polystyrene bead molding method. Methods of making polyethylene / polystyrene copolymer beads are described in US Pat. No. 4,138,353.
    Foam beads may be molded by any means known in the art. For example, a product is produced by loading foam beads into a mold, and then heating the beads with, for example, steam to agglomerate and fuse the beads. If desired, the beads may be impregnated with air or other blowing agent at high temperature and high pressure before loading the beads into the mold. It can also be heated before loading the beads. Foam beads can be molded into blocks or shaped articles by appropriate molding methods known in the art (some methods are described in US Pat. Nos. 3,504.068 and 3,953,558). Excellent examples of such methods and molding methods are shown in the above publications p191, p-197-198 and p-227-229 to C.P. Park.
    Blowing agents useful in the production of this foam structure include inorganic blowing agents, organic blowing agents and degradable chemical blowing agents. Examples of suitable inorganic blowing agents include carbon dioxide, nitrogen, argon, water, air, nitrogen and helium. Organic blowing agents include aliphatic hydrocarbons having 1 to 6 carbon atoms, aliphatic alcohols having 1 to 3 carbon atoms and fully or partially halogenated aliphatic hydrocarbons having 1 to 4 carbon atoms. Examples of aliphatic hydrocarbons include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane and neopentane. Examples of aliphatic alcohols include methanol, ethanol, n-propanol and isopropanol. Examples of fully or partially halogenated aliphatic hydrocarbons include fluorocarbons, chlorocarbons and chlorofluorocarbons. Examples of fluorocarbons are methyl fluoride, perfluoromethane, ethyl fluoride, 1,1-difluoroethane (HFC-152a), l, l, l-trifluoroethane (HFC-143a), l , l, l, 2-tetrafluoroethane, 2,2-difluoropropane, l, 1,1-trifluoropropane, perfluoropropane, dichloropropane, difluoropropane, perfluorobutane and Perfluoro cyclobutane is mentioned. Examples of partially halogenated chlorocarbons and chlorofluorocarbons used in the present invention include methyl chloride, methylene chloride, ethyl chloride, l, l, l-trichloroethane, 1,1-dichloro-l-fluoroethane ( HCFC-141b), l-chloro-1,1-difluoroethane (HCFC-142b), l, 1-dichloro-2,2,2-trifluoroethane (HCFC-123) and l-chloro-1 And 2,2,2-tetrafluoroethane (HCFC-124). Examples of fully halogenated chlorofluorocarbons are trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane (CFC-ll3), 1,1, l -Trifluoroethane, pendafluoroethane, dichlorotetrafluoroethane (CFC-114), chloroheptafluoropropane and dichlorohexafluoropropane. Examples of chemical blowing agents include azodicarbonamide, azodiisobutyronitrile, benzene sulfone hydrazide, 4,4-oxybenzenesulfonyl semicarbazide, p-toluenesulfonyl semicarbazide, barium azodicarboxylate, N, N'- dimethyl- dinitrosoterephthalamide and trihydrazinotriazine are mentioned. Preferred blowing agents are isobutane, HFC-152a and mixtures thereof.
    The amount of blowing agent in the polymer molten material to prepare the foam forming gel is 0.2-5.0 g mol / kg polymer, preferably 0.5-3.0 g mol / kg polymer, most preferably l-0.50 g Moles / kg polymer.
    Various additives, such as stability control agents, nucleating agents, inorganic fillers, pigments, antioxidants, acid scavengers, ultraviolet absorbers, flame retardants, processing aids and extrusion aids, may be incorporated into the foam structure.
    A stability control agent may be added to this foam structure in order to improve dimensional stability. Preferred stability control agents include amides and esters of C l0 ~ C 24 fatty acid. Such stability control agents are shown in US Pat. Nos. 3,644,230 and 4,214,054. Most preferred stability control agents include stearyl stearamide, glycerol monostearate, glycerol monobehenate and sorbitol monostearate. Typically, such stability control agents are used in the range of about 0.1 to about 10 parts per 100 parts of polymer.
    This foam structure exhibits excellent dimensional stability. Preferred foams recover at least 80% of the initial volume. This initial volume is measured 30 seconds after foam foaming. The volume is measured by an appropriate method such as water volume replacement.
    In addition, a nucleating agent may be added to control the bubble size of the foam. Preferred nucleating agents include inorganic materials such as calcium carbonate, talc, clay, titanium dioxide, silica, barium sulfate, diatomaceous earth, a mixture of citric acid and sodium bicarbonate and the like. The amount of nucleating agent used may range from about 0.01 to about 5 parts by weight per 100 parts by weight of the polymer resin.
    This foam structure is substantially uncrosslinked or uncrosslinked. The alkenyl aromatic polymer material contained in this foam structure is substantially not crosslinked. The foam structure comprises up to 5% gel as measured by Method A of ASTM D-2765-84. Some crosslinking that occurs naturally without the use of crosslinkers or radiation is acceptable.
    This foam structure has a density of less than 250 kg / cm 3, more preferably less than l00 kg / cm 3 and most preferably less than 10-70 kg / cm 3. The foam has an average bubble size of 0.05 to 5.0 mm, more preferably 0.2 to 2.0 mm and most preferably 0.3 to 1.9 mm as measured by ASTM D3576.
    The foam structure may take on all kinds of physical shapes known in the art such as extruded sheets, rods, thick plates and profiles. The foam structure may be formed by molding the expandable beads into any one or the other of the above shapes.
    This foam structure may be an independent bubble or a continuous bubble. Preferably this foam contains at least 80% of free bubbles as measured by ASTM D2856-A.
    Such stronger and more resilient foam structures are very useful for sports and leisure applications, and cushion packaging applications.
    Foam structure:
    The foamed structure is composed of an ethylenic copolymer composition (A), (A '), (A ") or (A"'), and is strong, elastic and low density.
    In addition, the structures of the present invention are more thermally stable than EVA foam structures and do not produce unpleasant odors during foam expansion, manufacture and use. Soft strong crosslinked foam structures are useful in sporting goods, medical devices and cushioning goods. When forming the foamed structure, it is also possible to use blends of the above ethylene-based copolymer compositions (A), (A '), (A ") or (A"') with other suitable ethylene-based polymers or other natural or synthetic polymers. . Examples of suitable ethylene-based polymers include low density polyethylene (LDPE) (eg high pressure, free radical polymerization technology), medium density polyethylene (MDPE) and high density polyethylene (HDPE) (eg described in US Pat. No. 4,076,698). Homopolymers and copolymers such as those produced using Ziegler catalysts), ethylene / ester copolymers, ethylene / vinylacetate copolymers, copolymers of ethylene and ethylenically unsaturated carboxylic acids, and α-ethylenic materials. Other suitable polymers include polystyrene (including high impact polystyrene), styrene / butadiene block copolymers, polyisoprene and other rubbers. Blends containing high melting point resins in major proportions are preferred. Regardless of the composition, the ethylenic polymer material preferably comprises at least 50% by weight, more preferably at least 70% by weight of ethylenic monomer units. The ethylenic polymer material may be entirely composed of ethylenic monomer units. Preferred blends are the ethylene-based copolymer compositions (A), (A '), (A ") or (A"') and other conventional ethylene-based polymers, such as LDPE, HDPE, ethylene / acrylic acid copolymers (EAA). ) And LLDPE.
    The foam structure of the present invention may take any physical shape known in the art, for example in the form of a sheet, flank or burn stock. Other useful foams are articles produced by expansion and / or fusion of expandable or expandable particles, formable expandable particles, or these beads.
    The production of foam structures and methods for processing them are presented in the D.Klempner and KCFrisch edited by CPPark, Chapter 9, Handbook of Polymer Foams and technology, Munich, Vienna, New York, Barcelona Publishers (1991). have.
    The foam structure of the present invention blends and heats the ethylene copolymer composition (A), (A '), (A ") or (A"') and a degradable chemical blowing agent to form a foamable plasticized or molten polymer material. The foamable molten polymer material containing the crosslinking agent is extruded from the die, and the polymer material is heated to release the foaming agent to form a foam structure. Polymeric materials and chemical blowing agents can be mixed and melt blended by means known in the art, such as extruders, mixers or blenders. The chemical blowing agent is preferably dry blended with the polymer material before the polymer material is heated and melted, but may be added when the polymer material is in the molten phase. Crosslinking can be brought about by the addition of a crosslinking agent or by radiation. The temperature rise for causing crosslinking and for expanding or foaming can be simultaneously or sequentially. When using a crosslinking agent, it is mix | blended with a polymeric material similarly to a chemical blowing agent. In addition, when a crosslinking agent is used, the expandable polymer molten material is preferably heated or exposed to a temperature of less than 150 ° C to prevent degradation of the crosslinking agent or blowing agent, thereby preventing premature crosslinking. When using radiation crosslinking, the foamable polymeric material is preferably heated or exposed to a temperature below 160 ° C. to prevent degradation of the blowing agent. The foamable molten polymer material is extruded through a die of the desired shape to form a foam structure. This expandable structure is then expanded by crosslinking at high temperatures such as an oven (typically 150 ° C. to 250 ° C.). When using spin crosslinking, the foam structure is irradiated to crosslink the polymer, which is then expanded to the above elevated temperatures. The structure of the present invention may advantageously be formed into a sheet or a sheet according to the above method using either a crosslinking agent or spinning.
    The foam structure of this invention can be made into a continuous thin plate structure by the extrusion method using the die of the long land described in GB2,145,961A. In this method, a polymer, a degradable blowing agent and a crosslinking agent are mixed in an extruder, the mixture is heated to crosslink the polymer, and the blowing agent is foamed in a die of long land; Pass through the die to form a foam structure. Contact of the foam structure with the die is lubricated with a suitable lubricant.
    The foamed structure of the present invention may also be made of crosslinked foamed beads suitable for forming articles. In order to make foamed beads, separate resin particles such as granular resin pellets are suspended in a substantially insoluble liquid such as water; Impregnating the crosslinker and blowing agent at elevated pressure and temperature in an autoclave or other pressure vessel; Emissions into atmospheric or reduced pressure zones produce foam beads. The polymer beads are impregnated with a blowing agent, cooled, released from the vessel, and then expanded by heating or steam. In the induction of the above method, the styrene monomer can be impregnated with the crosslinking agent in the suspension pellet to form a graft copolymer comprising an ethylenic polymer material. The blowing agent may be impregnated with the resin pellet in the suspended state or the non-aqueous solution state. The expandable beads are then expanded by steam heating and molded according to conventional methods to form expandable polystyrene foam beads.
    The foam beads can be molded by means known in the art. For example, foamed beads are filled into a mold, the mold is compressed to compress the beads, and the beads are then heated, for example by steam, to fuse the beads to make an article. The beads may be preheated with air or other blowing agent, if desired, prior to filling the mold. The method and molding method are described in the above publications pp227-233; US Pat. No. 3,886, l00; US Pat. No. 3,959,189; US Pat. No. 4,168,353 and US Pat. No. 4,429,059. Foam beads may also be prepared by preparing a mixture of polymer, crosslinking agent and degradable blowing agent in a suitable mixing apparatus or extruder, molding the mixture into pellets, and then heating the pellets to crosslink and expand.
    There is a separate method of making crosslinked foam beads suitable for molding an article. The ethylene polymer material is melted and mixed with the physical blowing agent in a conventional foam extrusion apparatus to create a substantially continuous foam strand. The foamed strand is granulated or pelletized to form foamed beads. This foam beads are then crosslinked by spinning. The crosslinked foam beads are then fusion molded, and various articles are made as described above for the other foaming method. Further details on this method are found in US Pat. Nos. 3,616,365 and C.P.Park, above publications pp224-228.
    The foamed structure of the present invention can be produced in a burn stoke form by two different methods. One method uses a crosslinking agent and the other uses spinning.
    The foamed structure of the present invention mixes the ethylene copolymer composition (A), (A '), (A ") or (A"') with a crosslinking agent and a chemical foaming agent to make a slab, and the slab of the mixture in the mold It can be heated to crosslink the polymer material with a crosslinking agent, decompose the blowing agent, and expand the slab by releasing the pressure in the mold to form a burned stoke. If desired, burn stokes produced at pressure release can be reheated to further expand.
    The crosslinked polymer sheet can be produced by irradiating the polymer sheet with a high energy beam or by heating the polymer sheet containing the chemical crosslinking agent. The crosslinked polymer sheet is cut into the desired shape and then impregnated with high pressure nitrogen at a temperature above the softening point of the polymer, after which the pressure is released to nucleate and slightly expand the bubbles in the sheet. The sheet is reheated to low pressure above the softening point, and then the pressure is released to expand the foam.
    Blowing agents useful in the preparation of the foam structures of the present invention include degradable chemical blowing agents. These chemical blowing agents decompose at high temperatures to produce gases or vapors to inflate the polymer into foaming forms. This chemical blowing agent preferably takes the form of a solid so that it can be easily dry blended with the polymeric material. Examples of this chemical blowing agent include azodicarbonamide, azodiisobutyronitrile, benzenesulfohydrazide, 4,4-oxy benzenesulfonyl semicarbazide, p-toluenesulfonyl semicarbazide, barium azodicarboxylate , N, N'-dimethyl-N, N-dinitrosoterephthalamide, N, N'-dinitrosopentamethylenetetramine, 4,4-oxy bis (benzenesulfonylhydrazide) and trihydrazinonote Riamine is mentioned, Azodicarbonamide is preferable. Further information on chemical blowing agents can be found in the above publications pp205-208 by CPPark, and in the "Polyolefin Foam" Handbook of Polymer Foams and Technology by FAShutob, pp. 382-402, D. Klempner and KCFrisch, Hanser Publishers, Munich, Presented in Vienna, New York, Barcelona (1991).
    The chemical blowing agent blends with the polymeric material in an amount sufficient to release 0.2-5.0, preferably 0.5-3.0, most preferably 1.2-2.50 moles of gas or vapor per kg polymer.
    Useful crosslinkers for preparing the foam structures of the present invention are organic peroxides. Examples of useful organic peroxide crosslinkers include 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane; Dicumylperoxide, 2,5-dimethyl-2.5-di (t-butylperoxy) hexane; l-butylcumylperoxide, α, α'-di (butylperoxy) -diisopropylbenzene, di-t-butylperoxide and 2,5-dimethyl-2,5-di- (t-butylperoxy ) Hexane. Dicumyl peroxide is preferred. Further details on organic peroxide crosslinkers are presented in the above publication ppl98-204 to C. Park.
    Crosslinking by radiation can be performed by one of usual methods. Examples of types of useful radiation include electron beams or β-rays, γ-rays, X-rays, or Neutron rays. In the case of radiation crosslinking, it is believed that polymer groups are produced by radiation irradiation, and these groups are gathered together to crosslink. Further details regarding radiation crosslinking are presented in the above publication, ppl98-204, by C. Park.
    In some methods of making the foam structures of the present invention, physical blowing agents can be used. Examples of physical blowing agents include organic and inorganic blowing agents. Examples of suitable inorganic blowing agents include carbon dioxide, nitrogen, argon, water, air and helium. Examples of organic blowing agents include aliphatic hydrocarbons having 1 to 9 carbon atoms, aliphatic alcohols having 1 to 3 carbon atoms and fully and partially halogenated hydrocarbons having 1 to 4 carbon atoms. Examples of aliphatic hydrocarbons include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane and neopentane. Examples of aliphatic alcohols include methanol, ethanol, n-propanol and isopropanol. . Examples of fully and partially halogenated aliphatic hydrocarbons include fluorocarbons, chlorocarbons and chlorofluorocarbons. Examples of fluorocarbons are methyl fluoride, perfluoromethane, ethyl fluoride, 1,1-difluoroethane (HFC-152a), l, l, l-trifluoroethane (HFC-143a), l , l, 1,2-tetrafluoroethane (HFC-134a), pendafluoroethane, difluoromethane, perfluoroethane, 2,2-difluoropropane, l, l, l-trifluoro Propane, perfluoropropane, dichloropropane, difluoropropane, perfluorobutane and perfluorocyclobutane. Examples of partially halogenated chlorocarbons and chlorofluorocarbons used in the present invention include methyl chloride, methylene chloride, ethyl chloride, l, l, 1-trichloroethane, l, l-dichloro-1-fluoroethane (HCFC- 141b), 1-chloro-l, 1-difluoroethane (HCFC-142b). Chlorodifluoromethane (HCFC-22), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123) and l-chloro-1,2,2,2-tetrafluoroethane ( HCFC-124). Examples of fully halogenated chlorofluorocarbons are trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane (CFC-13), l, l, l-tree Fluoroethane, pentafluoroethane, dichlorotetrafluoroethane (CFC-ll4), chloroheptafluoropropane and dichlorohexafluoropropane.
    The amount of blowing agent to be blended into the polymer melt to produce an expandable polymer gel is 0.2-5.0, preferably 0.5-3.0, most preferably 1.0-0.50 mol / kg polymer.
    The crosslink density of the foam structure of the present invention is 5 to 90%, more preferably 30 to 70%, as measured by ASTM D2765-84 Method A.
    The foam structure of the present invention has a density of less than 500 kg / m 3, more preferably less than 250 kg / m 3 and most preferably less than 150 kg / m 3. The average pore diameter of the foam structure is 0.05 to 5.0, more preferably 1.0 to 2.0, most preferably 0.2 to 1.0 mm, as measured by ASTM D3576.
    The foam structure of the present invention may be a closed bubble or an open bubble. When the closed bubble of the foam structure of the present invention is measured by ASTM D2856-A, 90% or more is preferable.
    Moreover, various additives can be mix | blended with the foam structure of this invention. Examples of such additives include inorganic fillers, stability control agents, nucleating agents, colorants, antioxidants, acid removers, ultraviolet absorbers, flame retardants, processing aids and extrusion aids.
    gasket:
    The gasket is an ethylene copolymer composition (A), (A '), (A ") or (A"'). This gasket has the ability to compressively seal various containers without contaminating the contents. The novel gasket materials disclosed herein are particularly useful for containers for liquids.
    Some types of gaskets need to withstand temperatures higher than room temperature (about 25 ° C.) for a short time, especially when this application is for hotfill applications. For example, for products that need to be sterilized, it is necessary to attach a gasket having a melting point of 100 ° C. or higher. Therefore, the polymer suitable for the said use can be specifically selected by selecting the density suitable for the environment where the gasket is used.
    Moreover, according to the end use characteristic required, a gasket can be similarly manufactured also combining other polymers with an effective amount of composition (A), (A '), (A ") or (A"'). These other polymers are thermoplastic polymers (ie melt processable), examples of which include high branched low density polyethylene, non-uniformly branched linear low density polyethylene, ethylene / vinyl acetate copolymers and ethylene / acrylic acid copolymers, and the like. And polymers.
    Gaskets prepared from this composition (A), (A '), (A ") or (A"') must have sufficient hardness to withstand compression, but must have sufficient softness to form a suitable seal. Therefore, a variety of gaskets can be manufactured by giving hardness to this polymer according to use. In this specification, hardness is measured as hardness of shore A or shore D (measured using ASTM D-2240). Ethylene copolymer composition (A), (A '), (A ") or (A") constituting a gasket. The shore A hardness in the case of "') is 70-100 range, even when the petroleum oil normally added for the purpose of reducing the hardness of a polymer and the obtained gasket is not used.
    In addition, additives such as antioxidants, to the ethylene copolymer composition (A), (A '), (A ") or (A"'), do not interfere with the improved properties found by the present applicants. Phosphites, cling additives (e.g., PlB, etc.), slip additives (e.g., eramides, etc.), antiblocking additives, pigments and the like.
    Gaskets take many different forms, including O-rings and flat seals (eg, film-shaped gaskets having a thickness corresponding to the intended use).
    Examples of suitable end-uses include beverage caps, hot-fill caps, polypropylene caps, metal caps, high density polyethylene caps, gaskets for window glass, sealing containers, sealing caps, gaskets for medical devices, filters Urea, gaskets for pressure exhaust, hot melt gaskets, easy twist off caps, gaskets for electrochemical cells, gaskets for refrigerators, gaskets for galvanic cells, gaskets for leak proof cells, waterproof sheets, reusable gaskets , Synthetic cork material, thin cell membrane separator, magnetic rubber material, disc gaskets for alcoholic beverage bottle caps, cold-sealing seals, gaskets for plastic molding, telescopic joints, water stops, corrosion resistant pipe joints, soft magnetic plastics, pipe joint seals, integral Weatherproof plastic lids and hinges for electrical output, magnetic faced foamed articles, jar rings, lead Gaskets, glass seals, tamper proof sealing liners, pressure applicators, bottle caps and straws, large seasoning bottle liners, metal caps for apple sauce or salsa jars, jars for household cans, crowns Etc. can be mentioned.
    The gasket made from this ethylene copolymer composition (A), (A '), (A ") or (A"') has a number of advantages especially when it is used for food use. This advantage is as follows: taste and odor are improved compared to the polymer gaskets currently used, for example ethylene / vinyl acetate and the like; Low adhesion to polar substrates (e.g. polyethylene terephthalate, glass, etc.) (which is effective to lower the torque when removing the seal / cap); A small amount of extract (this is especially valid for foods with regard to compliance with the rules); Good adhesion to non-polar substrates (eg, polypropylene and high density polyethylene (such as linear homopolymer polyethylene or linear heterogeneous high density polyethylene)); Sufficient barrier to oxygen, carbon dioxide and water; Higher melting point compared to polymers currently used (eg ethylene / vinyl acetate, etc.); Stress cracking resistance is good; Good chemical resistance; Hardness can be changed (in certain packages it is necessary to increase or decrease the hardness of the gasket depending on the amount of torque required to seal the container and the internal pressure of the container).
    Various gasket manufacturing techniques include US Pat. No. 5,215,587 (McConnellogue et al.); US Pat. No. 4,085,186 (Rainer); U.S. Patent 4,619,848 to Kinght et al .; U.S. Patent 5,044,710 to Kinght; U.S. Patent No. 4,981,231 to Kinght; U.S. Patent 4,717,034 to Mum ford; US Patent No. 3,786,954 (Shull); US Patent No. 3,779,965 to Lefforge et al .; U.S. Patent 3,493,453 (Ceresa et al.): U.S. Patent 3,183,144 to Caviglia; US Patent No. 3,300,072 to Caviglia; U.S. Patent 4,984,703 to Burzynski; US Patent No. 3,41 4,938 to Caviglia; US Patent No. 4,939,859 to Bayer; U.S. Patent 5,137,164 to Bayer; And techniques disclosed in US Pat. No. 5,000,992 to Kelch.
    The gasket claimed in the present disclosure also uses conventional techniques, by using an extruded sheet or film, such as a blown film, cast film or an extruded coated film, and then punching or cutting a gasket from the sheet or film. It can manufacture. Multilayer film structures are also suitable for use in the manufacture of the gaskets disclosed herein, provided that at least one layer (preferably an inner layer located adjacent to the product) comprises the ethylene-based copolymer compositions (A), (A '), (A ") or (A"'). Foam multilayer gaskets containing this ethylene copolymer composition (A), (A '), (A ") or (A"') are also useful for this invention.
    Extrusion workpiece:
    Extruded articles include extrusion coated articles, products in the form of extrusion profiles and extrusion cast films, which are ethylene-based copolymer compositions (A), (A '), ( A ") or (A" ').
    In addition, the ethylene copolymer composition (A), (A '), (A ") or (A"') can also be blended with another polymer material, and can be used for manufacturing a single layer or a multilayer product, It is also possible to produce structures such as sealants, adhesives or bonding layers. Other polymer materials may be blended into the ethylene copolymer composition (A), (A '), (A ") or (A"') for the purpose of improving processability, film strength, heat sealing property or adhesion. .
    The ethylenic copolymer compositions (A), (A '), (A ") or (A"') can also be used in chemical and / or physically improved forms. Such improvement may be achieved by any known technique, and can be achieved, for example, by ionomerization and extrusion grafting.
    In this specification, it is defined as a draw down, which means stretching or stretching the molten polymer extrudate (web or filament) in the machine direction and often (low but at the same time) transverse direction.
    In this specification, the difference between the die width and the width of the extruded workpiece at the takeoff position or the final width of the manufactured product is defined as a neck in. This neck-in is affected by the expansion of the extrudate and, to a lesser extent, by the surface tension. The measured neck in value (at a constant output) is constant or decreases even if the drawdown rate is high, and in the case of normal ethylene polymers, the neck in value is generally lowered in molecular weight and / or narrowed in molecular weight distribution. It is a well-known fact that it increases.
    In addition, in the ethylene copolymer composition (A), (A '), (A ") or (A"'), the additives to the extent that the high drawdown and substantially low neck phosphorus which the applicants discovered are not impaired, For example, antioxidants, phosphites, cling additives (e.g., PlB, etc.), Standostab PEPQ (trademark), pigments, colorants, fillers and the like can be added. Additives for improving the antiblocking and friction coefficient characteristics in the ethylenic copolymer composition (A), (A '), (A ") or (A"'), including but not limited to But, in addition to untreated and treated silicon dioxide, talc, calcium carbonate and clay, primary, secondary and substituted fatty acid amides, and the like), release rolls for cooling rolls, silicone coating materials and the like can be further added. It is also possible to add other additives, for example to improve the antifogging properties of the transparent cast film, as described, for example, by Niemann in US Pat. No. 4,864,552. Another additive, e.g., quaternary ammonium compound, alone or ethyleneacrylic acid (EAA), which enhances the antistatic properties of the coatings, profiles and films of the present invention to enable the packaging or manufacture of electronic sensitive products. ) May be added in combination with copolymers or other functional polymers.
    The multi-layered structure comprising the ethylenic copolymer composition (A), (A '), (A ") or (A"') may be manufactured by any known means, and these known means include extrusion processing, lamination and these And combinations thereof. In addition, the ethylene copolymer composition (A), (A '), (A ") or (A"') can also be used in a coextrusion process operation, In this case, using the material which shows higher drawdown, At least one material that exhibits a lower drawdown is essentially supported.
    The ethylenic copolymer compositions (A), (A '), (A ") or (A"') can be used for the production of extrusion coatings, extrusion profiles and extrusion cast films, irrespective of monolayer or multilayer structure. Can be. When the ethylenic copolymer composition (A), (A '), (A ") or (A"') is used for coating purposes or for the purpose of a multilayer structure, the substrate or the adjacent material layer may be polar or nonpolar. Examples of this substrate include, but are not limited to, paper products, metals, ceramics, glass, various polymers (particularly other polyolefins), and combinations thereof. In the case of the extruded profile material, various products can be processed. Examples of the product include, but are not limited to, a gasket for a refrigerator, a jacket for wire and cable, a wire coating, a medical pipe material, a water pipe, and the like. . Extruded cast films made using ethylene-based copolymer compositions (A), (A '), (A ") or (A"') can be used for food packaging and industrial stretchwrap applications.
    pipe:
    The pipe is a silane modified product of the ethylene copolymer composition (A), (A '), (A ") or (A"'). The silane modification is added to the composition (A), (A '), (A ") or (A"') by adding a radical generator and a silane compound, and mixing it with a suitable mixer, such as Henschel mixer, for example, and extruder It can be manufactured by heating, kneading and heat-grafting to about 140-250 degreeC with a half-banley mixer etc.
    Radical generators used for silane modification include 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5- (t-butylperoxy) hexyne-3, and the like. This is preferable. As a silane compound used for silane modification, the silane compound which has hydrolyzable organic groups, such as a terminal vinyl group and an alkoxy group, is preferable, and vinyl trimethoxysilane, vinyl triethoxysilane, etc. are preferable.
    The pipe is obtained by crosslinking a molded product of the silane modified product of the composition (A), (A '), (A' ') or (A' ''). A molded object mix | blends a silanol condensation catalyst and shape | molds to a pipe shape normally using a pipe molding machine.
    As the silanol condensation catalyst, a known compound used as a catalyst for promoting dehydration condensation between silanol groups can be used. In addition, a masterbatch is separately prepared using a silanol condensation catalyst and a linear polyethylene before modification, and this and silane-modified linear polyethylene are dry blended by a mixer such as Henschel mixer and V blender, and then the mixture is pipe-molded. You may use it.
    The molded pipe is usually brought into contact with moisture for about 1 minute to 1 week in water, steam, or a humid atmosphere at about room temperature to about 130 ° C. By this, a silane crosslinking reaction advances with a silanol catalyst and a crosslinked pipe is obtained.
    Heat pipe stabilizers, anti-aging agents, weather stabilizers, hydrochloric acid absorbents, lubricants, organic or inorganic pigments, carbon black, flame retardants, antistatic agents, fillers and the like can be blended.
    Injection molded body:
    An injection molded product is obtained by injection molding the ethylene copolymer composition (A), (A '), (A ") or (A"'). An injection molded body can be manufactured by a conventionally well-known injection molding apparatus, and molding conditions can also use conventionally well-known conditions.
    Such injection molded bodies are excellent in heat resistance and environmental stress fracture resistance.
    Electric wire sheath:
    A wire sheath is a sheath (outermost sheath) which protects an electric wire or a cable.
    The wire sheath includes the ethylene-based copolymer composition (A), (A '), (A ") or (A"'), and if necessary, a conventionally known heat stabilizer, weather stabilizer, carbon black, pigment, and flame retardant. And anti-aging agents.
    The wire sheath has a 50% crack initiation time (F 50 ) (ASTM Dl698) of 600 hours or more and is measured by taber wear test (JIS K7204, load kg, truck wheel CS-17, 60 rpm, 1,000 times). It is preferable that the wear amount is less than l0 mg, and the Izod impact strength (ASTM D256, notched) measured at -40 ° C is 40 J / m 2 or more.
    The electric wire sheath can form the said ethylene-based copolymer composition (A), (A '), (A ") or (A"') by the conventionally well-known extrusion coating formation method.
    Such wire sheath has stress crack resistance, abrasion resistance and impact resistance at low temperatures.
    The ethylene copolymer composition (A), (A '), (A ") or (A"') can be used for the following draw-down extrusion method.
    The high drawdown extrusion method is the ethylene copolymer composition (A), (A '), (A ") or (A"') or composition (A), (A '), (A ") or (A" A method of extrusion coating on a substrate or preparing a cast film using a composition comprising ') (hereinafter referred to as thermoplastic composition), which comprises:
    (i) feeding the thermoplastic composition to at least one extruder,
    (ii) create at least one polymer stream melt blended with this thermoplastic composition,
    (iii) passing the molten polymer stream through a die and extruding to produce a main web.
    Improvements to the method include:
    (i) running the extruder at a line speed of at least 152 m / min,
    (a) covering the substrate with at least one layer of the thermoplastic composition by drawing down the web onto the substrate, or
    (b) cooling the web and drawing it down onto the take off device to produce the film using at least one layer of the thermoplastic composition,
    (ii) in the following uses, transporting or collecting the coated substrate or the film.
    With the present invention, lower neck in, higher draw down rate, and higher draw to resonance resistance (unstable melt flow rate phenomenon) than those obtained when using ethylene polymers prepared using conventional Ziegler catalysts Is obtained.
    In this specification, a drawdown is defined to mean stretching or unfolding a molten polymer extrudate (web or filament) in the machine direction and often (low or simultaneously).
    In this specification, the difference between the web width at the die width and the takeoff position is defined as a neck in. This neck-in is affected by the expansion of the extrudate and, to a lesser extent, by the surface tension. The measured neck in value (at a constant output) is constant or decreases even with a higher draw down rate, and in the case of ordinary ethylene polymers, the neck in value is generally lowered in molecular weight and / or narrowed in molecular weight distribution. It is a well known fact that according to the increase.
    In the present invention, in the composition (A), (A '), (A ") or (A"'), an additive, for example, antioxidant, phosphite, cling additive (for example, PlB, etc.), Standostab PEPQ (trademark), pigments, colorants, fillers and the like can be added. Additives that improve antiblocking and coefficient of friction characteristics can be further added to this extruded coating and film. Examples of this additive include, but are not limited to, untreated and treated silicon dioxide, talc, calcium carbonate and clay, and primary, secondary and substituted fatty acid amides, cooling roll release agents, silicone coating materials, and the like. have. For example, as described by Niemann in US Pat. No. 4.486.552, other additives may be added that, for example, enhance the antifogging properties of the transparent cast film. Ethylene acrylic acid (EAA) copolymerization alone or with other additives, such as quaternary ammonium compounds, which enhance the antistatic properties of the coatings, profiles and films of the present invention to enable the packaging or manufacture of electronic sensitive products. It can also be added in combination with retention or other functional polymers.
    Compositions (A), (A '), (A ") or (A"') for use in the preparation of the compositions and articles of the invention are irrespective of whether the resulting film or coating used is a single layer structure or a multilayer structure. , Linear ethylene polymers and / or high pressure ethylene polymers can be blended or used as only one dendritic polymer component. Moreover, this composition (A), (A '), (A ") or (A"') and homopolymers are blended together, or composition (A), (A '), (A ") or (A"' ), Homopolymers and other polymers can be blended to improve processability, film strength, heat sealability or adhesion.
    Examples of some materials suitable for blending with the compositions (A), (A '), (A ") or (A"') include, but are not limited to, low density ethylene such as high pressure low density ethylene homopolymers (LDPE) Olefin polymers prepared at low to medium pressures such as polymers, ethylene / vinyl acetate copolymers (EVA), ethylene / carboxylic acid copolymers, ethylene / acrylate copolymers, polybutylene (PB) and ethylene / α-olefin polymers ( High density polyethylene, medium density polyethylene, polypropylene, ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and ultra low density polyethylene) and graft modified polymers, and combinations thereof.
    Suitable high pressure ethylenic copolymers include at least one α, β-ethylenically unsaturated comonomer (e.g., acrylic acid, methacrylic acid and acetic acid), as described by McKinney et al. In US Pat. No. 4,599,392. And copolymers prepared by copolymerizing with vinyl). Suitable high pressure ethylenic copolymers comprise from 0.1 to 55% by weight of the comonomer in total, more preferably from 1 to 35% by weight of the comonomer in total, and most preferably from 2 to 28% by weight of the comonomer in total. It contains. The high pressure ethylene copolymer may be chemically and / or physically modified by any of the known techniques, for example, ionomerization, extrusion grafting, or the like.
    However, suitable polymer blends comprise at least one ethylene-based copolymer composition (A), (A '), (A ") or (A"'), and preferably these compositions (A), (A '). ), (A ″) or (A ″ ′) may comprise at least about 5%, more preferably at least about 10%, of the blend composition.
    In the case of the multilayer film and the film of the present invention, at least one composition (A), (A '), (A ") or (A"') may be included in arbitrary layers and any number of layers. However, in the case of multi-layered films and coating structures, at least one composition (A), (A '), (A ") or (A"') has an outer layer (also called a skin layer or surface layer in the art) and sealant. Most preferably included in the layer.
    The blend compositions of the present invention can be prepared by any suitable means known in the art, which includes turnable dry blender means, melt blend means by compound or sidearm extrusion, multiple reactor polymerization and combinations thereof. have. Moreover, the multilayer structure of this invention can also be manufactured by arbitrary well-known means, As this means, a coextrusion, lamination | stacking, and a combination thereof are mentioned. The composition of the present invention can also be used in coextrusion operations in which a material exhibiting a higher drawdown is used and essentially supporting one or more materials exhibiting a lower drawdown.
    Regardless of monolayer or multilayer structures, the blend compositions and nonblend compositions of the invention can be used to coat a variety of polar and nonpolar substrates. Examples of the substrate include, but are not limited to, paper products, metals, ceramics, glass, various polymers (particularly other polyolefins), and combinations thereof.
    The present invention relates to an ethylenic copolymer composition and its use.
    The present invention also relates to the use of the ethylene copolymer composition.
    Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
    In addition, in this invention, the physical property evaluation of the film was performed as follows.
    (Haze)
    It measured according to ASTM-D-1003-61.
    (Gloss)
    Measured according to JlS Z8741.
    (Dart impact strength)
    It measured according to ASTM Dl709A method.
    Preparation Example 1
    [Production of Catalyst Component]
    5.0 kg of silica dried at 250 ° C. for 10 hours was suspended in 80 liters of toluene and then cooled to 0 ° C. Thereafter, 28.7 liters of toluene solution of methylaluminoxane (Al; 1.33 mol / liter) was added dropwise over 1 hour. At this time, the temperature in the system was kept at 0 ° C. Then, it was made to react at 0 degreeC for 30 minutes, Then, it heated up to 95 degreeC over 1.5 hours, and made it react at this temperature for 20 hours. After that, the temperature was lowered to 60 ° C and the supernatant liquid was removed by the decantation method.
    The solid component thus obtained was washed twice with toluene and then resuspended in 80 liters of toluene. 20.0 liters of toluene solution (Zr; 14.0 mmol / liter) of bis (methylcyclopentadienyl) zirconium dichloride was dripped in this system over 80 minutes at 80 degreeC, and also it was made to react at 80 degreeC for 2 hours further. Thereafter, the supernatant was removed and washed twice with hexane to obtain a solid catalyst containing 3.6 mg of zirconium per lg.
    [Preparation of Prepolymerization Catalyst]
    To 85 liters of hexane containing 17 mol of triisobutylaluminum, 0.85 kg of the solid catalyst obtained above and 77 g of l-hexene were added, and prepolymerization of ethylene was carried out at 35 ° C. for 3.5 hours to obtain 1 g of solid catalyst. A prepolymerization catalyst was obtained in which 3 g of polyethylene was prepolymerized.
    〔polymerization]
    Ethylene and 1-hexene were copolymerized at a total pressure of 20 kg / cm 2 -G and a polymerization temperature of 80 ° C. using a continuous fluidized bed gas phase polymerization apparatus. In order to continuously supply 0.05 mmol / h and triisobutylaluminum at a rate of 10 mmol / h in terms of zirconium atoms, and to maintain a constant gas composition during polymerization, ethylene, l-hexene, hydrogen, and nitrogen were prepared. It was supplied continuously (gas composition; 1-hexene / ethylene = 0.020, hydrogen / ethylene = 9.5x10 <-4> , ethylene concentration = 50%). The yield of the polymer was 4. l kg / h.
    Reference Example 1
    [Film forming]
    Using the pellet of the ethylene-alpha-olefin copolymer (A-1) manufactured by the manufacture example 1, the inflation film was obtained on condition of the following. Using a single-screw extruder with a 20 mmφ / L / D = 26 and a single slit air ring, a 25 mmφ die, a rip width of 0.7 mm, an air flow rate of 90 liters / minute, an extrusion amount of 9 g / min, blow ratio = l.8, winding speed = The film of thickness = 30 micrometers was obtained by inflation molding at 2.4 m / min and processing temperature = 200 degreeC. The results are shown in Tables 1 and 3.
    Example l
    The ethylene-α-olefin copolymer (A-1) and the high pressure method low density polyethylene (Dl) shown in Table 2 were melt-kneaded at a weight ratio (A-1) / (Dl): 96/4 to pelletize the pellet. Using the same method as in Reference Example 1 to obtain an inflation film. The results are shown in Table 3.
    Preparation Example 2
    [Production of Catalyst Component]
    5.0 kg of silica dried at 250 ° C. for 10 hours was suspended in 80 liters of toluene and then cooled to 0 ° C. Thereafter, 28.7 liters of toluene solution of methylaluminoxane (Al; 1.33 mol / liter) was added dropwise over 1 hour. At this time, the temperature in the system was kept at 0 ° C. Then, it was made to react at 0 degreeC for 30 minutes, Then, it heated up to 95 degreeC over 1.5 hours, and made it react at this temperature for 20 hours. The temperature was then lowered to 60 ° C. and the supernatant was removed by the decantation method.
    The solid component thus obtained was washed twice with toluene and then resuspended in 80 liters of toluene. 5.8 liters of toluene solution of bis (l, 3-n-butylmethylcyclopentadienyl) zirconium dichloride (Zr; 34.0 mmol / liter) and toluene solution of bis (methylcyclopentadienyl) zirconium dichloride in this system 6.0 liters of Zr; 14.0 mmol / liter) was dripped at 80 degreeC over 30 minutes, and also it was made to react at 80 degreeC for 2 hours further. Thereafter, the supernatant was removed and washed twice with hexane to obtain a solid catalyst containing 3.6 mg of zirconium per lg.
    [Preparation of Prepolymerization Catalyst]
    To 85 liters of hexane containing 17 mol of triisobutylaluminum, 0.85 kg of the solid catalyst obtained above and 77 g of 1-hexene were added and prepolymerized ethylene at 35 ° C. for 3.5 hours to obtain 3 g of lg per solid catalyst. A prepolymerization catalyst obtained by prepolymerization of polyethylene was obtained.
    [olymerization]
    Copolymerization of ethylene and 1-hexene was carried out at a total pressure of 20 kg / cm 2 -G and a polymerization temperature of 80 ° C. using a continuous fluidized bed gas phase polymerization apparatus. The prepolymerization catalyst prepared above was continuously fed with 0.05 mmol / h and triisobutylaluminum at a rate of 10 m mol / h in terms of zirconium atoms and ethylene, 1-hexene, hydrogen, nitrogen to maintain a constant gas composition during polymerization. Was fed continuously (gas composition; 1-hexene / ethylene = 0.020, hydrogen / ethylene = 9.5x10 <-4> , ethylene concentration = 50%), and the ethylene-alpha-olefin copolymer (C-1) was obtained.
    Reference Example 2
    This ethylene-alpha-olefin copolymer (C-1) was melt-kneaded and pelletized, and the inflation film was obtained by the method similar to the reference example 1 using this pellet. The results are shown in Tables 1 and 3.
    Example 2
    The ethylene-α-olefin copolymer (Cl) and the high-pressure method low density polyethylene (Dl) shown in Table 2 were melt-kneaded and pelletized by weight ratio (C-1) / (Dl): 96/4, and this pellet was used. In the same manner as in Reference Example 1 to obtain an inflation film. The results are shown in Table 3.
    Reference Example 3
    Ethylene-α-olefin copolymer (C-2) in the same manner as in Production Example 1 except that the gas composition was adjusted so that the density and MFR were the ethylene-α-olefin copolymer (C-2) shown in Table 1. Got. This ethylene-alpha-olefin copolymer (C-2) was melt-kneaded and pelletized, and it carried out similarly to the reference example 1 using this pellet, and obtained the inflation film. The results are shown in Table 3.
    Example 3
    The ethylene-α-olefin copolymer (C-2) and the high-pressure method low density polyethylene (Dl) shown in Table 2 were melt-kneaded and pelletized by a weight ratio (C-2) / (Dl) = 96/4. Inflation film was obtained in the same manner as in Reference Example 1 using. The results are shown in Table 3.
    Reference Example 4
    The ethylene-α-olefin copolymer (C-3) was prepared in the same manner as in Production Example 1, except that the gas composition was adjusted so that the density and the MFR became the ethylene-α-olefin copolymer (C-3) shown in Table 1. ) This ethylene-alpha-olefin copolymer (C-3) was melt-kneaded and pelletized, and it carried out similarly to Reference Example 1 using this pellet, and obtained the inflation film. The results are shown in Table 3.
    Example 4
    The ethylene-α-olefin copolymer (C-3) and the high pressure method low density polyethylene (Dl) shown in Table 2 were melt-kneaded and pelletized by a weight ratio (C-3) / (D-1) = 96/4. Using an pellet, it carried out similarly to the reference example 1, and obtained the inflation film. The results are shown in Table 3.
    Comparative Example
    [Production of Catalyst Component]
    Toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr; 14.0 mmol / liter) instead of 20.0 liters of toluene solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (Zr ; 34.0 mmol / liter) A solid catalyst component was prepared in the same manner as in [Preparation of Catalyst Component] in Preparation Example 1, except that 8.2 liters were used.
    [Preparation of Prepolymerization Catalyst]
    A prepolymerization catalyst was obtained in the same manner as in Production Example 1 except that the solid catalyst component obtained in [Preparation of the Catalyst Component] was used.
    〔polymerization]
    Production Example 1 and the composition of the prepolymerization catalyst obtained in the above [Preparation Polymerization Catalyst] were used, except that the gas composition was adjusted so that the density and MFR were the ethylene-α-olefin copolymer (A-2) shown in Table 1. In the same manner, an ethylene l-hexene copolymer was produced. Melt properties and the like of the obtained copolymer are shown in Table 1. The ethylene-alpha-olefin copolymer (A-2) was melt-kneaded and pelletized, and it carried out similarly to the reference example 1 using this pellet, and obtained the inflation film. The results are shown in Table 3.
    Comparative Example 2
    The ethylene-α-olefin copolymer (A-2) and the high-pressure method low density polyethylene (Dl) shown in Table 2 were melt-kneaded and pelletized at a weight ratio (A-2) / (D-1) = 96/4. Using an pellet, it carried out similarly to the reference example 1, and obtained the inflation film. The results are shown in Table 3.
    Comparative Example 3
    Toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr; 14.0 mmol / liter) Toluene solution of bis (l, 3-dimethylcyclopentadienyl) zirconium dichloride (Zr; 28.0 mmol / Liter) A solid catalyst component was prepared in the same manner as in [Preparation of Catalyst Component] in Preparation Example 1, except that 10.0 liters were used.
    [Preparation of Prepolymerization Catalyst]
    A prepolymerization catalyst was obtained in the same manner as in Production Example 1, except that the solid catalyst component obtained in [Production of catalyst component] was used.
    〔polymerization]
    Production Example 1 except that the gas composition was adjusted such that the density and MFR were made to the ethylene-α-olefin copolymer (A-3) shown in Table 1 using the prepolymerization catalyst obtained in [Preparation of Prepolymerization Catalyst]. In the same manner as in the ethylene-l-hexene copolymer was prepared. Melt properties and the like of the obtained copolymer are shown in Table 1. The ethylene-alpha-olefin copolymer (A-3) was melt-kneaded and pelletized, and it carried out similarly to the reference example 1 using this pellet, and obtained the inflation film. The results are shown in Table 3.
    Comparative Example 4
    The ethylene-α-olefin copolymer (A-3) and the high pressure method low density polyethylene (Dl) shown in Table 2 were melt-kneaded and pelletized in a weight ratio (A-3) / (D-1): 96/4, and this Using an pellet, it carried out similarly to the reference example 1, and obtained the inflation film. The results are shown in Table 3.
    Reference Example 5
    Ethylene-α-olefin air was prepared in the same manner as in Reference Example 4 except that the gas composition was adjusted so that the density and MFR were ethylene-α-olefin copolymers (C-5) and (C-6) shown in Table 4. Copolymer (C-5) and (C-6) were obtained. This ethylene / alpha-olefin copolymer (C-5) and (C-6) were melt-kneaded and pelletized by weight ratio (C-5) / (C-6): 60/40 (Ll), and this pellet Inflation film was obtained like Example 1 using. The results are shown in Tables 5 and 6.
    Example 5
    The ethylene-α-olefin copolymer composition (L-1) and the high pressure method low density polyethylene (Dl) shown in Table 2 were melt-kneaded and pelletized by a weight ratio (L-1) / (Dl): 97/3, and this pellet Inflation film was obtained by carrying out similarly to the reference example 1 using the test strip. The results are shown in Table 6.
    Reference Example 6
    The ethylene-α-olefin copolymer (C-7) was prepared in the same manner as in Production Example 2, except that the gas composition was adjusted so that the density and MFR became the ethylene-α-olefin copolymer (C-7) shown in Table 4. ) This ethylene-α-olefin copolymer (C-7) and (C-6) were melt-kneaded and pelletized at a weight ratio (C-7) / (C-6): 60/40 to pelletize (L-2). Using an pellet, it carried out similarly to the reference example 1, and obtained the inflation film. The results are shown in Tables 5 and 6.
    Example 6
    The ethylene-α-olefin copolymer composition (L-2) and the high-pressure method low density polyethylene (Dl) shown in Table 2 were melt-kneaded and pelletized by a weight ratio (L-2) / (Dl): 97/3, and this pellet The inflation film was obtained like reference example 1 using the test sheet. The results are shown in Table 6.
    Reference Example 7
    Ethylene-α-olefins were prepared in the same manner as in Production Example 2, except that the gas composition was adjusted so that the density and MFR were ethylene-α-olefin copolymers (C-8) and (C-9) shown in Table 4. Copolymers (C-8) and (C-9) were obtained. This ethylene-α-olefin copolymer (C-8) and (C-9) were melt-kneaded and pelletized in a weight ratio (C-8) / (C-9): 60/40 to pelletize (L-3), and Using an pellet, it carried out similarly to Example 1, and obtained the inflation film. The results were shown to Tables 5 and 6.
    Example 7
    Pelletization of the ethylene-α-olefin copolymer composition (L-3) and high pressure method low density polyethylene (D-1) shown in Table 2 by melt kneading at a weight ratio (L-3) / (D-1): 97/3 Using this pellet, it carried out similarly to the reference example 1, and obtained the inflation film. The results are shown in Table 6.
    * 1: Value of 80 x exp (-100 (d-0.88)) + 0.1 for MFR <10 g / 10 min.
    MFR> For the 10g / 10 bun, 80 × (MFR-9) 0.26 × exp (-100 (d-0.88)) + 0.1 in value.
    * 2: value of 400 × d-248
    * 3: Value of 9.0 x MFR -0.65
    * 4: Value of 2.0 x MFR -0.84
    * 5: Value of (0.039Ln (C-2) +0.0096) × x + 2.87.
    C = carbon number of the comonomer (for 1-hexene: C = 6)
    X = mol% of comonomer
    * 6: (0.039Ln (C-2) +0.1660) × x + 2.87
    C = carbon number of the comonomer (for 1-hexene: C = 6)
    X = mol% of comonomer
    * 7: value of 7.5xlog (MFR) +12.5.
    * 8: Value of 7.5xlog (MFR) -1.2.
    * 9: formability AA: MT≥3, BB: 2≤MT <3, CC: MT <2
    * 1: Value of 80 x exp (-100 (d-0.88)) + 0.1 for MFR <10 g / 10 min.
    MFR> For the 10g / 10 bun, 80 × (MFR-9) 0.26 × exp (-100 (d-0.88)) + 0.1 in value.
    * 2: value of 400 × d-248
    * 3: Value of 9.0 x MFR -0.65
    * 4: Value of 2.0 x MFR -0.84
    * 10: value of 9.0 x MFR -0.65 .
    * 11: Value of 2.2 x MFR -0.84 .
    * 12: value of 100 × MFR.
    * 13: For FI≥100 × MFR (FI: Liquidity Index, MFR: Melt Flow Rate),
    carbon number (C) of an alpha olefin = 4-6:
    0.45 / (1-d) × log (3 × MT 1.4 ) × (C-3) 0.1
    Carbon number (C) of an alpha olefin = 7-20:
    Value of 0.50 / (1-d) × log (3 × MT 1.4 )
    For FI <100 × MFR (FI: Liquidity Index, MFR: Melt Flow Rate),
    carbon number (C) of an alpha olefin = 4-6:
    Value of 0.25 / (1-d) × log (3 × MT 1.4 ) × (C-3) 0.1
    Carbon number (C) of an alpha olefin = 7-20:
    Value of 0.50 / (1-d) × log (3 × MT 1.4 )
    (Where, d: density (g / cm 3) and MT: melt tension (g))
    * 14: value of 100 × MFR
    * 15: formability
    AA: MT≥3, BB: 2≤MT <3, CC: MT <2
    权利要求:
    Claims (16)
    [1" claim-type="Currently amended] (A) an ethylene-α-olefin copolymer and (E) a high pressure radical method low density polyethylene,
    The ethylene-α-olefin copolymer (A) is a copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms and further has the following characteristics:
    (A-i) Melt tension (MT) and melt flow rate (MFR) at 190 ° C satisfy the following relationship,
    9.0 × MFR -0.65>MT> 2.2 × MFR -0.84
    (A-ii) Flow activation energy ((E a ) × 10 -4 J / molK) obtained from the shift factor of time-temperature overlap of the flow curve, carbon number (C) of α-olefin in the copolymer and α in the copolymer -The content of olefin (x mol%) satisfies the following relationship,
    (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 −4 ≤ (0.039Ln (C-2) +0.1660) × x + 2.87
    (A-iii) When the copolymer is inflation-formed to produce a film having a thickness of 30 µm, the haze of the film satisfies the following relationship.
    When the flow index (FI) and the melt flow rate (MFR), defined as the shear rate when the shear stress at 190 ° C reaches 2.4 × 10 6 dyne / cm 2, are FI ≧ 100 × MFR,
    If carbon number (C) of an alpha olefin is 6,
    Haze 〈0.45 / (1-d) × log (3 × MT 1.4 ) × (C-3) 0.1
    If the carbon number (C) of the α-olefin is 7 or 8,
    Haze 〈0.50 / (1-d) × log (3 × MT 1.4 )
    When the fluidity index (FI) and the melt flow rate (MFR), defined as the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 6 dyne / cm 2, are FI <100 × MFR,
    If carbon number (C) of an alpha olefin is 6,
    Haze 〈0.25 / (1-d) × log (3 × MT 1.4 ) × (C-3) 0.1
    If the carbon number (C) of the α-olefin is 7 or 8,
    Haze <0.50 / (1-d) × log (3 × MT 1.4 )
    (Where d denotes density (g / cm 3) and MT denotes melt tension (g))
    Has;
    The high pressure radical low density polyethylene (E) has the following characteristics:
    (E-i) Melt flow rate measured at 190 ° C and 2.16 kg load ranges from 0.1 to 50 g / 10 minutes,
    (E-ii) Molecular weight distribution (Mw / Mn: Mw = weight average molecular weight, Mn = number average molecular weight) measured by gel permeation chromatography and melt flow rate (MFR) satisfy the following relationship.
    7.5 × log (MFR) -1.2≤Mw / Mn≤7.5 × log (MFR) +12.5
    Ethylene copolymer composition, characterized in that it has a.
    [2" claim-type="Currently amended] The method of claim 1,
    The ethylene-α-olefin copolymer (A)
    (a) an organoaluminum oxy compound,
    (b-I) at least one transition metal compound selected from transition metal compounds represented by the following general formula (I):
    ML 1 x ------ (I)
    (Wherein M is a transition metal atom selected from Group 4 of the periodic table; L 1 is a ligand that coordinates to transition metal atom M, and at least two ligands L 1 of these are at least one selected from hydrocarbons having 3 to 10 carbon atoms) X is a substituted cyclopentadienyl group having a group of and a ligand L 1 other than the substituted cyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom; Is the valence of the transition metal M)
    (b-II) At least one transition metal compound selected from transition metal compounds represented by the following general formula (II):
    ML 2 x ------ (II)
    (Wherein M is a transition metal atom selected from Group 4 of the periodic table; L 2 is a ligand that coordinates to transition metal atom M, and at least two of them, L 2, is a methylcyclopentadienyl group or an ethylcyclopentadienyl group) And ligands L 2 other than the methylcyclopentadienyl group or the ethylcyclopentadienyl group are a C1-C12 hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom; X is a transition metal Valence of M)
    An ethylene copolymer composition obtained by copolymerizing ethylene with an α-olefin having 6 to 8 carbon atoms in the presence of a catalyst for olefin polymerization.
    [3" claim-type="Currently amended] The method according to claim 1 or 2,
    The ethylene-α-olefin copolymer (A) is a catalyst for olefin polymerization in which the organoaluminum oxy compound (a), the transition metal compound (bI) and the transition metal compound (b-II) are supported on the carrier (c). The ethylene copolymer composition obtained by copolymerizing ethylene and the C6-C8 alpha-olefin under the following.
    [4" claim-type="Currently amended] (B) an ethylene-α-olefin copolymer, (C) an ethylene-α-olefin copolymer, and (E) a high pressure radical method low density polyethylene,
    The ethylene-α-olefin copolymer (B) is a copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms and further has the following characteristics:
    (B-i) density is in the range of 0.880 to 0.970 g / cm 3,
    (B-ii) Melt flow rate (MFR) at 190 ° C. and 2.16 kg load is in the range of 0.02 to 200 g / 10 minutes,
    (B-iii) The decane soluble fraction (W) and the density (d) at room temperature satisfy the following relationship,
    For MFR≤10g / 10min,
    W <80 x exp (-100 (d-0.88)) + 0.1
    In the case of MFR> 10g / 10 minutes,
    W <80 x (MFR-9) 0.26 x exp (-100 (d-0.88)) + 0.1
    (B-iv) The temperature (Tm) and the density (d) of the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) satisfy the following relationship,
    Tm <400 × d-248,
    (B-v) Melt tension (MT) and melt flow rate (MFR) at 190 ° C satisfy the following relationship,
    9.0 × MFR -0.65>MT> 2.2 × MFR -0.84
    (B-vi) Flow activation energy ((E a ) × 10 -4 J / molK) obtained from the shift factor of time-temperature overlap of the flow curve, α-olefin carbon number (C) in the copolymer and α- in the copolymer The content of olefins (x mol%) satisfies the following relationship,
    (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 −4 ≤ (0.039Ln (C-2) +0.1660) × x + 2.87,
    (B-vii) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC satisfies the following relationship,
    2.2 &lt; Mw / Mn &lt;3.5;
    Has,
    The ethylene-α-olefin copolymer (C) is a copolymer of ethylene and an α-olefin having 6 to 8 carbon atoms and has the following characteristics:
    (C-i) density ranges from 0.880 to 0.970 g / cm 3,
    (C-ii) Melt flow rate (MFR) at 190 ° C and 2.16 kg load is in the range of 0.02 to 200 g / 10 minutes,
    (C-iii) The decane soluble fraction (W) and the density (d) at room temperature satisfy the following relationship,
    If MFR≤10g / 10min,
    W <80 x exp (-100 (d-0.88)) + 0.1
    MFR> 10g / 10 minutes
    W <80 x (MFR-9) 0.26 x exp (-100 (d-0.88)) + 0.1,
    (C-iv) The temperature (Tm) and the density (d) of the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) satisfy the following relationship,
    Tm <400 × d-248,
    (C-v) Melt tension (MT) and melt flow rate (MFR) at 190 ° C satisfy the following relationship,
    MT≤ 2.2 × MFR -0.84
    Has;
    The high pressure radical low density polyethylene (E) has the following characteristics:
    (E-i) Melt flow rate measured at 190 ° C and 2.16 kg load is in the range of 0.1-50 g / 10 minutes,
    (E-ii) The molecular weight distribution (Mw / Mn: Mw = weight average molecular weight, Mn = number average molecular weight) measured by gel permeation chromatography and the melt flow rate (MFR) satisfy the following relationship,
    7.5 × log (MFR) -1.2≤Mw / Mn≤7.5 × log (MFR) +12.5
    Has;
    The ratio of the melt flow rate (MFR (C)) of the said copolymer (C) and the melt flow rate (MFR (B)) of the said copolymer (B) satisfy | fills the following conditions.
    1 <(MFR (C)) / (MFR (B)) ≤20
    Ethylene copolymer composition, characterized in that.
    [5" claim-type="Currently amended] The method of claim 4, wherein
    The ethylene-α-olefin copolymers (B) and (C) are both ethylene-1-hexene copolymers and the composition of ethylene-α-olefin copolymers (B) and (C) has the following properties:
    (A'-i) Melt tension (MT) and melt flow rate (MFR) at 190 ° C satisfy the following relationship,
    9.0 × MFR -0.65>MT> 2.2 × MFR -0.84
    (A'-ii) Flow activation energy ((E a ) × 10 -4 J / molK), carbon number of 1-hexene in copolymers (B) and (C), determined from the shift factor of time-temperature overlap of the flow curve (C) and the content (x mol%) of 1-hexene in copolymers (B) and (C) satisfy the following relationship,
    (0.039Ln (C-2) +0.0096) × x + 2.87 <E a × 10 −4 ≤ (0.039Ln (C-2) +0.1660) × x + 2.87
    (A'-iii) When the composition is inflation-molded to produce a film having a thickness of 30 µm, the haze of the film has the following relationship,
    When the fluidity index (FI) and the melt flow rate (MFR), defined as the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 6 dyne / cm 2, satisfy FI ≧ 100 × MFR,
    Haze 〈0.45 / (1-d) × log (3 × MT 1.4 ) × (C-3) 0.1
    When the fluidity index (FI) and the melt flow rate (MFR) defined by the shear rate when the shear stress at 190 ° C reaches 2.4 × 10 6 dyne / cm 2 satisfy the FI <100 × MFR,
    Haze 〈0.25 / (1-d) × log (3 × MT 1.4 ) × (C-3) 0.1
    (Where d is density (g / cm 3), MT is melt tension (g), and C is 1-hexene carbon number, i.e. 6
    Ethylene copolymer composition, characterized in that it has a.
    [6" claim-type="Currently amended] The method of claim 5,
    The composition of the said ethylene-alpha-olefin copolymer (B) and (C) adds the said characteristic (A'-1)-(A'-iii), and the following characteristic:
    (A'-iv) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC satisfies the following conditions,
    2.0≤Mw / Mn≤2.5
    Ethylene copolymer composition, characterized in that it further has.
    [7" claim-type="Currently amended] (A) the ethylenic copolymer composition of any one of claims 1 to 3
    (D) (a) an organoaluminum oxy compound and
    (b-III) Copolymerization of ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst for olefin polymerization comprising a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton, characteristic:
    (D-i) density ranges from 0.850 to 0.980 g / cm 3,
    (D-ii) intrinsic viscosity measured in decalin at 135 ° C. in the range of 0.4 to 8 dl / g;
    Ethylene-α-olefin copolymer (wherein ethylene-α-olefin copolymer (A) is not the same as ethylene-α-olefin copolymer (D)) having an ethylene copolymer composition.
    [8" claim-type="Currently amended] (A ') the ethylene-based copolymer composition of any one of claims 4 to 6
    (D) (a) an organoaluminum oxy compound and
    (b-III) In the presence of a catalyst for olefin polymerization comprising a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton, ethylene and an α-olefin having 3 to 20 carbon atoms are copolymerized, and characteristic:
    (D-i) density ranges from 0.850 to 0.980 g / cm 3,
    (D-ii) intrinsic viscosity measured in decalin at 135 ° C. in the range of 0.4 to 8 dl / g;
    Ethylene-α-olefin copolymer having a ethylene-α-olefin copolymer (B) and (C) is not the same as ethylene-α-olefin copolymer (D)
    Ethylene copolymer composition, characterized in that.
    [9" claim-type="Currently amended] The molded object characterized by the ethylene-based copolymer composition of any one of claims 1 to 8.
    [10" claim-type="Currently amended] The method of claim 9,
    The molded body is a single layer film or a single layer sheet.
    [11" claim-type="Currently amended] The method of claim 9,
    The molded article characterized in that the molded article is a multilayer film or a multilayer sheet.
    [12" claim-type="Currently amended] The method of claim 9,
    A molded article characterized in that the molded article is an injection molded article.
    [13" claim-type="Currently amended] The method of claim 9,
    A molded article characterized in that the molded article is an extrusion molded article.
    [14" claim-type="Currently amended] The method of claim 9,
    A molded article characterized in that the molded article is a fiber.
    [15" claim-type="Currently amended] The method of claim 9,
    A molded article characterized in that the molded article is a foamed molded article.
    [16" claim-type="Currently amended] The method of claim 9,
    The molded article characterized in that the molded article is an electric wire sheath.
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    同族专利:
    公开号 | 公开日
    CA2288686C|2004-02-24|
    WO1999046325A1|1999-09-16|
    CA2288686A1|1999-09-16|
    EP0982362A1|2000-03-01|
    CN1256703A|2000-06-14|
    ID22889A|1999-12-16|
    KR20020043241A|2002-06-08|
    CN1769336A|2006-05-10|
    KR100352785B1|2002-09-16|
    KR100352784B1|2002-09-16|
    CN100398597C|2008-07-02|
    CN1313526C|2007-05-02|
    US6329465B1|2001-12-11|
    EP0982362A4|2002-03-06|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1998-03-10|Priority to JP5863698
    1998-03-10|Priority to JP98-58636
    1999-03-10|Application filed by 나까니시 히로유끼, 미쓰이 가가쿠 가부시키가이샤
    2001-02-15|Publication of KR20010012350A
    2002-09-16|Application granted
    2002-09-16|Publication of KR100352785B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP5863698|1998-03-10|
    JP98-58636|1998-03-10|
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