Compositions Comprising a Substantially Random Interpolymer of at Least One Alpa-Olefin and at Least

专利摘要:
Disclosed are compositions comprising one or more substantially random copolymers of ethylene and vinylidene aromatic monomers or hindered aliphatic vinylidene monomers and optionally one or more C 3 -C 20 α-olefin monomers, and one or more tackifiers do. The compositions of the present invention are useful in adhesives and are useful in many fields, for example packaging and cardboard sealing, masking tapes, transparent office tapes, labels, decals, bandages, decorative and protective sheets (such as liners in shelves and drawers), floors Used to connect tiles, sanitary napkin / incontinence strips, sunscreens, and gaskets to automotive windows. The compositions of the present invention may find further use in various fields of application, such as sealants, coatings, molded articles, multilayer structures.
公开号:KR20000068456A
申请号:KR1019997001831
申请日:1997-09-04
公开日:2000-11-25
发明作者:패리크디팩；게스트마틴제이；스페쓰데이비드알
申请人:그래햄 이. 테일러；더 다우 케미칼 캄파니；
IPC主号:

专利说明:

Compositions Comprising a Substantially Random Interpolymer of at Least One Alpa-Olefin and at Least One Vinylidene Aromatic Monomer or Hindered Aliphatic Vinylidene Monomer}
The present invention relates to an olefin composition. In particular, the present invention relates to at least one substantially random copolymer of at least one α-olefin and a vinylidene aromatic monomer or a hindered aliphatic vinylidene monomer, preferably at least one pressure sensitive adhesive and optionally at least one extension or modification composition. Or, together with processing aids, at least one substantially random copolymer of ethylene and optionally at least one α-olefin and vinylidene aromatic monomer.
Substantially random copolymers of at least one alpha-olefin with vinylidene aromatic monomers or hindered aliphatic vinylidene monomers, including materials such as copolymers of alpha-olefin / vinyl aromatic monomers, are known in the art and are described in US Pat. As described in US Pat. No. 5,460,818, it provides a range of material structures and properties that make it useful in a variety of applications such as compatibilizers for blending polyethylene and polystyrene.
One particular aspect described in D'Anniello et al, Journal of Applied Polymer Science, Volume 58, pages 1701-1706 (1995) is that such copolymers can exhibit good elastic and energy dissipation properties. In other aspects, the selected copolymer may be useful for adhesive systems, as described in US Pat. No. 5,244,996 to Mitsui Petrochemical Industries Ltd.
Despite the utility of these rights, the industry is striving to improve the applicability of such substantial random copolymers. For example, in some cases it may be desired to manipulate the glass transition temperature of the substantially random copolymer so that the material based on the substantially random copolymer is applied as, for example, molded articles and sealants and adhesives.
The glass transition temperature of the polymer is one of the major physical variables that determine the mechanical properties. Below the glass transition temperature, polymers are typically rigid hard plastics that withstand loads. Above the glass transition temperature, the material exhibits more rubbery behavior. When the glass transition temperature is in the range of room temperature, the physical properties observed in the polymer may vary depending on the ambient conditions. Therefore, it is advantageous to be able to adjust the glass transition temperature of the polymer to achieve the required physical properties.
For example, in the case of substantially random copolymers having a glass transition temperature of about -25 to about 25 ° C., in some cases it is desirable to increase the glass transition temperature. For example, substantially random copolymers having a glass transition temperature of about room temperature are susceptible to harmful blocking. In addition, when the glass transition temperature is about room temperature, the product properties change with the actual temperature, which leads to undesirable product changes. In addition, when the glass transition temperature is room temperature, optimized utility is required in certain applications, such as in pressure sensitive adhesives.
One way to control the glass transition temperature of a copolymer is to change the type of comonomer and its amount present in the copolymer. For example, this approach is used to control the glass transition temperature of the acrylic copolymer.
An alternative to changing the comonomer content is to add another material with a different glass transition temperature to the base material. By the way, the addition of a low molecular weight brittle diluent can increase the glass transition temperature, but it is typically known to cause a decrease in mechanical properties such as tensile strength. Adding the kind of material described by the tackifier to a substantially random copolymer, in particular to an elastomeric copolymer, dilutes the polymer network structure, resulting in worse tensile properties, i.e., breaking tensile strength and elongation at break than the actual random copolymer alone. This was expected.
Compared to the substantially unmodified substantially random copolymers, the glass transition temperature is increased, and in particular comprises substantially random copolymers of at least one α-olefin and at least one vinylidene aromatic or hindered aliphatic monomer having a glass transition temperature above room temperature. It is necessary to provide a composition. There is a need for such compositions that are achieved without significant modification of the tensile properties. Comprising substantially random copolymers of one or more alpha-olefins and one or more vinylidene aromatic or hindered aliphatic monomers, which have better performance properties than unmodified polymers and further extend the usefulness of this type of interesting material. There is a need for improved hot melt adhesive formulations.
Hot melt adhesives generally comprise three components: a polymer, a tackifier and a wax. Each component may comprise a blend of two or more components, ie the polymer component may comprise a blend of two different polymers. The polymer provides bonding strength to the adhesive bonds. The tackifier provides tack to the adhesive that holds the item to be bonded, while setting and decreasing the viscosity of the system that allows the adhesive to be easily applied to the substrate. Moreover, tackifiers can be used to control the glass transition temperature of the formulation. The wax shortens the opening / closing time and reduces the viscosity of the system. The hot melt adhesive may typically further comprise oil as a filler and / or to reduce the viscosity of the system.
Hot melt adhesives based on polymers already used include ethylene vinyl acetate copolymer (EVA), atactic polypropylene (APP), amorphous polyolefins, low density polyethylene (LDPE) and homogeneous linear ethylene / alpha-olefin copolymers. have. Conventional hot melt adhesives typically reduce the viscosity of the system to a level that allows for easy application to a substrate using a large amount of tackifier, for example, a viscosity of up to about 5000 cps.
Pressure sensitive adhesives are materials that are active and permanently tacky at room temperature in their application and adhere firmly to a variety of dissimilar surfaces by application of light pressure, such as pressing by fingers. Despite its active tack, the pressure sensitive adhesive can be removed from the smooth surface without leaving significant residue. Pressure sensitive adhesives include protective tapes, transparent office tapes, labels, decals, bandages, decorative and protective sheets (such as liners in shelves and drawers), floor tiles, sanitary napkin / incontinence strips, sunscreens and Widely used in lifelong applications such as gasket bonding of automotive windows.
Historically, pressure sensitive adhesives were based on natural rubber and wood rosin, which were supported by solvents. Products providing such adhesives were prepared by applying a solution of adhesive on an appropriate backing layer and removing the solvent by volatilization process. However, waterborne adhesives and solid hot melt adhesives (HMA) have been developed in accordance with the increasing cost of solvents and the legal regulations for their release.
Historically, adhesives have been used in four types of polymers: elastomers (natural rubber, styrene-isoprene-styrene block copolymers, styrene-butadiene-styrene block copolymers and styrene-butadiene random copolymers), acrylics (butyl acrylate, Copolymers of 2-ethyl hexyl acrylate and methyl methacrylate, and the like), hydrocarbons (such as atactic polypropylene, amorphous polypropylene, poly-1-butene and low density polyethylene), and ethylene vinyl acetate. Recently, hot melt adhesives based on homogeneous linear and substantially linear ethylene polymers have been disclosed and patented.
Diene-based elastomers can be used in solvent-based, water-based and hot melt adhesives. However, such elastomer-based adhesive systems have disadvantages in that the unsaturated sites in the block copolymer backbone make the hot melt adhesive readily decomposed by the action of oxygen and ultraviolet rays.
Acrylic systems are stable to oxygen and ultraviolet light, but are inferior to diene-based elastomer systems in terms of tack balance, peel and creep durability required for pressure sensitive adhesive applications. In addition, such systems are typically only available in solvent-based and water-based systems, making them more disadvantageous for the reasons mentioned above.
Hydrocarbon-based systems have been developed to provide improved stability to oxygen and ultraviolet light, at least in part compared to diene-based elastomer systems, as well as the ability to be used in hot melt adhesive systems. Such hydrocarbon-based systems, including atactic polypropylene, higher grade alpha-olefins and copolymers of propylene, or poly-alpha-olefins, exhibit poor blends of properties. In particular, poly-1butene tends to crystallize slowly after application to the substrate, resulting in a severe loss of tack. When oil is added to increase the tack, the oil tends to migrate from the adhesive to the backing layer or substrate. Atactic polypropylene and poly-alpha-olefins exhibit low tensile strength, which leaves a low bond strength to delamination and residue on the substrate surface after delamination. Hydrocarbon-based systems are typically undesirable because of the limited capacity of low density polyethylene to accommodate the components of the formulations required to produce hot melt adhesives with suitable mechanical properties. Ethylene vinyl acetate based systems have increased elastic performance because higher vinyl acetate levels are selected, but are limited in terms of reduced compatibility with formulation components.
Hot melt adhesives based on homogeneous linear ethylene / alpha-olefin copolymers are disclosed in US Pat. No. 5,530,054.
The present invention relates to ethylene and vinylidene aromatic comonomers or hindered aliphatic vinylidene comonomers, and optionally at least one substantially random of a third comonomer selected from the group consisting of at least one C ₃ -C ₂₀ alpha-olefin. A composition comprising a copolymer and at least one tackifier. The invention also relates to one or more of comonomers of ethylene and vinylidene aromatic comonomers or hindered aliphatic vinylidene comonomers, and optionally a third comonomer selected from the group consisting of at least one C ₃ -C ₂₀ alpha-olefin. A composition comprising a substantially random copolymer, at least one tackifier, and at least one extension or modification composition or processing aid. In addition, the present invention provides the above extended or modified composition wherein the polymer or copolymer of paraffin wax, crystalline polyethylene wax, styrene block copolymer, ethylene vinyl acetate, styrene and / or alkyl-substituted styrene (such as alpha-methyl styrene), and ethylene And a homogeneous linear or substantially linear copolymer of at least one C ₃ -C ₂₀ alpha-olefin. The present invention also relates to such compositions in the form of layers of multi-layer food packaging structures, coatings, sealants, molded articles or adhesives of noise reduction devices.
Unless otherwise indicated, the following test procedure is used.
Density is measured according to ASTM D-792. The sample is annealed for 24 hours at atmospheric conditions before measurement.
Melt index (I ₂ ) is measured at 190 ° C./2.16 kg conditions (formally known as “condition (E)”) according to ASTM D-1238.
Molecular weight was determined by gel permeation chromatography (GPC) on a Waters 150 ° C high temperature chromatography apparatus (Polymer Laboratories 103, 104, 105 and 106) equipped with three mixed porous columns and operated at a system temperature of 140 ° C. Is measured. The solvent is 1,2,4-trichlorobenzene, from which a sample of 0.3% by weight solution is prepared for injection. The flow rate is 1.0 mL / min and the injection amount is 100 μl.
Molecular weight measurements were derived using a narrow molecular weight distribution polystyrene standard (manufactured by Polymer Laboratories) with its elution volume. Corresponding polyethylene molecular weights are described in the appropriate Mark-Houwink coefficients of polyethylene and polystyrene (Williams and Word, Journal of Polymer Science, Polymer Letters, Vol. 6, (621) 1968). Is derived by deriving the following equation.
M _polyethylene = a * (M _polystyrene) b
In the above equation, a = 0.4316 and b = 1.0. The weight average molecular weight (M _W ) is calculated by the usual method according to the formula M _W = Σw _i * M _i , where w _i and M _i represent the weight fraction and molecular weight of the fraction eluted from the GPC column, respectively.
Melt viscosity is measured in a disposable aluminum sample chamber using a viscometer (Brookfield Laboratories DVII + Viscometer) according to the following procedure. The spindle used is an SC-31 heated melt spindle suitable for viscosity measurements in the range of 10 to 100,000 cps. The cutting blade is used to cut the sample into pieces small enough to fit into the 1 inch wide and 5 inch long sample chamber. The sample is placed in a chamber and then inserted into a Brookfield Thermogel and properly secured by bent needle-nose pliers. The sample chamber has a notch at the bottom that fits the bottom of the Brookfield thermogel to prevent the chamber from rotating when the spindle is inserted and rotated. The sample is heated to 350 ° F. and additional sample is added until the molten sample is about 1 inch (2.54 cm) below the top of the sample chamber. The viscometer device is lowered and the spindle submerged in the sample chamber. The descent continues until the bracket on the viscometer is aligned on the thermogel. The viscometer continues to rotate and is set at a shear rate that induces a torque expressed in the range of 30 to 60%. The marking is made for about 15 minutes or every minute until the value stabilizes and the final marking is recorded.
G ', G "and peak tan deltas are measured as follows: Samples are examined using melt rheology techniques on an Rheometrics RDA-II Dynamic Analyzer. Temperature-step using a 7.9 mm diameter parallel plate form. The sweep is operated at approximately -70 ° C to 250 ° C at 5 ° C per step with a 30-second equilibrium delay in each step.The oscillation frequency is 1 radian / second and the initial 0.1% strain The autostrain function of) increases with a 100% adjustment in positive amount each time the torque is reduced to 10 g-cm The plate is used with an initial gap of 1.5 mm at 160 ° C. Maintained in the atmosphere to minimize oxidative degradation. Graph of G '(dynamic storage modulus of sample), G "(dynamic loss modulus of sample), tan delta (G' / G") and peak tan delta (of glass transition temperature) Graph).
The glass transition temperature is measured using a differential scanning calorimeter (DSC) at a scanning rate of 10 ° C./min from −75 to 150 ° C.
Probe tack is measured according to ASTM D2979-71 using Digital Polyken Probe Tack Tester TMI 80-02-01 (available from Testing Machines, Inc., New York). .
In the present invention, the term "copolymer" is used to denote a binary or terpolymer or the like. That is, at least one other comonomer is polymerized with ethylene to form a copolymer.
The term "hydrocarbyl" means any aliphatic, cycloaliphatic, aromatic, aryl substituted aliphatic, aryl substituted cycloaliphatic, aliphatic substituted aromatic, or cycloaliphatic substituted aromatic group. Aliphatic or cycloaliphatic groups are preferably saturated. Similarly, the term "hydrocarbyloxy" means a hydrocarbyl group having an oxygen bond between the hydrocarbyl group and the carbon atom to which it is attached.
In the present invention, in substantially random copolymers comprising alpha-olefins and vinylidene aromatic monomers or hindered aliphatic vinylidene monomers, the term "substantially random" means that the monomer distribution of the copolymer is described in J.C. Bernoulli statistical model or first or second Markovian as described in Randall, Polymer Sequence Determination, Carbon-13 NMR Method, Academic Press New York, 1977, pp 71-78. It can be described by a statistical model. Preferably, the substantially random copolymer comprising alpha-olefins and vinylidene aromatic monomers does not comprise at least 15% of the total vinylidene aromatic monomers in blocks of at least 3 units of vinylidene aromatic monomers. More preferably, the copolymer is not characterized by high isotactic or syndiotactic. This indicates that the peak region corresponding to the main chain methylene and methine carbons representing the mesodiode sequence or racemic diad sequence in the 13 C-NMR spectrum of the substantially random copolymer exceeds 75% of the total peak region of the main chain methylene and methine carbons. It means not to.
Any number listed in the present invention includes all values from the low value to the high value of the increment of one unit provided that there is at least two units of space between any low value and the high value. . As an example, if the amount of a component or a process variable such as temperature, pressure and time, etc. is said to be for example 1 to 90, preferably 20 to 80, more preferably 30 to 70, it is 15 to 85 It is understood that values such as, 22 to 68, 43 to 51, 30 to 32 and the like are explicitly listed herein. For values less than 1, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate. These are only examples of particularly intended, and all possible combinations of numerical values between the lowest and highest values are considered to be expressly described herein in a similar manner.
Copolymers suitable for use as the composition of the present invention or as a component thereof are copolymers prepared by polymerizing at least one alpha-olefin with at least one vinylidene aromatic monomer and / or at least one hindered aliphatic vinylidene monomer. Non-limiting examples include copolymers of ethylene, at least one vinylidene aromatic monomer, and optionally at least one alpha-olefin.
Examples of suitable alpha-olefins include those containing 2 to about 20, preferably 2 to about 12, more preferably 2 to about 8 carbon atoms. Especially preferred are ethylene, propylene, butene-1, 4-methyl-1-pentene, hexene-1 and octene-1. Other suitable alpha-olefin monomers include norbornene.
Examples of suitable vinylidene aromatic monomers are those represented by the following formula.
Wherein R ¹ is selected from the group of radicals consisting of hydrogen, alkyl radicals having from 1 to about 4 carbon atoms, preferably hydrogen or methyl; Each R ² is independently selected from hydrogen and alkyl radicals of 1 to about 4 carbon atoms, preferably hydrogen or methyl, Ar is a phenyl group, or halo, C _1-4 alkyl and C _1- Phenyl group substituted with 1 to 5 substituents selected from the group consisting of ₄ -haloalkyl; n has a value of 0 to about 6, preferably 0 to about 2, more preferably 0. Exemplary monovinylidene aromatic monomers include styrene, vinyl toluene, alpha-methyl styrene, t-butyl styrene, chlorostyrene and include all isomers of these compounds. Especially suitable such monomers are styrene, and lower alkyl- or halogen-substituted derivatives thereof. Preferred monomers include styrene, alpha-methyl styrene, lower alkyl- or phenyl ring substituted derivatives of styrene such as ortho- meta- and para-methylstyrene, ring halogenated styrenes, para-vinyl toluene, or mixtures thereof. More preferred monovinylidene aromatic monomer is styrene.
The term "hindered aliphatic or cycloaliphatic vinylidene monomer" means an addition polymerizable vinylidene monomer corresponding to the formula:
Wherein, A ¹ is (sterically bulky) aliphatic substituent which is bulky arrangement of up to 20 carbon atoms, R ¹ is selected from the group consisting of alkyl radicals having from hydrogen, and from 1 to about 4 carbon atoms, preferably Hydrogen or methyl; Each R ² is independently selected from hydrogen and alkyl radicals of 1 to about 4 carbon atoms, preferably hydrogen or methyl, or alternatively R ¹ and A ¹ together form a ring structure. As used herein, the term "bulky atomic arrangement" means that the monomers providing such substituents are not capable of addition polymerization with standard Ziegler-Natta polymerization catalysts at rates comparable to ethylene polymerization. Preferred hindered aliphatic or cycloaliphatic vinylidene monomers are tertiary or quaternary substitutions of one carbon atom providing ethylenic unsaturation. Examples of such substituents are cyclic aliphatic groups such as cyclohexyl, cyclohexenyl, cyclooctenyl, or cyclic alkyl or aryl substituted derivatives, tert-butyl, and norbornyl. Most preferred hindered aliphatic vinylidene compounds are various isomeric vinyl-ring substituted derivatives of cyclohexene and substituted cyclohexene, and 5-ethylidene-2-norbornene. Especially suitable are 1-, 3-, and 4-vinylcyclohexene.
Copolymers of at least one alpha-olefin and at least one monovinylidene aromatic monomer and / or at least one hindered aliphatic or cycloaliphatic vinylidene monomer used in the present invention are substantially random polymers. These copolymers usually contain from about 1 to about 65 mole% of at least one vinylidene aromatic monomer and / or hindered aliphatic or cycloaliphatic vinylidene monomers, and from about 35 to about 99 mole% of at least one carbon atom. Aliphatic alpha-olefins that are 20. If the substantially random copolymer has less than 1 to 5 mole percent of one or more vinylidene aromatic monomers and / or hindered aliphatic or cycloaliphatic vinylidene monomers, the substantial random copolymer will impart crystalline properties to the adhesive system. If the substantially random copolymer has 5 to less than 25 mole percent of one or more vinylidene aromatic monomers and / or hindered aliphatic or cycloaliphatic vinylidene monomers, the substantial random copolymer will impart elastomeric properties to the adhesive system. If the substantially random copolymer has 25-50 mole percent of one or more vinylidene aromatic monomers and / or hindered aliphatic or cycloaliphatic vinylidene monomers, the substantially random copolymer will impart amorphous properties to the adhesive system.
When a substantially random copolymer is used as the strength imparting component of the adhesive, the copolymer has a number average molecular weight (Mn) of usually about 1,000 or more, preferably about 5,000 to about 1,000,000, more preferably about 10,000 to about 500,000, Most preferably 50,000 to about 300,000. As described below, very low molecular weight ethylene polymers, one of which comprises an ultra low molecular weight copolymer of ethylene and one or more vinylidene aromatic monomers and / or hindered aliphatic or cycloaliphatic vinylidene monomers, If not, it can be suitably used in the embodiments of the present invention as a tackifier or modifier.
As described below, certain amounts of atactic vinylidene aromatic homopolymers can be formed by homopolymerization of vinylidene aromatic monomers at elevated temperatures during the preparation of substantial random copolymers. In general, the higher the polymerization temperature, the higher the amount of homopolymer formed. The presence of vinylidene aromatic homopolymers is generally not harmful for the purposes of the present invention and can be tolerated. If necessary, the vinylidene aromatic homopolymer can be separated from the copolymer by extraction techniques such as selective precipitation from a copolymer or a solution with no solvent for the vinylidene aromatic homopolymer. For the purposes of the present invention it is preferred that there are up to 20% by weight, preferably up to 15% by weight, more preferably up to 10% by weight of vinylidene aromatic homopolymer, based on the total weight of the copolymer.
Substantially random copolymers can be modified by typical grafting, hydrogenation, functionalization or other reactions well known to those skilled in the art. The polymer can be easily sulfonated or chlorolated to provide derivatives functionalized according to established techniques.
Substantially random copolymers are prepared by polymerizing a mixture of polymerizable monomers in the presence of a metallocene or constrained geometry catalyst.
Substantial random copolymers may be prepared as described in US Patent Application No. 545,403, filed Jul. 3, 1990, corresponding to EP-A-0,416,815, filed by James C. Stevens et al. Preferred operating conditions for this polymerization reaction are pressures from atmospheric pressure to 3000 atmospheres (300 MPa) and temperatures from -30 to 200 ° C.
Examples of suitable catalysts and methods of making substantially random copolymers are described in EP-A-416,815; EP-A-514,828; EP-A-520,732; US application 241,523, filed May 12, 1994; US 5,055,438, 5,057,475, 5,096,867, 5,064,802, 5,132,380, 5,189,192, 5,321,106, 5,347,024, 5,350,723, 5,374,696, and 5,399,635.
In addition, substantially random alpha-olefin / vinylidene aromatic copolymers are described in WO 95/32095 (John G. Bradfute et al., W. R. Grace &Co.); WO 94/00500 to R. B. Pannell, Exxon Chemical Patents, Inc .; Plastics Technology, p. 25 (September 1992).
In addition, substantially random alpha-olefin / vinylidene aromatic copolymers can be prepared by the method described in JP 07/278230 using a compound represented by the following formula.
In the above formula, Cp ¹ and Cp ² are each a cyclopentadienyl group, an indenyl group, a fluorenyl group, or a substituent thereof; R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms, an alkoxyl group, or an aryloxyl group; M is a Group IV metal, preferably Zr or Hf, most preferably Zr; R ³ is an alkylene group or silandiyl group used to crosslink Cp ¹ and Cp ² .
Also suitable are substantially random copolymers having at least one alpha-olefin / vinyl aromatic / vinyl aromatic / alpha-olefin tetrad. This copolymer contains an additional signal having an intensity that is at least three times greater than peak to peak noise. This signal is present in the chemical shift ranges 43.75-44.25 ppm and 38.0-38.5 ppm. In particular, main peaks are observed at 44.1, 43.9 and 38.2 ppm. Quantum test NMR experiments show that the signal in the chemical shift region 43.75-44.25 ppm is methine carbon and the signal in the region 38.0-38.5 ppm is methylene carbon.
To measure the carbon-13 NMR chemical shift of the copolymer, the following procedures and conditions are used. 5 to 10% by weight polymer solution is 50% by volume of 1,1,2,2-tetrachloroethane-d ₂ and 50% by volume of 0.10 mole chromium tris (acetylacetonate) in 1,2,4-trichlorobenzene It is prepared from a mixture consisting of. NMR spectra were obtained at 130 ° C. using reverse gated decoupling order, width greater than 90 ° and pulse delay greater than 5 seconds. Spectra were referenced to the isolated methylene signal of the polymer assigned to 30,000 ppm.
This new signal is followed by a sequence containing two head-tail vinyl aromatic monomers with one or more alpha-olefin insertions before and after, such as ethylene / styrene / styrene / ethylene tetrad, where the styrene monomer insertion of tetrade is 1 2, which occurs exclusively in a head-to-tail fashion. Those skilled in the art that for such tetrades comprising vinyl aromatic monomers rather than styrene, and alpha-olefins rather than ethylene, cause ethylene / vinyl aromatic monomers / vinyl aromatic monomers / ethylene tetrades to produce carbon-13 NMR peaks with similar but slightly different chemical shifts. Is understood by.
The copolymer is prepared by carrying out the polymerization in the presence of a catalyst as represented by the following formula at a temperature of about −30 to about 250 ° C., optionally in the presence of an active promoter.
In the above formula, each C p is independently a substituted cyclopentadienyl group π-bonded to M; E is C or Si; M is a Group IV metal, preferably Zr or Hf, most preferably Zr; Each R is independently H, hydrocarbyl, silahydrocarbyl, or hydrocarbylsilyl (comprising about 30 or less, preferably 1 to 20, more preferably 1 to about 10 carbon or silicon atoms) ; Each R ′ is independently H, halo, hydrocarbyl, hydrocarbyloxy, silahydrocarbyl, hydrocarbylsilyl (up to about 30, preferably 1 to about 20, more preferably 1 to about 10 Carbon or silicon atoms), or two R ′ groups together may be C _1-10 hydrocarbyl substituted 1,3-butadiene; m is 1 or 2. In particular, suitable substituted cyclopentadienyl groups include those represented by the following formulas.
Wherein R is each independently H, hydrocarbyl, silahydrocarbyl, or hydrocarbylsilyl (up to about 30, preferably 1 to about 20, more preferably 1 to about 10 carbon or silicon atoms Or two R groups together form a divalent derivative of such a group. Preferably, R is independently of each other (including all suitable isomers) hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl or silyl or (where appropriate) these two R groups linked together. To form a molten ring system such as indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluororenyl or octahydrofluororenyl.
Examples of particularly preferred catalysts include racemic (dimethylsilandiyl (2-methyl-4-phenylindenyl) zirconium dichloride, racemic (dimethylsilandiyl (2-methyl-4-phenyl-indenyl) zirconium 1 , 4-diphenyl-1,3-butadiene, racemic (dimethylsilanediyl (2-methyl-4-phenylindenyl) zirconium di-C _1-4 alkyl, racemic (dimethylsilanediyl (2-methyl 4-phenylindenyl) zirconium di-C _1-4 alkoxide, or any combination thereof.
Further methods of preparing substantially random copolymers are described in the literature. Longo and Grassi, Makromol. Chem. Vol. 191, pages 2387-2396, 1990 and in D'Anniello et al., Journal of Applied Polymer Science, Vol. 58, pages 1701-1706, 1995, reported the use of a catalyst system based on methylalumoxane (MAO) and cyclopentadienyltitanium trichloride (CpTiCl ₃ ) to prepare ethylene-styrene copolymers. Xu and Lin, Polymer Preprints, Am. Chem. Soc., Div. Polvm. Chem., Vol. 35, pages 686, 587, 1994 reported a copolymerization using a TiCl ₄ / NdCl ₃ / Al (iBu) ₃ catalyst to provide a random copolymer of styrene and propylene. Lu et al., Journal of Applied Polymer Science, Vol. 53, pages 1453-1460, 1994, describe the copolymerization of ethylene and styrene using TiCl ₄ / NdCl ₃ / MgCl ₂ / Al (Et) ₃ catalysts. The preparation of copolymers of alpha-olefin / vinyl aromatic monomers such as propylene / styrene and butene / styrene is described in US Pat. No. 5,244,996 to Mitsui Petrochemical Industris Ltd.
The polymerization can be carried out in solution, slurry or gas phase polymerization. In addition, the polymerization may be carried out in a batch or continuous polymerization process. In a continuous process, ethylene, vinylidene aromatic monomers or hindered aliphatic vinylidene, and solvent and optional propylene or alternative tertiary monomers are fed continuously to the reaction zone from which the polymer product is continuously removed.
In general, substantially random copolymers can be polymerized under the conditions of a Ziegler-Natta or Kaminsky-Shin type of polymerization reaction, ie, reactor pressures from atmospheric to 3500 atmospheres (350 MPa). Reactor temperature is typically from -30 to 200 ° C. Preferably, the reactor temperature is at least 80 ° C., typically from 100 to 200 ° C., preferably from 100 to 150 ° C., and higher temperatures in this range, ie at least 100 ° C., are advantageous for producing low molecular weight polymers. Do. Polymerization at temperatures above the self polymerization temperature of each monomer can result in the formation of some homopolymer polymerization products resulting from free radical polymerization.
In the case of a slurry polymerization process, the substantially random copolymer may use the catalyst described above supported on an inert support such as silica. As a practical limitation, slurry polymerization takes place in liquid diluents where little polymerization product is dissolved. Preferably, the diluent for slurry polymerization is at least one hydrocarbon having 5 or less carbon atoms. If desired, saturated hydrocarbons such as ethane, propane or butane may be used in whole or in part as diluents. Similarly, alpha-olefin monomers or mixtures of other alpha-olefin monomers can be used wholly or partly as diluents. Most preferably, the diluent comprises a single or a plurality of monomers to be polymerized into at least the major part.
The glass transition temperature of the substantially random copolymer increases with increasing molar ratio of vinylidene aromatic comonomer or hindered aliphatic vinylidene comonomer. This suggests that by adjusting the content of vinylidene aromatic comonomer or the hindered aliphatic vinylidene comonomer, the tackiness of the adhesive system can be controlled. In particular, a substantially random ethylene / styrene copolymer comprising less than 1 to 5 mole percent styrene will have a Tg of approximately −15 to -20 ° C., and a substantially random ethylene / styrene copolymer comprising more than 25 mol% styrene It will have a Tg of approximately 0 to 30 ° C., where Tg is measured by differential scanning calorimetry. Thus, very low molecular weight copolymers of ethylene and one or more vinylidene aromatic comonomers or hindered aliphatic vinylidene comonomers can be used as optional tackifier components of the adhesive system. Those skilled in the art will appreciate that the incorporation of third monomers, such as other alpha-olefins, produces glass transition temperatures different from those described above.
In addition to or as an alternative to the control of the styrene content of substantially random copolymers, where compositions having a glass transition temperature of at least −10 ° C. are required, in particular when the composition is required to maintain elastomeric properties, such compositions are at least It would be desirable to include at least one substantially random copolymer and at least one tackifier.
In the present invention, the term "adhesive" refers to any of various hydrocarbon-based compositions useful for raising the glass transition temperature of a substantially random copolymer to at least 5 ° C. or more and / or imparting tack to a hot melt adhesive comprising a substantially random copolymer. Means. ASTM D-1878-61T is defined as "the property of a material that can cause a strong bond that can be measured immediately upon contact with other surfaces."
Tackifying resins are obtained by polymerization of petroleum and terpene feed streams and by derivation of wood, gum and tall oil rosin. Several types of tackifiers include wood rosin, tall oil and tall oil derivatives, cyclopentadiene derivatives as described in British patent application GB 2,032,439A. Other types of tackifiers include aliphatic C ₅ resins, polyterpene resins, hydrogenated resins, mixed aliphatic-aromatic resins, rosin esters, natural and synthetic terpenes, terpene phenols, hydrogenated rosin esters.
Rosin is a commercially produced material naturally produced in oleo rosin of pine and is typically derived from oleo resinous extracts of living trees, from old stumps, and from tall oil produced as a by-product of kraft paper making. After obtained, the rosin can be treated by hydrogenation, dehydrogenation, polymerization, esterification and other workup processes. Rosin is typically classified as gum rosin, wood rosin or tall oil rosin, indicating its origin. This material can be used in the form of esters of unmodified and polyhydric alcohols, and can be polymerized through molecular inherent unsaturation. These materials are commercially available and can be blended into the adhesive composition using standard blending techniques. Representative examples of such rosin derivatives include pentaerythritol esters of tall oil, gum rosin, wood rosin or mixtures thereof.
Examples of the aliphatic resins may be purchased under the trade names Escorez, Piccotac, Mercures, Wingtack, Hi-Rez, Quintone, Tackirol and the like. Examples of the polyterpene resin include those available under the trade names Nirez, Piccolute, Wingtack, Zonarez, and the like. Examples of the hydrogenated resin include those available under the trade names Escorez, Arkon, Clearon and the like. Examples of mixed aliphatic-aromatic resins include those available under the trade names Escorez, Regalite, Hercures, AR, Imprez, Norsolene M, Marukorez, Arkon M, Quintone, Wingtack, and the like. One kind of particularly preferred pressure sensitive adhesives includes styrene / alpha-methylene styrene pressure sensitive adhesives available from Hercules. Other tackifiers can be used provided they are compatible with homogeneous linear or substantially linear ethylene / alpha-olefin copolymers and optional plasticizers.
Suitable adhesives may be selected based on the evaluation criteria described in Hercules in J. Simons, Adhesive Age, "The HMDA Concept: A New Method for Selection of Resin", November 1996 sus. This reference discusses the importance of the polarity and molecular weight of the resin in determining compatibility with polymers. For practical random copolymers useful in the practice of the present invention, it is pointed out that low molecular weight polar resins are preferred.
The tackifier is typically present in the composition of the present invention in an amount of at least 10, typically at least 20% by weight or more. The tackifier will be present in a weight percent of up to 90, preferably up to 75, most preferably up to 70.
In the case of substantially random copolymers of one or more alpha-olefins and monovinylidene aromatic monomers, in particular in the case of substantially random copolymers having a high content of monovinylidene aromatic monomers, the preferred pressure-sensitive adhesive is somewhat to promote compatibility. Will have aromatic properties. As an initial indicator, compatible tackifiers are also known to be compatible with ethylene / vinylacetate having 28% by weight of vinyl acetate. Particularly suitable types of tackifiers are the trade names Wintack 86 and Hercotac 1149, Eastman H-130, and styrene / alpha-methyl styrene tackifiers. Another preferred tackifier is Piccotex 75, a pure monomeric hydrocarbon resin having a glass transition temperature of 33 ° C. available from Hercules.
Notably, when a commercial pressure sensitive adhesive is used, the glass transition temperature is increased in comparison with the unmodified substantially random copolymer, and the tensile strength is increased without a significant decrease in breaking elongation. There is an unexpected advantage associated with the increase in the glass transition temperature of the substantially random copolymer. Although this effect is true for substantially random copolymers with higher or lower comonomer content, this effect is the most resilient 45-65% by weight of monovinylene aromatics or hindered aliphatic comonomers of substantially random copolymers. It is said to be the best for substantially random copolymers having This is in contrast to expectations, and typically, when low molecular weight brittle solids are applied to an elastomeric solid, the low molecular weight material dilutes the polymer network structure, resulting in less tensile and breaking strength than that of the polymer alone.
Improved tensile strength is of value in numerous applications such as adhesives, elastomeric membrane applications, automotive parts, wire and cable sheaths, durable articles (such as appliances), gaskets and shoe soles.
For example, in the case of adhesive formulations, when the glass transition temperature of the substantially random copolymer is -20 ° C or lower, the composition exhibits poor peel strength and tack. By the addition of the adhesive, the peeling strength of a formulation increases by raising glass transition temperature to 0 degreeC.
In the case of improved durability against blocking, it is desired to avoid the bonding of polymer pellets or the bonding between each other during transport and storage. Thus, using a composition of the present invention comprising substantially random copolymers and tackifiers, such as the glass transition temperature is above the temperature during transport and storage, increases the stiffness of the polymer pellets and improves durability against deformation during transport and storage. To exercise. In another embodiment, the pellets of the substantially random copolymer may be coated with the adhesive to produce a surface composition comprising the adhesive and the substantially random copolymer to minimize blocking.
Compositions of the present invention comprising an adhesive will have additional utility in the field of noise reduction. For example, in order to reduce noise, the material must be able to dissipate high energy over a wide frequency range of normal sound under atmospheric conditions. This occurs when the glass transition temperature is about -20 to about 10 ° C. Compositions of the present invention exhibiting glass transition temperatures in this range will reduce noise in various structures, such as automobiles.
Processing aids, also referred to as plasticizers herein, are optionally provided to reduce the viscosity of compositions such as adhesives and are obtained from phthalates, such as dioctyl phthalate and diisobutyl phthalate, natural oils such as lanolin, paraffin, petroleum refining Naphthene and aromatic oils, and liquid resins obtained from rosin or petroleum feeds.
Exemplary types of oils useful as processing aids are white mineral oils (such as the trade name "Kaydol" oil available from Witco Rotor) and the trade name "Shellflex 371" naphthene oil (available from Shell Oil Company). Another suitable oil is the trade name "Tuflo" oil (available from Lyondell).
When processing aids are used, they are used in an amount of at least 5% in the compositions of the present invention. Processing aids are typically present in amounts of up to 60% by weight, preferably up to 30% by weight and most preferably up to 20% by weight.
Compositions comprising ethylene and one or more vinylidene aromatic monomers or hindered aliphatic vinylidene monomers and substantially random copolymers of optional C ₃ -C ₂₀ alpha-olefins are optionally modified by inclusion of an extension or modified composition. Can be. Exemplary extension or modification compositions include paraffin waxes, crystalline polyethylene waxes, and / or homogeneous linear or substantially linear ethylene / alpha-olefin copolymers.
Similarly, the compositions of the present invention may further comprise homogeneous linear or substantially linear ethylene / alpha-olefin copolymers as extension or modification compositions. In particular, when such a copolymer is an elastomer, modification of the composition with a homogeneous linear or substantially linear ethylene / alpha-olefin copolymer extends the composition when it is a composition comprising substantially random copolymers having a high styrene content, Adhesives comprising substantially random copolymers with a low styrene content tend to improve the tack and modulus of the adhesives.
Homogeneous linear or substantially linear ethylene / alpha-olefin copolymers are ethylene polymers prepared using single site, single site metallocenes, or single site strained geometry catalysts. The term homogeneous means that any comonomer is randomly distributed within the molecules of a given copolymer and substantially all of the copolymer molecules have the same ethylene / comonomer ratio in that copolymer. DSC melt peaks of homogeneous linear or substantially linear ethylene polymers will expand as the density decreases and / or the number average molecular weight decreases. However, unlike heterogeneous polymers, when the homogeneous polymer has a melt peak of 115 ° C. or higher (as in the case of polymers having a density of 0.940 g / cm ³ or higher), such polymers typically do not additionally have a distinct low temperature melt peak. .
The homogeneous linear or substantially linear copolymers useful in the present invention are further different from the low density polyethylenes produced in high pressure processes. In one example, low density polyethylene is an ethylene homopolymer having a density of 0.900 to 0.935 g / cm ³ , while uniform linear or substantially linear copolymers useful in the present invention have a density ranging from 0.900 to 0.935 g / cm ³ . Requires the presence of reducing comonomers.
Uniform linear or substantially linear copolymers useful in the present invention are typically characterized by having a narrow molecular weight distribution (Mw / Mn). For linear and substantially linear copolymers the Mw / Mn is typically 1.5 to 2.5, preferably 1.8 to 2.2.
Additionally or alternatively, the homogeneity of the polymer can be described by the Short Chain Branching Distribution Index (SCBDI) or Composition Distribution Breadth Index (CDBI), which has a comonomer content within the median 50% of the total molar comonomer content. It is defined as the weight percent of the molecule. The SCBDI of a polymer can be easily calculated from data obtained from techniques known in the art such as, for example, temperature rising elution classification (abbreviated as TREF), which is described, for example, in Wild et al., Journal of Polymer Science, Poly. Phys. Ed., Vol. 20, p. 441 (1982), US Pat. No. 4,798,081 (Hazlitt et al.) Or US Pat. No. 5,089,321 (Chum et al.). For homogeneous linear or substantially linear copolymers useful in the present invention, the SCBDI or CDBI is preferably at least 50%, more preferably at least 70%, and at least 90% of SCBDI and CDBI are easily obtained.
Substantially linear ethylene copolymers are homogeneous copolymers with long chain branches. Due to the presence of such long chain branches, the substantially linear ethylene copolymers are further characterized by having a melt flow rate (I ₁₀ / I ₂ ) which can vary independently of the polydispersity index and is also referred to as molecular weight distribution (Mw / Mn). . This feature is consistent with substantially linear ethylene polymers with high processability despite narrow molecular weight distribution. When substantially linear ethylene copolymers are used in the practice of the present invention, such copolymers are characterized as having a copolymer backbone substituted with 0.1 to 3 long chains per 1000 carbons.
Qualitatively and quantitatively methods for determining the amount of long chain branching are known in the art. Qualitative methods for determining the presence of long chain branches can be found, for example, in US Pat. Nos. 5,272,236 and 5,278,272. As described, a gas extrusion flow meter (GER) can be used to measure the rheological process index (PI), the critical shear rate at the onset of surface melt fracture, and the critical shear stress at the onset of total melt fracture, The presence or absence of long chain branching as described below is indicated.
Quantitative methods for determining the presence of long chain branches include, for example, US Pat. Nos. 5,272,236 and 5,278,272; Randall (Rev. Macromol. Chem. Phys., C29 (2 & 3), p. 285-297) discussing the determination of long chain branching using 13C nuclear magnetic resonance spectroscopy, Zimmm, GH and Stockmayer, WH, J. Chem. Phys., 17, 1301 (19490); and gel permeation chromatography coupled with low angle laser light scattering detector (GPC-LALLS), and gel permeation chromatography coupled with differential viscometer detector (GPC-DV). See Rudin, A., Modern Methods of Polymer Characterization, John Wiley & Sons, New York (1991) pp. 103-112, and A. Willen de Groot and P. Steve Chum, both of The. Dow Chemical Company, at the October 4, 1994 conference of the Federation of Analytical Cmemistry and Spetroscopy Society (FACSS) in St. Louis, Missouri, reports that the presence of long chain branches in linear ethylene polymers where GPC-DV is substantially Illustrates that this is a useful technique to quantify In particular, deGroot and Chum have found that the presence of long chain branches in substantially linear ethylene polymers correlates well with the level of long chain branches measured using ¹³ C NMR.
The homogeneous linear or substantially linear extending polymer will be a copolymer of ethylene with one or more C ₃ -C ₂₀ α-olefins. Exemplary C ₃ -C ₂₀ α-olefins include propylene, isobutylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene and 1-octene. Preferred C ₃ -C ₂₀ α-olefins are homogeneous linear or substantially mono-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene and 1-octene, more preferably 1-hexene and 1-octene The linear extending polymer may also be a copolymer of ethylene, one or more C ₃ -C ₂₀ α-olefins and unconjugated dienes having 6 to 15 carbon atoms. Representative examples of suitable nonconjugated dienes include (a) straight chain acyclic dienes such as 1,4-hexadiene, 1,5-heptadiene and 1,6-octadiene; (b) 5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene; And branched chain acyclic dienes such as 3,7-dimethyl-1,7-octadiene; (c) monocyclic alicyclics such as 4-vinylcyclohexene, 1-allyl-4-isopropylidene cyclohexane, 3-allylcyclopentene, 4-allylcyclohexene, and isopropenyl-4-butenylcyclohexene Dienes; (d) dicyclopentadiene; Alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornene (eg 5-methylene-2-norbornene); 5-methylene-6-methyl-2-norbornene; 5-methylene-6,6-dimethyl-2-norbornene; 5-propenyl-2-norbornene; 5- (3-cyclopentenyl) -2-norbornene; 5-ethylidene-2-norbornene; Polycyclic alicyclic melted and crosslinked ring dienes such as 5-cyclohexylidene-2-norbornene and the like.
Preferred unconjugated dienes include 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 7-methyl-1,6-octadiene, Piperylene and 4-vinylcyclohexene. Suitable conjugated dienes are piperylenes.
The ethylene / α-olefin copolymer will have a density of 0.850 to 0.965 g / cm ³ , preferably 0.850 to 0.900 g / cm ³ and most preferably 0.870 to 0.890 g / cm ³ .
The ethylene / α-olefin copolymer can be high molecular weight or low molecular weight. Suitable number average molecular weights are from 3,000 to 100,000, preferably from 3,000 to 60,000. In certain applications, ethylene / a-olefin copolymers having a number average molecular weight of less than 20,000, preferably less than 12,000, will be preferred.
Homogeneously branched linear ethylene / a-olefin copolymers can be prepared using polymerization methods (eg, described in US Pat. No. 3,645,992 by Elston) that provide a uniform short chain branching distribution. In its polymerization process, Elstone uses a soluble vanadium catalyst system to prepare such polymers. However, Mitsui Petrochemical and Exxon Chemical Company are using single site catalyst systems to produce polymers with so-called uniform linear structures. Homogeneous linear ethylene / α-olefin copolymers are currently available from Mitsui Petrochemical Company under the trade name “Tafmer” and from Exxon Chemical Company under the trade name “Exact”. .
Substantial linear ethylene / α-olefin copolymers are available from The Dow Chemical Company as trade name Affinity polyolefin plastomers.
In other embodiments, ultra low molecular weight ethylene polymers can be used as extension or modification compositions. Ultra low molecular weight ethylene polymers are disclosed and claimed in WO 97/26287.
The ultralow molecular weight polymers used are comonomers selected from the group consisting of C ₃ -C ₂₀ α-olefins, styrene, alkyl substituted styrenes, tetrafluoroethylene, vinylbenzocyclobutane, unconjugated dienes and cycloalkenes, ethylene alone It may be a polymer or a copolymer of ethylene.
The ultra low molecular weight polymer will have a number average molecular weight of less than 8200, preferably less than 6000, more preferably less than 5000. Such ultra low molecular weight polymers typically have a number average molecular weight of at least 800, preferably at least 1300.
In contrast to paraffin wax and crystalline ethylene homopolymer or copolymer wax, the ultra low molecular weight polymer will have an M _w / M _n of 1.5 to 2.5, preferably 1.8 to 2.2.
Ultra low molecular weight ethylene polymers are characterized by a peak crystallization temperature which results in low polymer and blend viscosity, but greater than the peak crystallization temperature of the corresponding high molecular weight material of the same density. In adhesive applications, the increase in peak crystallization temperature changes the increased heat resistance, such as improved creep resistance in pressure sensitive adhesives and improved shear adhesion failure temperature (SAFT) in hot melt adhesives.
When the ultra low molecular weight ethylene polymer is a copolymer of ethylene and one or more vinylidene comonomers or hindered aliphatic vinylidene comonomers, it can be used as an adhesive (discussed above). Moreover, as mole% of ethylene increase, the crystallinity of the copolymer will increase in the same way. Thus, ultralow molecular weight copolymers of ethylene and less than 10 mole percent of one or more vinylidene aromatic comonomers or hindered aliphatic vinylidene comonomers may be useful as waxes to control the opening and closing times of the adhesive system.
In other embodiments, typical waxes can be used as extension or modification compositions. Modification of the adhesive with paraffin wax or crystalline polyethylene wax will improve creep resistance and high temperature performance, such as SAFT, and will reduce the opening and closing times of the adhesive including substantially random copolymers with high styrene content.
Exemplary typical waxes are CP, under the trade names Polywax 500, Polywax 1500, Polywax 1000, and Polywax 2000, and petroleum incorporated (Tulsa, Oklahoma) and product symbols 1230, 1236, 1240, 1245, 1246, 1255, 1260, and 1262. It is available from the hall.
Polywax 2000 has a molecular weight of about 2000, a M _w / M _n of about 1.0, a density at 16 ° C. of about 0.97 g / cm ³ and a melting point of about 126 ° C.
CP Hall 1246 paraffinic wax is available from CP Hall (Stow, Ohio). CP Hall 1246 paraffinic wax has a melting point of 143 ° F. (62 ° C.), a viscosity of 210 ° F. (99 ° C.) of 4.2 centipoise and a specific gravity at 73 ° F. (23 ° C.) of 0.915.
Typical waxes useful in the adhesives of the invention will typically have a density of at least 0.910 g / cm ³ . Such wax will have a density of less than 0.970 g / cm ³ , preferably less than 0.965 g / cm ³ .
Additives such as antioxidants (hindered phenols such as Irganox 1010, Irganox B900, Irganox 1076), phosphites (Irgafos 168), UV stabilizers, Kling additives (polyisobutylene) antiblocking additives, colorants, pigments and Fillers may also be included in the compositions of the present invention that do not interfere with the improved properties found by the inventors.
Such additives may be used in functionally equivalent amounts known to those skilled in the art. For example, the amount of antioxidant used prevents the polymer or composition from carrying out oxidation at the temperature and environment in which it is used during manufacture, storage of the polymer and end use. The amount of such antioxidants is usually from 0.05 to 10, preferably from 0.1 to 5, more preferably from 0.1 to 2% by weight, based on the weight of the composition. In use, the antioxidant is most typically present in an amount of less than 0.5% by weight based on the total weight of the composition.
Similarly, any amount of other presumed additives provides the desired color from the colorant or pigment to give the polymer or polymer blend barrier, to produce the desired amount of filler load, and to produce the desired result. It is functionally equivalent in order to. Such additives may typically be used in the range of about 0.05 to about 50, preferably about 0.1 to about 35, more preferably about 0.2 to about 20 weight percent, based on the weight of the substantially random copolymer, but the filler is substantially random air. Up to 90% by weight based on the weight of the coalescing may be used.
Compositions of the present invention can be prepared by standard melt blending procedures. In particular, the substantially random copolymer (s), tackifier (s) and optional processing aid (s) are obtained at a temperature suitable for obtaining the formation of a uniform melt blend, typically at a temperature of 100-200 ° C. Melt blended under an inert gas blanket until lost. Any method of mixing that produces a uniform blend without reducing hot melt components is satisfied through the use of a heating vessel with a stirrer.
Moreover, substantially random copolymer (s), tackifier (s) and optional extension or modification composition (s) may be provided to the extrusion coater for application to the substrate. The composition may be made of a polymer component (ultra low molecular weight polymer or wax) in a second reactor and in addition to a multiple reactor process to produce substantially random copolymers in the reactor, and other components may optionally be prepared in a second reactor or sidearm ( sidearm) at the downstream stream point of the second reactor, such as via an extruder.
In a preferred embodiment, the composition of the present invention will be provided in the form of an adhesive comprising at least one substantially random copolymer. Typically, the adhesive will comprise from 5 to 75% by weight of one or more adhesives, more preferably from 10 to 70% by weight of one or more adhesives. As described above, the tackifier will preferably have aromatic properties. In some cases, the tackifier will be an ultra low molecular weight copolymer of ethylene and one or more vinylidene aromatic comonomers or hindered aliphatic vinylidene comonomers, the copolymer of one or more vinylidene aromatic comonomers or hindered aliphatic vinylidene comonomers It contains 25 mol% or more.
The adhesive of the present invention may also comprise one or more modifying compositions as described above. When such a modified composition is used, it will typically be present in the adhesive system in an amount of 5 to 75% by weight. Such modified compositions are typical waxes or ultra low molecular weight ethylene polymers. In some cases, the ultra low molecular weight ethylene polymer will be a copolymer of ethylene and one or more vinylidene aromatic comonomers or hindered aliphatic vinylidene comonomers, and the copolymer may be one or more vinylidene aromatic comonomers or hindered aliphatic vinylidene comonomers. It contains less than 10 mol%.
Moreover, the adhesives of the present invention may comprise a number of substantially random copolymer components having different amounts of vinylidene aromatic monomer or hindered aliphatic vinylidene monomer content, which differ in molecular weight, vinylidene aromatic monomer or hindered aliphatic vinyl. Leeden monomer content and molecular weight are different.
It will be apparent that adhesives containing very high amounts of substantially random copolymers can be devised. For example, such an adhesive may comprise from 5 to 75 weights of substantially random copolymers of ethylene and one or more vinylidene aromatic comonomers or hindered aliphatic vinylidene comonomers as the strength imparting component of the adhesive, the copolymer comprising at least about 10,000 Mn. Having less than 10-25 mol% of at least one vinylidene aromatic comonomer or hindered aliphatic vinylidene comonomer; As a wax, substantially random copolymers of 5-75% by weight of ethylene and one or more vinylidene aromatic comonomers or hindered aliphatic vinylidene comonomers, the copolymers have less than about 8,200 Mn and one or more vinylidene 5 to 75 weight percent of a random random copolymer of aromatic comonomers or hindered aliphatic vinylidene comonomers, and as an adhesive, ethylene and one or more vinylidene aromatic comonomers or hindered aliphatic vinylidene comonomers Wherein the copolymer has a Mn of less than about 8,200 and comprises at least 25 mole percent of one or more vinylidene aromatic comonomers or hindered aliphatic vinylidene comonomers.
As described in J. Class and S. Chu, Handbook of Pressure Sensitive Adhesive Technology, Second Edition, D. Satas, e., 1989, pp 158-204, the requirements for pressure-sensitive adhesive behavior are: And temperature and ratio dependent viscoelastic properties of the formulation.
In other words, in order to be suitable pressure sensitive, the blend has a glass transition temperature of -20 to 25 ° C., preferably -10 to 10 ° C. as indicated by the tangent δ peak temperature at 1 radian / sec as measured by dynamic mechanical spectroscopy. Should have The wide glass transition peak is good when the peak is wide, and the adhesive will perform over a wide temperature range, thus increasing its utility. Moreover, adhesives with broad glass transition peaks are typically characterized by increased tack and peel strength.
In accordance with what is known as the Dalquist criterion, in other words, for proper pressure reduction, the formulations are 1 × 10 ⁵ to 6 × 10 ⁶ dynes / cm ² , preferably 1 × 10 ⁵ , as measured by dynamic mechanical spectroscopy. It should have a plateau shear modulus at 25 ° C. from 1 radian / sec to 3 × 10 ⁵ dynes / cm ² . Materials stronger than this, ie materials having a Plato shear modulus at 25 ° C. of 1 × 10 ⁷ dynes / cm ² , will not show surface tack at room temperature. Less powerful materials, ie materials having a Plato shear modulus at 25 ° C. of 1 × 10 ⁴ dynes / cm ² , will usefully lack sufficient adhesive strength.
In particular, preferred pressure sensitive adhesives for use at low degrees of peeling will have a G ′ of 3 × 10 ⁵ to 1 × 10 ⁶ dynes / cm ² (0.3 to 1 MPa) and a glass transition temperature of −50 to −30 ° C. Preferred pressure sensitive adhesives for use at the freezer level will have a G ′ of 8 × 10 ⁴ to 2 × 10 ⁵ dynes / cm ² (0.08 to 0.2 MPa) and a glass transition temperature of -45 to 30 ° C. Preferred pressure sensitive adhesives for use at cold and cold levels will have a G ′ of 2 × 10 ⁵ to 1 × 10 ⁶ dynes / cm ² (0.2 to 1 MPa) and a glass transition temperature of −25 to −10 ° C. Preferred pressure sensitive adhesives for use in pressure sensitive adhesive tapes will have a G ′ of 7 × 10 ⁵ to 5 × 10 ⁶ dynes / cm ² (0.7 to 5 MPa) and a glass transition temperature of −10 to 10 ° C. Preferred pressure sensitive adhesives for use at high degrees of peeling will have a G ′ of 2 × 10 ⁵ to 6 × 10 ⁵ dynes / cm ² (0.2 to 0.6 MPa) and a glass transition temperature of 0 to 10 ° C. Preferred pressure sensitive adhesives for use in disposables will have a G ′ of 4 × 10 ⁵ to 2 × 10 ⁶ dynes / cm ² (0.4 to 2 MPa) and a glass transition temperature of 10 to 30 ° C.
The glass transition temperature is a function of the tackifier content, the presence and content of processing aids, the styrene content and the molecular weight of the substantially random copolymer. Thus, the glass transition temperature or amount of the pressure-sensitive adhesive can be increased to increase the glass transition temperature of the composition of the present invention, the amount of processing aid can be reduced, and vinylidene aromatic monomer or impaired aliphatic in substantially random copolymers. The amount of vinylidene monomer can be increased. Plato shear modulus is a function of the presence and amount of treatment aid and the styrene content and the molecular weight of the substantially random copolymer. To reduce G ', it is possible to increase the amount of processing aids in the composition and to increase the amount of vinylidene aromatic monomers or hindered aliphatic vinylidene monomers in substantially random copolymers.
The composition of the present invention will be utilized in the use of adhesives, in particular hot melt adhesives are typically used. Some representative examples include packaging, boxes and packaging seals, bookbinding, lamination of veneers on substrates, tapes and labels. The composition may also be utilized as a multilayer food packaging structure, wherein at least one layer of the structure is aluminum. The composition can be easily extruded onto a variety of substrates including but not limited to carpet backing, floor tiles, sheets, fabrics and nonwovens. The composition may be similarly shaped into various shapes including but not limited to soles, seals, toys, durables, wires and cables, and gaskets.
The following examples are provided to illustrate certain aspects of the invention rather than to limit the scope of the invention.
Example 1 Preparation of Adhesives Based on Substantially Random Copolymers of Ethylene and Monovinylidene Aromatic Comonomers
Polymerization of substantially random copolymers of ethylene and monovinylidene aromatic comonomers
Polymer A was prepared in a semi-continuous batch reactor stirred at 1 gallon (3.8 liters). The reaction mixture consisted of about 1100 g of cyclohexane and 818 g of styrene. Prior to addition to the reactor, the solvent, styrene and ethylene were purified to remove water and oxygen. Inhibitors in styrene were also removed. The temperature in the vessel was adjusted to a fixed point of 60 ° C. by varying the refrigerant flow in the reactor's cooling coils. The vessel was then adjusted to a fixed point of 100 psig (4.8 kPa) with ethylene. Hydrogen was added in controlled form to control molecular weight. Monocyclopentadienyl titanium containing catalyst (e.g., titanium: (N-1,1-dimethylethyl) dimethyl (1- (1,2,3,4,5-eta) -2,3,4,5-tetra Methyl-2,4-cyclopentadien-1-yl) silaneaminato)) (2-) N-dimethyl, CAS # 135072-62-7, Tris (pentafluorophenyl) boron, CAS # 001109-15- 5, catalyst components comprising modified methylaluminoxane form 3A, CAS # 146905-79-5), were flow-controlled, mixed, and added to the vessel at a molar ratio of 1 / 1.5 / 20, respectively. After start, the polymerization proceeded with ethylene fed to the reactor required to maintain vessel pressure. In this case, about 50 g of ethylene was charged to the reactor and ethylene was flowed into the reactor at a maximum rate of 5.6 g / min and the total amount of ethylene added was 87 g. The run continued for 30 minutes. At the end of the run the catalyst flow was stopped, ethylene was removed from the reactor and about 1000 ppm of Irganox 1010 antioxidant was added to the solution on the polymer and the polymer was separated from the solution. The resulting polymer can be separated from the solution by desorption using a devolatilizing extruder.
Preparation of Adhesive Blend
Substantially random copolymers, tackifiers, plasticizers, styrene block copolymers and antioxidants shown are simultaneously indicated in a Hake Rheocord 40 mixer using a 200 g mixing vessel maintained at about 130 ° C. at 95 revolutions / minute. Added. Mix for about 5 minutes until the components melt.
The brand name Escorez 5300 petroleum hydrocarbon resin is an adhesive available from Exxon Chemical Company, Houston, Texas.
The trade name Irganox B900 hindered phenolic antioxidants are available from Ciba Geygi.
Prioil 355 is a mineral oil.
Example 1 was tested for initial viscosity and viscosity after 3 days using a Brookfield viscometer at 350 ° F. (177 ° C.), probe tag, modulus (G ′) and peak tan delta. Formulations and measured properties are shown in Table 1. In the case of modulus and peak tan delta, the values taught were inferred from the resulting computer generated points.
As shown in Table 1, the adhesive of Example 1 meets the Dalquist criteria, including its suitability as a typical pressure sensitive adhesive. It is preferable that the adhesive agent of Example 1 also has a glass transition temperature in the range of -45-30 degreeC. Data relating to Example 1 in conjunction with the Dalquist criteria can be suitably used as a high peeling label and / or pressure sensitive adhesive tape.
Examples 2-8 and Comparative Examples A and B: Hot Melt Adhesives for Bonding Aluminum
Preparation of Ethylene Styrene Copolymers B and C
The polymer is prepared in a 400 gallon (1500 liter) stirred semicontinuous batch reactor using the process conditions described in Table 2 below. The reaction mixture consists of a mixture of cyclohexane (85% by weight) and isopentane (15% by weight) and about 250 gallons (950 liters) of solvent comprising styrene. Prior to addition, the solvent, styrene and ethylene are purified to remove water and oxygen. Inhibitors in styrene are also removed. The inert material is removed by purging the vessel with ethylene. The vessel is then subjected to ethylene controlled pressure. Hydrogen is added to adjust the molecular weight. By varying the jacket water temperature in the vessel, the temperature in the vessel is adjusted to a fixed point. Prior to polymerization, the vessel is heated to the desired running temperature and the catalyst component: titanium: (N-1,1-dimethylethyl) dimethyl (1- (1,2,3,4,5-eta) -2,3 , 4,5-tetramethyl-2,4-cyclopentadien-1-yl) silaneaminato)) (2-) N-dimethyl, CAS # 135072-62-7, tris (pentafluorophenyl) boron, Catalyst components comprising CAS # 001109-15-5, modified methylaluminoxane form 3A, CAS # 146905-79-5), respectively, were flow-controlled, mixed, and Added. After start, the polymerization proceeded with ethylene fed to the reactor required to maintain vessel pressure. In this case, hydrogen was added to the main space of the reactor to maintain the molar ratio relative to the ethylene concentration. At the end of the run, the catalyst flow is stopped, ethylene is removed from the reactor and then about 1000 ppm of Irganox 1010 antioxidant is added to the solution and the polymer is separated from the solution. The resulting polymer is separated from the solution by desorption using a devolatilizing extruder.

The copolymer and vinyl aromatic polymer properties are shown in Table 3. Unblended polymers provide a comparative example of the present invention.
Test site and property data for the copolymer were generated according to the following procedure:
The plaque is compression molded as follows. The sample is melted at 190 ° C. for 3 minutes and compression molded at 190 ° C. under a pressure of 20,000 lbs for another 2 minutes. The molten material is then quenched with a press equilibrated at room temperature.
Differential Scanning Calorimetry (DSC) measurements are made as follows. Dupont DSC-2920 is used to measure the heat transition temperature and the transition heat for the copolymer. The sample is first heated to 200 ° C. to remove the previous thermal history. Heating and cooling curves are recorded at 10 ° C./min. The melting (from the second row) and the crystal temperatures are recorded from the peak temperatures of endotherms and exotherms, respectively.
Melt shear rheology measurements are performed as follows. Oscillating shear rheological measurements are performed with a rheometry RMS-800 rheometer. Rheological properties are observed at an isothermal fixed temperature of 190 ° C. in a frequency sweep mode. In the data in the table, η is the viscosity and η (100 / 0.1) is the viscosity ratio of the values recorded at a frequency of 100 / 0.1 radians / second.
Shore A hardness is measured at 23 ° C. according to ASTM-D240.
Flexural modulus is evaluated according to ASTM-D790.
Tensile properties of compression molded samples were measured using an Instron 1145 tensioner with extensometer. ASTM-D638 samples are tested at a strain of 5 min ⁻¹ . The average of four tensile measurements is shown. Yield stress and yield strain are recorded at the bending point in the stress / strain curve. Fracture energy is the area under the stress / strain curve.
Tensile stress relaxation is measured as follows. Uniaxial tensile stress relaxation is evaluated using an Instron 1145 tensioner. A compression molded film (about 20 mil, 0.0508 cm thick) with a 1 "(2.54 cm) gauge length is deformed to a strain of 50% at a strain of 20 min ^-1 . Ten minutes of force required to maintain 50% elongation The magnitude of the stress relaxation is defined as (f _i -f _f / f _i ), where f _i is the initial force and f _f is the final force.
Thermomechanical analysis (TMA) data is generated using the Perkin Elmer TMA 7 Series instrument. Test penetration of 1 mm is measured on a 2 mm thick compression molded part using a heating ratio of 5 ° C./min and a load of 1 Newton.
The roller blades were used to make the formulations described in Table 4 in 60 ml of Brabender mixer. The vessel was heated to 130 ° C. prior to polymer introduction. Blade speed was 30 revolutions / minute. After the polymer was melted (about 5 minutes) other components were added in small amounts for 10-30 minutes. The addition rate was dependent on the mixing ratio of incorporating the material into the mixture. In the case of large discrepancies in the melt viscosity of the materials to be mixed, higher temperatures and longer mixing times were used. After the addition was complete, mixing was continued for 10 minutes or until the sample was visually homogeneous.
Adhesive samples were prepared from 3.17 x 15 cm strips of aluminum foil 0.002 cm thick. The surface was wiped with methyl ethyl ketone prior to binding to remove any surface contamination. Samples were prepared in a tetrahedral press with a set of plates at 177 ° C. Samples were compression molded between silicon release paper layers using the following procedure: (1) equilibrate at 177 ° C. for 30 seconds under contact pressure, (2) tilt to ram pressure of 11.2 kg / cm ² , and (3) 2 Hold pressure for minutes and release. The pressure corresponds to about 1.4 kg / cm ² on the sample.
Samples were tested in T-peel geometry (ASTM-1876) using an Instron tensile tester. Crosshead speed was 2.5 cm / min. Sample compositions and performance are shown in Table 4.
The comparison of Examples 3 to 6 of Table 4 illustrates the fact that formulations including suitable tackifiers exhibit improved peel strengths over ethylene / styrene copolymers without formulation. Formulation 7 illustrates the negative effect of an affinity or only partially affinity tackifier. As illustrated in Example 8, the addition of wax to the high peel strength adhesive of Example 3 reduced the peel strength compared to the adhesive of Example 3, but the comparative ethylene / octene copolymer of Comparative Examples A and B It produces better peel strength than the blend.
Examples 9-21 and Comparative Examples C, D and E:
The blend used in the following examples was prepared by the method described above. In the case of Examples 9-12, the polymer used was polymer D, 42% by weight of styrene and a substantially random heterogeneous ethylene / styrene copolymer having 1 g / 10 min of melt index (I ₂ ). In the case of Examples 13-16, the polymer used was polymer E, substantially random ethylene / styrene copolymer with 57% by weight of styrene. In the case of Examples 17-21, the polymer used was polymer F, substantially random ethylene / styrene copolymer with 65% by weight of styrene. The adhesive used was Piccotex 75, which is a pure monomer resin with a glass transition temperature as measured by DSC at 31 ° C. and is available from Hercules. The extension or modification composition used was Tuflo 6056, which is a mineral oil available from Lyondell Petrochemical.
The resulting formulations were evaluated for glass transition temperature, fracture elongation, fracture elongation, bond strength, G ', 100% modulus, 200% modulus and roughness.
For tensile measurements, the samples were molded at 10 tonnes ram pressure for 5 minutes at 115 ° C. The Instron tensile system was fixed at a crosshead speed of 50 cm / min. Modulus was obtained as the slope of the stress-strain curve at 100 and 200% elongation (measured by crosshead displacement). Roughness was the area under the stress-strain curve.
In the case of the G 'measurement, a rheometry RDSII Solids Analyzer was used with an 8 mm diameter parallel plate operating in shear mode. The test rate was 1 radian / second. The temperature was 5-10 ° C. and allowed to equilibrate for 2 minutes before data collection.
Formulations and resulting properties are shown in Table 5 below.
Table 5 shows that adding a tackifier to the substantially random ethylene / styrene copolymer increases the tensile roughness of the copolymer. The increase in roughness (as a result of increased strain-hardening of the blend) contributes to an increase in peel strength of the bonded aluminum specimen. The aluminum-aluminum bond is made at 177 ° C. for 120 seconds under 8 pounds / in ² (0.055 MPa) pressure. As illustrated in Table 6, the addition of a tackifier to the substantially random ethylene / styrene copolymer increases the roughness of the substantially random ethylene / styrene copolymer having less than 5% crystallization by DSC, i.e., mainly having amorphous properties. Have the ability.
Examples 21-23 and Comparative Examples F and G: PSA Tape
Samples of pressure sensitive adhesive tape were prepared by coating from a melt on a 0.051 mm thick polyester backside and covered with silicone release paper for storage and transportation. The applicator was a unit available from Chemsultants International. The adhesive layer ranged from 0.09 to 0.115 mm thick. The test was performed according to the pressure sensitive tape counseling (PSTC) standard. A 180 ^° peel test on stainless steel was performed at 30 cm / min at 5 minutes and 24 hours residence time. A shear test (holding force) was performed at room temperature with an overlap of 12.7 x 25.4 mm on a 1000 g load and mirror cleaned stainless steel.
For comparative example F, the polymer was vector 4113 styrene / isoprene / styrene block copolymer available from Dexco Company. For Comparative Example G, the polymer was Vector 4114 styrene / isoprene / styrene block copolymer available from Dexco Company. In the case of Examples 21-23, the polymer was a substantially heterogeneous copolymer of Polymer E.
The formulations used and the resulting adhesive properties are shown in Tables 6 and 7:

Tables 6 and 7 show low tackifying pressure-sensitive adhesive formulations wherein substantially random ethylene / styrene copolymers having styrene of 39 to 65, preferably 45 to 55% by weight, have improved warpage resistance compared to styrene block copolymer formulations. Can be combined to obtain.
Adhesive Blocking Research
The properties obtained from the literature as well as the adhesives evaluated in the study are shown in Table 8 below:
The formulations were prepared and evaluated, the formulations used and the resulting properties are shown in Table 9 below.
Table 9 shows that a wide range of pressure sensitive adhesive structures can improve the tensile properties of substantially random copolymers. Rosin esters, wood rosin, pure monomers, C ₅ -C ₉ , aromatic modified C ₅ , partially hydrogenated C ₅ -C ₉ and cycloaliphatic classes have been shown to be effective. Particularly noteworthy in Table 9 is that, for example, 100 parts of the substantially random copolymer component and 100 parts of the pressure-sensitive adhesive produce a material having a higher tensile strength than the substantial random copolymer alone, preferably two times or more, more preferably than the substantially random copolymer alone. Creating a material with a maximum tensile strength of more than three times.
Glass transition temperature control for high styrene content polymers
Substantially random copolymers of ethylene and styrene having 73.7 to 74.9% by weight of styrene and 1 g / 10 min of melt index (I ₂ ) are melt blended in the indicated amounts of Endex pure monomers available from Hercules. The glass transition temperatures of the tested formulations, the resulting formulations, are shown in Table 10 below.
The data shown in Table 10 illustrates the use of pressure sensitive adhesives to raise the glass transition temperature of styrene containing copolymers above ambient temperature.
These and other aspects will be readily apparent to those skilled in the art. Accordingly, the invention is intended to be limited by the following claims.

权利要求:
Claims (18)
[1" claim-type="Currently amended] 5 to 95% by weight of one or more substantially random copolymers of ethylene and vinylidene aromatic monomers or hindered aliphatic vinylidene monomers and optionally one or more C ₃ -C ₂₀ α-olefin monomers, and one or more tackifiers 5 to 95 weight percent and said substantially random copolymer comprises 1-65 mol% vinylidene aromatic monomer or hindered aliphatic vinylidene monomer.
[2" claim-type="Currently amended] The composition of claim 1, wherein said at least one substantially random copolymer is a copolymer of ethylene and a vinylidene aromatic monomer represented by the following formula:

Wherein R ¹ is selected from the group of radicals consisting of hydrogen and an alkyl radical comprising up to 3 carbons, and Ar is a phenyl group or a group consisting of halo, C _1-4 alkyl and C _1-4 haloalkyl Phenyl group substituted with 1 to 5 substituents selected from.
[3" claim-type="Currently amended] The method of claim 1, wherein the substantially random copolymer is at least one third selected from the group consisting of ethylene, vinylidene aromatic monomers or hindered aliphatic vinylidene monomers, and C ₃ -C ₂₀ α-olefins and norbornene A composition which is a copolymer of monomers.
[4" claim-type="Currently amended] The copolymer of claim 1 wherein the substantially random copolymer is a copolymer of ethylene, vinylidene aromatic monomers, and optionally one or more third monomers selected from the group consisting of C ₃ -C ₂₀ α-olefins and norbornene. Composition.
[5" claim-type="Currently amended] The composition of claim 1 comprising from 25 to 95% by weight of said substantially random copolymer, and from 5 to 75% by weight of at least one pressure sensitive adhesive.
[6" claim-type="Currently amended] 6. The method of claim 1, wherein the one or more tackifiers are wood rosin, tall oil derivatives, cyclopentadiene derivatives, natural and synthetic terpenes, terpene-phenols, styrene / alpha-methyl styrene resins, and blends. Selected from the group consisting of aliphatic-aromatic tackifying resins.
[7" claim-type="Currently amended] 2. The composition of claim 1 comprising paraffin wax, crystalline polyethylene wax, ultra low molecular weight ethylene polymer, homogeneous linear or substantially linear ethylene / alpha-olefin copolymers, polystyrene, styrene block copolymers, ethylene vinyl acetate, and amorphous polyolefins. The composition further comprises 5 to 75% by weight of one or more modified or extended compositions selected from the group.
[8" claim-type="Currently amended] The composition of claim 1 further comprising 1 to 60% by weight of one or more processing aids selected from the group consisting of phthalate esters, natural oils, paraffin oils, naphthenic oils and aromatic oils.
[9" claim-type="Currently amended] The composition of claim 1 in the form of an adhesive, a layer of a multilayer food packaging structure, a coating, a sealant or a molded product, a calendered product, or an extruded product.
[10" claim-type="Currently amended] 5 to 95 weight percent of one or more substantially random copolymers of ethylene and vinylidene aromatic monomers or hindered aliphatic vinylidene monomers and optional one or more C ₃ -C ₂₀ α-olefin monomers, wherein the substantially random air The coalescence comprises from 1 to 65 mole percent vinylidene aromatic monomers or hindered aliphatic vinylidene monomers, tackifiers, waxes, homogeneous linear or substantially linear ethylene / alpha-olefin copolymers, ultra low molecular weight ethylene polymers, processing aids And 95-5% by weight of at least one second component selected from the group consisting of: and mixtures thereof.
[11" claim-type="Currently amended] The adhesive of claim 10 wherein said substantially random copolymer comprises 25 to 65 weight percent vinylidene aromatic monomer or hindered aliphatic vinylidene monomer.
[12" claim-type="Currently amended] The method of claim 10 or 11, wherein the content of the vinylidene aromatic monomer or the hindered aliphatic vinylidene monomer is different, the molecular weight is different, or both the content and the molecular weight of the vinylidene aromatic monomer or the hindered aliphatic vinylidene monomer An adhesive comprising a plurality of different substantially random copolymer components.
[13" claim-type="Currently amended] The method of claim 12,
(a) ethylene and at least one vinylidene aromatic comonomer or hindered aliphatic vinylidene comonomer, having at least about 10,000 Mn and less than 5 to 25 mole% of at least one vinylidene aromatic comonomer or hindered aliphatic 5-75 wt% of a substantially random copolymer comprising vinylidene comonomer;
(b) ethylene and at least one vinylidene aromatic comonomer or hindered aliphatic vinylidene comonomer, having up to about 8,200 Mn and less than 1 to 5 mole% of at least one vinylidene aromatic comonomer or hindered 5 to 75 weight percent of a substantially random copolymer comprising aliphatic vinylidene comonomers; And
(c) ethylene and at least one vinylidene aromatic comonomer or hindered aliphatic vinylidene comonomer, having up to about 8,200 Mn and at least 25 mol% of at least one vinylidene aromatic comonomer or hindered aliphatic vinyl 5 to 75 weight percent of a substantially random copolymer comprising a lidene comonomer
Adhesive comprising.
[14" claim-type="Currently amended] 14. The adhesive according to any one of claims 10 to 13, wherein said substantially random copolymer is a copolymer of ethylene, at least one vinylidene aromatic monomer and optionally at least one alpha-olefin monomer.
[15" claim-type="Currently amended] The package, cardboard, bookbinding, tape, label, decal, bandage, decorative sheet, protective sheet, ceramic tile, vinyl tile, vinyl flooring, carpet backing layer, nonwoven fabric according to any one of claims 10-14. Adhesive applied to a substrate selected from the group consisting of: fabrics, personal care appliance attaching strips, sunscreens, gaskets, caulks, wood, or decorative boards.
[16" claim-type="Currently amended] An adhesive comprising at least one layer comprising an ethylene and a vinylidene aromatic monomer or a hindered aliphatic vinylidene monomer and at least one substantially random copolymer of optional at least one C ₃ -C ₂₀ alpha-olefin monomer. Coextruded or laminated multilayer film.
[17" claim-type="Currently amended] The coextruded or laminated multilayer film of claim 16, wherein the adhesive is attached to a metal foil.
[18" claim-type="Currently amended] (a) 25 to 65% by weight of vinylidene aromatic monomer or hindered aliphatic vinylidene, consisting of ethylene and vinylidene aromatic monomers or hindered aliphatic vinylidene monomers and optionally one or more C ₃ -C ₂₀ alpha-olefin monomers; 40 to 60 weight percent of a substantially random copolymer comprising monomers;
(b) 40 to 60 weight percent of a tackifier; And
(c) 0 to 10% by weight of processing aids
A tape comprising an adhesive applied to a substrate, wherein the adhesive has a storage modulus (G ′) at 25 ° C. of 2 × 10 ⁵ to 5 × 10 ⁶ dyne / cm ² (0.2 to 5 MPa).

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引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
1996-09-04|Priority to US2562296P

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1996-09-04|Priority to US60/025,622

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1997-09-04|Application filed by 그래햄 이. 테일러, 더 다우 케미칼 캄파니

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2000-11-25|Publication of KR20000068456A

优先权:

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申请号 | 申请日 | 专利标题

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US2562296P| true| 1996-09-04|1996-09-04|

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US60/025,622|1996-09-04|