Heat shrinking polyester film roll

专利摘要:
The heat shrinkable polyester film roll of the present invention has (1) a heat shrinkage in the maximum shrinkage direction at 85 ° C of 20% or more, and (2) a melt specific resistance at 275 ° C of 0.70 × 10 8 Ω · cm or less. (3) When the sample is taken out every about 100 m and the displacement of the thickness in the maximum shrinkage direction is measured for each sample, the thickness distribution value represented by the following formula in each sample is 7% or less. Thickness distribution = (maximum thickness-minimum thickness) / average thickness * 100 Thereby, the container coating film excellent in stable workability and printability can be taken out in an excellent yield.
公开号:KR20040028967A
申请号:KR10-2004-7001526
申请日:2002-07-30
公开日:2004-04-03
发明作者:사또시 하야까와；노리미 다보따；요시노리 다께가와；가쯔야 이토；시게루 고메다；가쯔히꼬 노세
申请人:토요 보세키 가부시기가이샤；
IPC主号:

专利说明:

Heat Shrinkable Polyester Film Roll {HEAT SHRINKING POLYESTER FILM ROLL}
[2] Heat-shrinkable plastic films are widely used in applications such as shrink packaging, shrink labels, cap seals, and the like, by utilizing shrinkage properties by heating. Especially, stretched films, such as a polyvinyl chloride film, a polystyrene film, and a polyester film, are labels, cap seals, or integrated packaging in various containers, such as a polyethylene terephthalate (PET) container, a polyethylene container, and a glass container. It is used for the purpose.
[3] However, polyvinyl chloride-based films have problems such as low heat resistance and generation of hydrogen chloride gas at the time of incineration or the cause of dioxins. On the other hand, since polystyrene-based films are poor in solvent resistance, an ink of a special composition must be used at the time of printing. In addition, when the polyvinyl chloride-based film or polystyrene-based film is used as a shrink label of a PET container (PET bottle, etc.), there is a problem in that the container and the label must be separated when the container is recycled.
[4] Since the polyester film does not have the above-mentioned problem, it is very expected as a shrink label to replace the polyvinyl chloride film or polystyrene film, and the usage amount also tends to increase as the usage of PET containers increases.
[5] However, the heat shrinkable polyester film is also required to be further improved in its shrinkage characteristics. Particularly, when coating shrinks in containers such as PET bottles, polyethylene bottles, and glass bottles, shrinkage stains and wrinkles are likely to occur, so that letters or patterns printed on the film before shrinking may be distorted after the coating shrinks. There is a desire of the user to want to keep it as small as possible. Moreover, shrinkage stress is small and the adhesiveness of the film to a container may be inferior. Moreover, compared with a heat shrinkable polystyrene film, etc., a heat shrinkable polyester film may be inferior in shrinkage property at low temperature, and may be shrunk at high temperature in order to obtain a required shrinkage amount. However, shrinkage at high temperature may cause deformation or whitening of the bottle.
[6] In the case of coating a bottle using a heat-shrinkable film, conventionally, after printing the heat-shrinkable film (printing step), the film can be mounted on a container [label (tube-shaped label), tube, bag, etc. Shape, etc.]. And after attaching these process films to a bottle, it places on a belt conveyor etc., passes through a heating tunnel (shrink tunnel), heat-shrinks, and makes it adhere to a container. As the contraction tunnel, a steam tunnel in which steam is blown out by heat contraction, and a hot wind tunnel in which hot air is blown out by heat shrink is used.
[7] When the steam tunnel is used, excellent heat transfer efficiency and uniform heat shrinkage can be achieved as compared with the case of using a hot air tunnel, so that a good shrinkage finish appearance can be obtained. However, even when a steam tunnel is used, shrinkage finish may not be as good in a heat shrinkable polyester film as compared to a polyvinyl chloride film or a polystyrene film.
[8] In addition, the hot air tunnel has a characteristic that temperature spots are more likely to occur during heat shrinkage as compared with the case where a steam tunnel is used. Therefore, shrinkage whitening, shrinkage staining, wrinkles, distortion, etc. are likely to occur when heat-shrinking a polyester film having less shrinkage finish than that of a polyvinyl chloride film or a polystyrene film, and in particular, shrinkage whitening becomes a problem in product appearance. have.
[9] Moreover, the heat shrinkable film is also required to be excellent in stable workability and printability. In order to improve stable workability and printability, the thickness of a film may be made substantially uniform. When the film thickness is made substantially uniform, wrinkles can be prevented from occurring in the film, and since the meandering occurs easily during film travel, the workability can be improved. In addition, it is possible to prevent the printing from being partially pulled out during film printing. In other words, it is important to increase the uniformity of the film thickness in the heat shrinkable film.
[10] As a method of making film thickness uniform, the method of electrostatically bonding a film and a roll is known, when cooling a melt-extruded film with a casting roll. In order to make the film electrostatically close to the roll, it is important for how many charge carriers are present on the surface of the molten film immediately after extrusion before contacting the roll. In order to increase the charge carriers, it is effective to lower the specific resistance by modifying the polyester, and much effort is required. For example, Japanese Unexamined Patent Publication No. 3-54129 adds magnesium compounds, sodium or potassium compounds, and phosphorus compounds in the production of polyethylene terephthalate (PET), and the concentration of Mg atoms is 30 to 400 ppm, Na atoms or K. It is disclosed to lower the specific resistance of PET film by setting the concentration of atoms to 3.0 to 50 ppm and the atomic ratio (Mg / P) of Mg and P to 1.2 to 20. Furthermore, in this publication, a magnesium compound is added at the time of esterification rate 20-80%, sodium or potassium compound is added until the intrinsic viscosity reaches 0.2, and since the esterification rate advanced 90% or more, By adding a phosphorus compound until the intrinsic viscosity reaches 0.2, the production of insoluble foreign matter is suppressed and the quality of the film is improved.
[11] An object of this invention is to provide the heat shrinkable polyester film roll which can take out the container coating film excellent in stable workability and printability with good yield.
[1] The present invention relates to a heat shrinkable polyester film, and more particularly to a heat shrinkable polyester film for label use.
[30] 1 is a schematic perspective view showing an example of an electrode used in the present invention.
[31] 2 is a schematic perspective view showing another example of the electrode used in the present invention.
[32] 3 is a schematic perspective view showing another example of the electrode used in the present invention.
[33] Best Mode for Carrying Out the Invention
[34] A heat shrinkable polyester film roll winds a heat shrinkable polyester film (henceforth simply called a film). The heat-shrinkable polyester film can be obtained in the following manner.
[35] (1) First, polyester which consists of a dicarboxylic acid component and a polyhydric alcohol component is melt-extruded from an extruder, is cooled with an electroconductive cooling roll (casting roll etc.), and film-formed (unstretched film).
[36] In addition, in the said extrusion, a copolyester is pulled alone or a some polyester (copolymer polyester, homo polyester etc.) is mixed and extruded. For this reason, the said film contains a base unit (crystal unit, such as polyethylene terephthalate, etc.), and the 2nd alcohol component different from the polyhydric alcohol component (ethylene glycol component etc.) which comprises the said base unit.
[37] (2) Next, when the polyester film containing a second alcohol component is stretched, a heat-shrinkable polyester film can be obtained.
[38] It is preferable that extending | stretching is uniaxial stretching, but biaxial stretching which extends small in the direction different from the direction (circumferential direction) of this uniaxial stretching may be sufficient. The stretching direction (circumferential direction) is not particularly limited, and may be a flow direction (length direction) of the film, or may be a direction orthogonal to the flow direction (hereinafter referred to as a width direction). Preferably, from the viewpoint of production efficiency, the width direction of the film is the main direction.
[39] The roll obtained from the heat-shrinkable polyester film is useful for modifying (labeling) a container. That is, the film for container coating is obtained by taking out a film from a film roll, printing, and cutting it to a suitable shape. The container coating film is processed into a form (label (tubular label), tube type, bag type) that can be attached to the container, and then the processing film is attached to the container to provide a heating device (steam tunnel, hot air tunnel, etc.). The container can be covered by heat shrinking a film using the film.
[40] EMBODIMENT OF THE INVENTION Hereinafter, the heat shrinkable polyester film of this invention and its manufacturing method are demonstrated in detail.
[41] [Heat-shrinkable polyester film]
[42] [Heat shrinkage rate]
[43] In the heat-shrinkable polyester film used in the present invention, a sample taken out in a square shape of 10 cm × 10 cm may be pulled up by dipping for 10 seconds in 85 ° C. hot water, and immediately raised by dipping for 10 seconds in 25 ° C. water. The thermal contraction rate in the maximum shrinkage direction at the time is 20% or more. If the heat shrinkage rate of the film is less than 20%, the amount of heat shrinkage of the film is insufficient when coating shrinkage occurs in a container or the like, and appearance defects are not preferable. More preferable thermal contraction rate is 30% or more, More preferably, it is 40% or more. The upper limit of the heat shrinkage ratio is preferably 80% (particularly 75%).
[44] Here, the thermal contraction rate in the maximum contraction direction means the thermal contraction rate in the direction in which the sample is most contracted, and the maximum contraction direction is determined by the length of the square in the longitudinal or transverse direction (or inclined direction). In addition, the heat shrinkage percentage (%) is 10 cm × 10 cm in the hot water of 85 ℃ ± 0.5 ℃, immersed for 10 seconds in the unloaded state for 10 seconds, and then thermally contracted in water at 25 ℃ ± 0.5 ℃ It is the value calculated | required according to the following formula after measuring the length of the longitudinal and horizontal direction (or the diagonal direction) of a film after immersion for 10 second.
[45] Thermal contraction rate = 100 * (length before contraction-length after contraction) ÷ (length before contraction)
[46] The means for making the heat shrinkage within the above range is not particularly limited, but for example, a method of forming a polyester without stretching the appropriate amount of the second alcohol component and stretching the unstretched film at an appropriate magnification may be mentioned. have.
[47] A diol component may be sufficient as the said 2nd alcohol component, and a trivalent or more alcohol component may be sufficient as it. Examples of diols that form the diol component include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 1,6-hexanediol, and 3-methyl-1 Alkylene glycols such as, 5-pentanediol, 2-methyl-1,5-pentanediol, 1,9-nonanediol, and 1,10-decanediol; Cyclic alcohols such as 1,4-cyclohexanedimethanol; Ether glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, bisphenol compounds or alkylene oxide adducts thereof; Dimerdiol and the like. Trimethyl or more alcohols include trimethylolpropane, glycerin, pentaerythritol and the like.
[48] The ratio of the second alcohol component is, for example, about 3 to 80 mol%, preferably about 5 to 75 mol%, more preferably about 10 to 70 mol%, in 100 mol% of the polyhydric alcohol component. It is about 25-55 mol%.
[49] Preferred second alcohol components include cyclic alcohol components (1,4-cyclohexanedimethanol components), diol components having 3 to 6 carbon atoms (propanediol component, butanediol component, hexanediol component and the like) and the like.
[50] The use of the cyclic alcohol component can increase the degree of non-crystallization of the film, so that the heat shrinkage rate can also be increased. In addition, shrinkage finish (such as suppression of shrinkage whitening, suppression of shrinkage stains, suppression of wrinkles, suppression of distortion, and / or suppression of vertical lines, etc.) can also be improved. In addition, the coating film taken out from the heat-shrinkable film roll can be attached to the container by adhering with a solvent (such as tetrahydrofuran or 1,3-dioxolane), such as a label (tubular label), tubular or bag type. Form], but solvent adhesion can also be improved by using a cyclic alcohol component (1,4-cyclohexanedimethanol component, etc.).
[51] The proportion of the cyclic alcohol component is, for example, 5 mol% or more in 100 mol% of the polyhydric alcohol component.
[52] By the way, in a heat-shrinkable polyester film, when the film is heated and reaches a certain temperature in the heat-shrink step, depending on the composition of the polyester constituting the film, the heat shrinkage rate is saturated, and even if heated at a higher temperature than that The above shrinkage may not be obtained. Such a film has the advantage of being capable of heat shrinking at a relatively low temperature, but shrinkage whitening tends to occur when heat shrinking with the hot wind tunnel or when heat shrinking after long term storage in an atmosphere of 30 ° C. or higher before heat shrinking. This shrinkage whitening phenomenon is considered to be because the molecular chain of polyester partially crystallizes and the refractive index of light in the crystal portion is different from that in the amorphous portion.
[53] However, the present inventors found that the shrinkage whitening can be significantly suppressed by setting the ratio of the cyclic alcohol component (1,4-cyclohexanedimethanol component, etc.) to 10 mol% or more in 100 mol% of the polyhydric alcohol component. It was. In addition, shrinkage staining can be significantly suppressed.
[54] 12 mol% or more is more preferable, and, as for the quantity of cyclic alcohol component (1, 4- cyclohexane dimethanol component), 14 mol% or more is more preferable.
[55] Moreover, it is required to suppress the quantity of cyclic alcohol component to 80 mol% or less in 100 mol% of polyhydric alcohol components. When there are too many cyclic alcohol components, since the shrinkage rate of a film becomes too high more than necessary, there exists a possibility that the position shift of a label and distortion of a pattern may arise in a heat shrink process. Moreover, since the solvent resistance of a film falls, it is unpreferable since whitening of a film arises by the solvent (ethyl acetate etc.) of an ink in a printing process, or the bursting resistance of a film falls. Therefore, 70 mol% or less is more preferable, as for 1, 4- cyclohexane dimethanol component, 60 mol% or less is more preferable, 30 mol% or less (for example, 25 mol% or less) is especially preferable.
[56] On the other hand, when the carbon number contains about 3 to 6 diols (C _3-6 diol), the glass transition temperature (Tg) of the polyester film can be lowered, and the low temperature shrinkage of the film can be improved. In the case of containing C _3-6 diol, the glass transition temperature (Tg) of the film can be adjusted, for example, to about 60 to 75 ° C.
[57] The proportion of the C _3-6 diol component is, for example, about 2 to 40 mol%, preferably about 3 to 35 mol%, more preferably about 5 to 30 mol%, especially 7 in 100 mol% of the polyhydric alcohol component. It is about 25 mol%.
[58] It is preferable to use together the said cyclic alcohol (1, 4- cyclohexane dimethanol etc.) and C _3-6 diol. When used together, the total amount of the cyclic alcohol component and the C _3-6 diol component is, for example, about 10 to 80 mol%, preferably about 15 to 70 mol%, more preferably 20 in 100 mol% of the polyhydric alcohol component. It is about 60 mol%, especially about 25-50 mol%. The proportion of the C _3-6 diol component is, for example, about 2.5 to 150 moles, preferably about 4 to 120 moles, and more preferably about 7 to 100 moles, relative to 100 moles of the cyclic alcohol component.
[59] In addition, as mentioned above, polyhydric alcohol components other than the said 2nd alcohol component are alcohol components (ethylene glycol etc.) which comprise a crystalline unit (ethylene terephthalate unit etc.). The more alcohol component for a crystalline unit, the higher the rupture resistance, strength, heat resistance, etc. of a film can be made. In this case, the amount of the alcohol component for the crystalline unit is 20 mol% or more, preferably 30 mol% or more, more preferably 40 mol% or more, particularly 50 mol% or more in 100 mol% of the polyhydric alcohol component.
[60] Moreover, as dicarboxylic acids which form the dicarboxylic acid component of a film, various dicarboxylic acids can be used in addition to the dicarboxylic acids (terephthalic acid, its ester formation derivative, etc.) which form the said base unit (crystalline unit). And various aromatic dicarboxylic acids, ester-forming derivatives thereof, various aliphatic dicarboxylic acids and the like can be used. As aromatic dicarboxylic acid, in addition to the said terephthalic acid, isophthalic acid, naphthalene-1,4- or -2,6- dicarboxylic acid, 5-sodium sulfoisophthalic acid, etc. are mentioned, for example. Moreover, derivatives, such as a dialkyl ester and a diaryl ester, are mentioned as an ester derivative. Examples of the aliphatic dicarboxylic acid include dimer acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, oxalic acid, and succinic acid.
[61] Although the draw ratio (stretch ratio of the main direction) of the said film can be suitably selected according to the kind and ratio of a 2nd alcohol component, For example, about 3.0-5.5 times, Preferably it is 3.2-5.4 times, More preferably Preferably 3.4 to 5.3 times. In addition, when the 2nd alcohol component is a cyclic alcohol component (1, 4- cyclohexane dimethanol component), when it is a _C3-6 diol component, or when combining them, the draw ratio is about 2.3 to 7.3 times, for example. Preferably, it is about 2.5 to 6.0 times.
[62] Melt Resistance
[63] The heat shrinkable polyester film used in the present invention has a melt specific resistance of 0.70 × 10 ⁸ Ω · cm or less at a temperature of 275 ° C. When such a film is used, the uniformity of a film thickness can be improved as demonstrated in detail below, and the processability (stable workability) at the time of processing into the form which can print to a film, or a film can be attached to a container can be improved.
[64] That is, in the present invention, in cooling the film melt-extruded from the extruder with an electrically conductive cooling roll (casting roll, etc.), an electrode is disposed between the extruder and the casting roll, and a voltage is applied between the electrode and the casting roll (that is, The film is supplied with electricity from the electrode) and the film is adhered to the roll electrostatically. When the melt specific resistance is small, the adhesion between the film and the roll (electrostatic adhesion) can be enhanced. When the electrostatic adhesion to the roll is low, the thickness of the cast unstretched film disc becomes uneven, and in the stretched film on which the unstretched film is stretched, the nonuniformity of the thickness is further expanded, but the electrostatic adhesion is sufficiently high. In the case, thickness can be made uniform also in a stretched film.
[65] When the uniformity of the film thickness is increased, color shifting can be prevented and printability can be improved when the film is subjected to multi-color printing in which a plurality of colors are superimposed.
[66] In addition, when the uniformity of the film thickness is increased, even when the film is processed in a tube or the like by solvent adhesion, the overlapping of the adhesive portions is easy. Moreover, when multi-color printing on a film, it can prevent that a wrinkle becomes easy to enter into a film, can prevent the film from meandering while running, and can improve workability (stable workability).
[67] In addition, by increasing the uniformity of the film thickness, it is possible to prevent the difference in partial winding hardness from occurring in the state where the film is wound in a roll shape, and to relax or wrinkle the film, thereby preventing the appearance of the film from being greatly damaged. .
[68] In addition, when the melt specific resistance is decreased to increase the electrostatic adhesiveness, not only the uniformity of the film thickness can be increased, but also the productivity of the film can be increased, and the appearance of the film can be improved. That is, when electrostatic adhesiveness is high, the stability of the cooling solidification of a film can be improved and a casting speed (production speed) can be raised. In addition, when the electrostatic adhesiveness is high, the cooling and solidification of the film becomes incomplete, and the air enters locally between the roll and the film, which can prevent the occurrence of pinner bubbles (defects in a string) on the film surface, and can improve the appearance of the film. .
[69] The melt specific resistance value is preferably 0.65 × 10 ⁸ Ω · cm or less, more preferably 0.60 × 10 ⁸ Ω · cm or less, particularly 0.3 × 10 ⁸ Ω · cm or less.
[70] In order to control a melt specific resistance value in the said range, it is preferable to contain an alkaline-earth metal compound and a phosphorus containing compound in a film. Even with alkaline earth metal compounds, the melt resistivity can be reduced, but when the phosphorus-containing compound coexists, the melt resistivity can be significantly reduced. It is not clear why the melting resistivity can be significantly lowered by combining the alkaline earth metal compound and the phosphorus-containing compound, but the inclusion of the phosphorus-containing compound can reduce the amount of foreign matter and increase the amount of charge carriers. Presumably because
[71] The content of the alkaline earth metal compound in the film is, for example, 20 ppm (by mass) or more, preferably 40 ppm (by mass) or more, more preferably 50 ppm (mass) based on the alkaline earth metal atom M ² . Reference), in particular 60 ppm (by mass). If the amount of alkaline earth metal compound is too small, the melt resistivity cannot be lowered. In addition, even if the content of the alkaline earth metal compound is excessively high, the effect of reducing the melt resistivity is saturated, and the harmful effects such as foreign matter generation and coloration are increased. Therefore, the content of the alkaline earth metal compound is based on the alkaline earth metal atom M ² , for example, 400 ppm or less (based on mass), preferably 350 ppm (based on mass) or less, more preferably 300 ppm (mass) Standard), in particular, about 160 ppm (by mass) or less.
[72] The content of the phosphorus compound in the film is based on the phosphorus atom P, for example 5 ppm (by mass) or more, preferably 20 ppm (by mass) or more, more preferably 40 ppm (by mass) or more, particularly It is 60 ppm (mass basis) or more. When the amount of the phosphorus compound is too small, the melt specific resistance cannot be lowered sufficiently, and the amount of foreign matter produced cannot be reduced. Moreover, even if the content of the phosphorus compound is excessively high, the effect of reducing the melt resistivity is saturated. In addition, since it is difficult to promote the production of diethylene glycol and to control the amount of production of diethylene glycol, there is a possibility that the physical properties of the film are different from those intended. Therefore, the content of the phosphorus compound is, for example, 500 ppm (by mass) or less, preferably 450 ppm (by mass) or less, more preferably 400 ppm (by mass) or less, particularly 350, based on the number of people P ppm (mass basis) or less [for example, 100 ppm (mass basis) or less].
[73] When the melt specific resistance of the film is lowered with the alkaline earth metal compound and the phosphorus compound, the mass ratio (M ² / P) of the alkaline earth metal atom M ² to the phosphorus atom P in the film is 1.2 or more (preferably 1.3 or more, more preferably 1.4 or more, in particular 1.6 or more). By setting the mass ratio (M ² / P) to 1.2 or more, the melt specific resistance can be significantly reduced. In addition, when the mass ratio (M ² / P) exceeds 5.0, the amount of foreign matter produced may increase or the film may be colored. Therefore, the mass ratio (M ² / P) is 5.0 or less, preferably 4.5 or less, more preferably 4.0 or less, particularly 3.0 or less. In order to further reduce the melt specific resistance of the film, it is preferable to contain the alkali metal compound in the film in addition to the alkaline earth metal compound and the phosphorus-containing compound. Even if the alkali metal compound is contained alone in the film, the melt resistivity cannot be lowered, but the melt resistivity can be remarkably lowered by adding to the coexistence system of the alkaline earth metal compound and the phosphorus containing compound. Although it is not clear about the reason, it is estimated that melting | fusing-resistance value is lowered by forming a complex with three of an alkali metal compound, an alkaline earth metal compound, and a phosphorus containing compound.
[74] The content of the alkali metal compound in film is, relative to the alkali metal atom M ¹ and, for example 0 ppm (mass basis) or more, preferably 5 ppm (mass basis) or more, more preferably 6 ppm (mass basis ), Especially 7 ppm (by mass). In addition, even if the content of the alkali metal compound is excessively high, the effect of reducing the melt resistivity is saturated, and the amount of foreign matter generated thereon increases. Therefore, the content of the alkali metal compound is, for example, 100 ppm (by mass) or less, preferably 90 ppm (by mass) or less, more preferably 80 ppm (by mass) or less, based on the alkali metal atom M ¹ . In particular, it is 30 ppm (mass basis) or less.
[75] Examples of the alkaline earth metal compound include compounds having hydroxides, alkoxides and aliphatic carboxylates (acetates, butyrates, and the like, preferably acetates), aromatic carboxylates (benzoates), and phenolic hydroxyl groups of alkaline earth metals; And salts (salts with phenols). Moreover, magnesium, calcium, strontium, barium, etc. (preferably magnesium) are mentioned as alkaline earth metal. Preferred alkaline earth metal compounds include magnesium hydroxide, magnesium methoxydegree, magnesium acetate, calcium acetate, strontium acetate, barium acetate and the like, in particular magnesium acetate. The alkaline earth metal compounds may be used alone or in combination of two or more thereof.
[76] Examples of the phosphorus compound include phosphoric acids (phosphoric acid, phosphorous acid, hypophosphorous acid, etc.) and esters thereof (alkyl esters, aryl esters, and the like), and alkylphosphonic acids, arylphosphonic acids, and esters thereof (alkyl esters, aryl esters, and the like). have. Preferred phosphorus compounds include phosphoric acid and aliphatic esters of phosphoric acid (alkyl esters of phosphoric acid, etc .; monophosphoric acid monoC _1-6 alkyl esters such as monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, dimethyl phosphate, phosphoric acid diethyl ester, phosphoric acid dibutyl ester of phosphoric acid di-C _1-6 alkyl ester, trimethyl phosphate ester, phosphoric acid triethyl ester, phosphoric acid tributyl ester of phosphoric tree C _1-6 alkyl ester and the like), an aromatic phosphoric acid ester ( Mono, di, or tri C _6-9 aryl esters of phosphoric acid such as triphenyl phosphate and tricresyl phosphate; and aliphatic esters of phosphorous acid (alkyl esters of phosphorous acid; and the like; for example, phosphorous acid such as trimethyl phosphite and tributyl phosphite Mono, di, or tri C _1-6 alkyl esters), alkylphosphonic acids (C _1-6 alkylphosphonic acids such as methylphosphonic acid, ethylphosphonic acid), alkyl Phosphonic acid alkyl esters (such as mono or di C _1-6 alkyl esters of C _1-6 alkylphosphonic acids such as dimethyl methyl phosphate and dimethyl ethyl phosphonic acid), and aryl phosphonic acid alkyl esters (dimethyl phenylphosphonate and phenyl phosphone) diethyl such as C _6-9 aryl phosphonic acid of a mono or di C _1-6 alkyl ester and the like), aryl phosphonic acid aryl esters (mono or di C _6-9 aryl such as phenyl phosphonic acid diethyl phenyl C _{6 -9} aryl ester etc.) etc. can be illustrated. Particularly preferred phosphorus compounds include phosphoric acid and trialkyl phosphates (such as trimethyl phosphate). These phosphorus compounds can be used individually or in combination of 2 or more types.
[77] As said alkali metal compound, salt with the compound which has hydroxide, carbonate, aliphatic carboxylate (acetate, butyrate, etc., preferably acetate), alkali carboxylate (benzoate), phenolic hydroxyl group of an alkali metal (Salts with phenol, etc.) etc. are mentioned. Moreover, as alkali metal, lithium, sodium, potassium, etc. (preferably sodium) are mentioned. Preferred alkaline earth metal compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium acetate acetate, potassium acetate and the like, in particular sodium acetate.
[78] [Thickness distribution value in the direction of maximum shrinkage]
[79] Moreover, even if it lowers a melt-resistance value as mentioned above and raises the uniformity of film thickness, it is inadequate only. That is, when forming a film roll, since the said film is long (for example, about 300 m-6000 m), there exists a possibility that the uniformity of thickness may fall depending on a measurement part.
[80] By the way, in the film roll of this invention, the film thickness is uniformized to a high level in the flow direction of a film. Therefore, according to the film roll of this invention, there is no possibility that the yield of the container coating film taken out from the film roll may fall.
[81] Also, in general, a plurality of the same type of container mounts (final product labels, bags, etc.) are manufactured from one heat-shrinkable film roll. In doing so, a difference in rigidity (elasticity) occurs, and there is a fear that the failure rate of the product may increase due to mounting failure. By the way, according to the present invention, since the samples at each extraction section have excellent uniformity, the product failure rate can be reduced and the yield can be increased.
[82] The film thickness does not necessarily have to be uniformized at a high level over the entire area of the heat-shrinkable film wound on the film roll, but at least in the normal region where the film properties are somewhat stable in the flow direction of the film. Can be. In other words, the heat-shrinkable film is produced by extruding molten plastic and then producing a film, but the physical properties of the film vary greatly until the film production process or the stretching process is stable (until the steady state is reached). . In addition, even after the film production process or the stretching process reaches a steady state, the film properties and the stretching conditions are changed, and the physical properties of the film greatly change. The present invention does not equalize the thickness of the film obtained when the film production process or the stretching process does not reach a steady state, and the film obtained when the film production process or the stretching process is operated in a steady state. The uniformity is higher than that of the conventional level.
[83] In addition, the number of the normal areas (normal operation) is not particularly limited, and there may be only one part (including the case of one part throughout the film roll) per one film roll, and may exist in a plurality of parts. The said normal region can be evaluated by measuring the thermal contraction rate of a film, for example. In the normal region, the heat shrinkage rate is stable, for example, within about 20% of the width (ie, the difference between the maximum value and the minimum value of the heat shrinkage rate is about 20% or less), and preferably within about 16%.
[84] And the uniformity of the film thickness in a normal area | region of the said end part <A> when the end part of the last side which winds up a film among the said normal areas is called the end part <A> and the end part of the side which starts winding is called the end part <B>. The first sample take-out part is installed within 2 m of the inner side, and the final take-out part is installed in the inside 2 m of the end portion <B>, and the sample take-out part is installed about every 100 m from the first take-out part. It can evaluate by measuring the film thickness of the sample taken out. In addition, "every about 100 m" means that the sample may be taken out at a portion of about 100 m ± 1 m (hereinafter, the same).
[85] The uniformity of the thickness can be determined by the thickness distribution value represented by the following formula.
[86] Thickness distribution = (maximum thickness-minimum thickness) / average thickness * 100
[87] The maximum thickness, the minimum thickness, and the average thickness were measured by using a contact thickness meter with a length of 20 cm and a width of 5 cm in the maximum shrinkage direction and taking a test piece from the roll to measure the displacement of the thickness with respect to the maximum shrinkage direction. It can be obtained by
[88] And according to the film roll of this invention, when the displacement of the thickness of the said largest shrinkage direction was measured about the sample of each part taken out from each extraction part, the thickness distribution value represented by the said formula in the sample of each part is 7% or less. Preferably it is 6% or less, More preferably, it is 5% or less, Especially 4% or less.
[89] In order for the sample of each part to have the said predetermined thickness distribution value, not only the film | membrane manufacturing process and extending | stretching process are reaching | attaining the steady state, but also it is insufficient, even the electrostatic adhesiveness of the film at the time of extruding molten polyester and cooling with a cooling roll There is a need to stabilize from the beginning of the film production to the end. Therefore, in the present invention, as the electrode to be used for the cooling, an electrode provided with a repelling device for electrode contamination surfaces and a supply device for electrode non-contamination surfaces is used. That is, when electrostatically bonding a film by providing electricity from an electrode during film manufacture of molten polyester, the said polyester contains several types of polymers (homopolymer, copolymer, etc.) and a monomer, and various low molecular weight components In many cases, the low molecular weight component volatilizes during the melt extrusion, thereby gradually contaminating the electrode. Therefore, if production of a film is continued, contamination of an electrode will become severe gradually, and sufficient electricity cannot be provided to a film, and there exists a possibility that the electrostatic adhesiveness of a film may fall. In the present invention, however, by using the specific electrode, the electrode contaminated surface can be evacuated, a non-contaminated surface can be supplied instead, and the electrode surface can be kept in a fresh state with little contamination. Therefore, there is no possibility that electrostatic adhesiveness may fall even if production of a film is continued, and the sample of each part can be made to have said predetermined thickness distribution.
[90] As said specific electrode, the electrode as shown in FIGS. 1-3, for example can be illustrated. That is, in the examples of FIGS. 1 to 3, the film 2 is melt-extruded from the die 1 provided in the extruder and the film 2 is cooled by the conductive cooling roll 3 to produce a film.
[91] (1) And in the example of FIG. 1, the wire-like electrode 10 which can face the film surface of the film 2 is arrange | positioned between the said extruder (die 1) and the conductive cooling roll 3. The wire electrode 10 is close to the film 2, and the distance between the film 2 and the wire electrode is about 5 to 20 mm (the distance between the film and the electrode described later is also the same). ). Therefore, static electricity can be provided to the film 2. One end of the wire electrode 10 is connected to a substantially cylindrical wire delivery device (supply device) 20 wound around the wire electrode 10, and the other end of the wire electrode 10 is a wire electrode 10. ) Is connected to a substantially cylindrical wire storage device (tagging device) 30 for winding up. By rotating the delivery device in the wire delivery direction and simultaneously rotating the wire storage device in the winding direction, the wire portion contaminated by the sublimation from the film can be retracted, and the wire electrode 10 is less contaminated. You can keep it fresh.
[92] (2) In the example of FIG. 2, the cylindrical electrode 11 is arrange | positioned between the die 1 and the electroconductive cooling roll 3, and the axial direction of this electrode 11 is parallel to the film surface of the film 2 It is controlled. This electrode 11 is approximated linearly with the film 2 at the outer peripheral surface, and can provide static electricity to the film 2. The cylindrical electrode 11 is connected to a rotational force generating device such as an omitted motor (in this case, the rotational force generating device also serves as both the supply device and the retracting device). Usually, as the electrode 11 is rotated, the film 2 and the proximal surface of the electrode 11 can be kept in a novel state with little contamination.
[93] (3) In the example of FIG. 3, between the die 1 and the conductive cooling roll 3, a plurality of electrode units (wire-like electrode unit, brush-like electrode unit, etc .; It is arranged. And all the electrode units 12 are provided with a proximity device (supply device) which moves each electrode unit 12 independently to a film, and a means (retro device) which separates each electrode unit 12 independently from a film. It is connected to the electrode support box 40. And by adhering each electrode unit 12 to the film 2 in turn, the novel electrode unit 12 with little contamination can provide static electricity to the film 2, and the fall of electrostatic adhesiveness can be prevented.
[94] In addition, when using the electrodes 10 and 11 of said (1) and (2), the cylindrical electrode 11 by sending out the wire-shaped electrode 10 from the delivery apparatus 20, or a rotating means is used. The rotation may be performed continuously or intermittently, but is preferably performed continuously.
[95] Although the material of an electrode is not specifically limited, It is preferable to use the tungsten electrode from a viewpoint of the stability of electrostatic adhesion and the strength of an electrode.
[96] In the case of using a wire-shaped electrode, the wire diameter is preferably in the range of about 0.15 to 0.35 mm from the viewpoint of the stability of electrostatic adhesion and the strength of the electrode.
[97] On the other hand, the cooling roll is not particularly limited, as long as it has conductivity, but the surface is preferably coated with a metal, and particularly, the surface is preferably chromium plated. Moreover, it is preferable that the surface of the cooling roll is controlled in 25-50 degreeC.
[98] The applied voltage is, for example, 6.5 kV or more, preferably 7.5 kV or more, more preferably 8.5 kV or more, and is usually 10 kV or less from the viewpoint of stability of electrostatic adhesion. The current value is, for example, 3.0 mA or more, preferably 3.5 mA or more, more preferably 4.0 mA or more, and usually 5.0 mA or less.
[99] In order for the sample of each part to have the said predetermined thickness distribution, the method of homogenizing the polyester raw material in (A) film manufacture, (B) film manufacture with the said method of stabilizing electrostatic adhesiveness from the beginning to the end of film manufacture. It is preferable to employ | adopt the method of stabilizing a process and the method of stabilizing the extending process of (C) film. In addition, either (A) homogenization of a raw material, stabilization of (B) film manufacture, and (C) extending | stretching may be employ | adopted, and it can also employ | adopt a combination of plurality (especially all). Preferred means is homogenization of the raw material (A).
[100] (A) Homogenizing polyester raw material in film manufacture
[101] That is, in the present invention, when forming a polyester as described above, a plurality of raw material polyesters having different compositions may be mixed (blended) to be pushed out. As a method of the said mixing and extrusion, the method specifically, shown by following (1)-(2) is employ | adopted in many cases. (1) A plurality of polyesters (polyester chips) having different compositions are continuously or intermittently supplied to a plurality of hoppers for each polyester, and finally, through the buffer hopper, the hopper immediately before or immediately above the extruder. To the final hopper. (2) Each polyester chip is mixed with this final hopper, combined with the extrusion amount of the extruder, and the mixed chip is quantitatively supplied to the extruder to prepare a membrane.
[102] By the way, the present inventors have found that in the case where the amount of chips remaining in the final hopper is large and small, the phenomenon of the raw material bias (raw material localization) in which the composition of the mixed chips supplied from the final hopper to the extruder is generated occurs. This phenomenon is likely to occur when the capacity or shape of the final hopper is inappropriate, especially when the shape and specific gravity of various polyester chips are different from each other. As a result, there exists a possibility that the content rate of the alkaline earth metal compound or phosphorus compound for improving electrostatic adhesiveness may fluctuate during manufacture of a film, and the thickness distribution value may fluctuate.
[103] As a method of obtaining a film with little fluctuation in the content of the alkaline earth metal compound or the phosphorus compound, a method of inhibiting raw material segregation (raw material localization) in the final hopper, for example, (i) matching the shape of each polyester chip A method, (ii) a method of reducing finely divided polyester chips, (iii) a method of optimizing the shape of the final hopper, (iv) a method of optimizing a capacity of the final hopper, and the like.
[104] (i) Method of matching the shape of each polyester chip
[105] When the shape of each polyester chip is matched, the said raw material bias can be reduced. In other words, if the size of the chip is different, when the mixed chip falls in the final hopper, the small chip is likely to fall first, so when the remaining amount of the chip in the final hopper decreases, the proportion of the large chip increases, resulting in raw material bias. On the other hand, matching the shape of each polyester chip can prevent the small chip from falling down first and reduce segregation of raw materials.
[106] Each polyester chip is normally taken out from the polymerization apparatus into strands in a molten state after polymerization, and immediately cooled by water, and then formed by cutting with a strand cutter. For this reason, a polyester chip becomes elliptical pillar shape of a cross section normally. Therefore, when matching the shape of each polyester chip, it is preferable to match the average length diameter (mm), average short diameter (mm), and average chip length (mm) of the cross-sectional ellipse of each polyester chip.
[107] Preferably, another polyester chip to be mixed with the most used polyester chip (most polyester chip), wherein the average long diameter (mm) and average short diameter (mm) of the cross-section ellipse, and the average chip length (mm) A polyester chip having a range within ± 20% of each of the most polyester chips, preferably a polyester chip within a range of ± 15%, respectively.
[108] The combination of most polyester chips and other polyester chips is not particularly limited, but a homopolyester chip (polyethylene terephthalate chip, polybutylene) is used as another polyester chip using a copolyester chip as the most polyester chip. Terephthalate chips and the like).
[109] (ii) a method of reducing finely divided polyester chips
[110] Since the fine powder (fine polyester chip) which arises in shaping | molding the raw material chip to be used etc. encourages generation | occurrence | production of raw material segregation, raw material segregation can be suppressed also by reducing the ratio of the said fine powder.
[111] It is preferable to control the ratio of the fine powder in a polyester chip within 1 mass% through the whole process until a raw material chip enters an extruder, and it is more preferable to control within 0.5 mass%.
[112] As a method of reducing fine powder, the method of removing (classifying removal etc.) the fine powder which generate | occur | produces in a process can be employ | adopted, for example. For example, a method of passing a sieve at the time of chip formation by a strand cutter, a method of passing a cyclone-type air filter in the case of conveying raw material chips, or the like can be adopted.
[113] (iii) how to optimize the shape of the final hopper
[114] For example, a funnel hopper is used as a final hopper, and the method of making the quadrilateral (side wall) approach vertically is mentioned. When the quadrilateral (side wall) is placed vertically, large chips can be easily dropped like small chips, and the upper end of the contents is lowered while maintaining a horizontal plane, which is effective for reducing segregation of raw materials.
[115] The inclination angle of the said quadrilateral (side wall) is 65 degreeC or more, Preferably it is 70 degreeC or more. Incidentally, the inclination angle of the quadrilateral (side wall) is the angle between the quadrilateral (side wall) on the funnel and the horizontal line segment (horizontal plane).
[116] When using a plurality of hoppers (hoppers for each chip supply, etc.) upstream of the final hopper, it is preferable that the inclination angle is 65 ° C or more, preferably 70 ° C or more, even in the plurality of hoppers.
[117] (iv) how to titrate the final hopper capacity;
[118] When the mixed chips mixed in the final hopper are discharged from the final hopper to the extruder over time, the mixed chips may be unevenly distributed in the feed.
[119] Therefore, if the presence time of the mixed chip in the hopper is shortened, that is, if the capacity of the hopper is small enough to discharge the mixed chip in a relatively short time, raw material segregation can be suppressed.
[120] The proper capacity of the hopper is, for example, in the range of 15 to 120 mass% of (discharge amount per hour of extruder), preferably in the range of 20 to 100 mass% of (discharge amount per hour of extruder), in particular 25 to It is accuracy in the range of 40 mass%.
[121] As a method of mixing two or more kinds of polyester chips having different compositions, a method of mixing each raw material continuously with an extruder and quantitatively feeding the extruder directly to the upper hopper (final hopper) is most preferable. It is also possible to premix what controls the raw material chip size within the above-mentioned range, and then feed it to the final hopper and the extruder through several intermediate (buffer) hoppers. When mixing plural kinds of raw materials, there is a method of quantitatively supplying plural kinds of raw materials into the hopper from a device for continuously quantitatively supplying raw material chips, or mixing in advance using a blender or the like. In this case, it is preferable to pay attention to the raw material chip size and the like so that raw material bias does not occur upon discharging the mixture.
[122] Any of the above (i) coincidence of chip shape, (ii) reduction of finely divided chips, (iii) optimization of hopper shape, and (iv) optimization of hopper capacity may be employed, but it is preferable to combine two or more techniques. It is most preferable to combine all four techniques.
[123] (B) How to stabilize the membrane manufacturing process
[124] As a method of stabilizing a film | membrane manufacturing process, the method of suppressing the fluctuation | variation of the discharge amount from an extruder, the method of suppressing the rotational speed fluctuation of a cooling roll (casting roll etc.), etc. are mentioned.
[125] When suppressing the discharge amount variation, for example, it is preferable to stabilize the discharge amount within a range of ± 2% of the average discharge amount. When suppressing the discharge amount variation, it is preferable to use a gear pump as the discharge means, for example.
[126] When the rotational speed fluctuation is suppressed, for example, it is preferable to stabilize the rotational speed within a range of ± 2% of the average rotational speed. When the rotational speed fluctuation is suppressed, for example, it is preferable to use an apparatus for controlling the rotation system of the roll drive system, for example, an inverter for rotational speed control.
[127] (C) Method to stabilize the stretching process of the film
[128] In order to provide heat shrinkability to a film, it is necessary to perform an extending | stretching process with respect to an unstretched film. When stabilizing the stretching process of a film, various devises for stabilization are performed with respect to a general stretching method.
[129] First, the general stretching method will be described. The timing of the stretching treatment is not particularly limited. For example, after cooling by the cooling roll (casting roll or the like), the film is first wound up into a roll, and the film is taken out of the roll to be stretched. Alternatively, after this cooling, the stretching treatment can be carried out continuously without winding in a roll.
[130] The stretching direction (maximum shrinkage direction of the film) may be the transverse (width) direction of the film, or may be the longitudinal direction (flow direction) of the film, but it is the point of production efficiency that the stretching direction is the transverse (width) direction of the film. Since it is practical in the following, the extending | stretching method at the time of making a extending | stretching direction (maximum shrinkage direction) into a horizontal direction is demonstrated as an example. In addition, when making extending | stretching direction (maximum shrinkage direction of a film) into a film longitudinal (length) direction, it can extend | stretch according to normal operation, for example, changing the extending | stretching direction in the following method by 90 degrees.
[131] When extending | stretching in a horizontal direction, extending | stretching process can be performed using conventional extending | stretching means, such as a tenter.
[132] A draw ratio is the grade (for example, about 23-7.3 times, preferably about 2.5-6.0 times) described in the column of the said [heat shrinkage rate]. Moreover, when extending | stretching to a horizontal direction, it is not only limited to uniaxial stretching to the horizontal direction by a tenter etc., but can also perform biaxial stretching extending | stretching also in a vertical direction. The draw ratio in the longitudinal direction is below the draw ratio in the lateral direction, for example, about 1.0 to 4.0 times, preferably about 1.1 to 2.0 times. If the draw ratio in the longitudinal direction is too large, the heat shrinkage in the direction orthogonal to the maximum shrinkage direction when measured in accordance with the method for measuring the heat shrinkage is too large (for example, greater than 10%), which is not preferable. The timing of biaxial stretching is not particularly limited, and may be either biaxial stretching or simultaneous biaxial stretching, for example, but may be re-stretched as necessary. In addition, when performing sequential biaxial stretching, extending | stretching order is not specifically limited, either, It can also extend | stretch in any order, such as vertical and horizontal, horizontal type | mold, vertical type | mold, and horizontal type | mold.
[133] After the stretching treatment, the heat treatment is performed at a predetermined temperature within the range of 50 ° C to 110 ° C, with 0-15% elongation or 0-15% relaxation, and if necessary, at a predetermined temperature within the range of 40-100 ° C. It is preferable to
[134] In addition, the film may be preheated prior to the stretching treatment.
[135] And when stabilizing the extending process of a film, various devises for stabilization are implemented with respect to the said general stretching method. For example, (i) control of stretching temperature, (ii) suppression of internal heat generation due to stretching, (iii) control of preheating (preheating) conditions, (iv) equalization of film surface temperature during stretching, and the like. have.
[136] (i) control of stretching temperature
[137] When controlling the stretching temperature, the stretching temperature is controlled so as not to be too high. When extending | stretching temperature is too high, film thickness distribution value may become large too much. Moreover, when extending | stretching temperature is too high, the elastic strength of a film may run short when high speed mounting of the obtained heat shrinkable film to a container (bottle etc.).
[138] It is preferable to control extending | stretching temperature to glass transition temperature (Tg) +40 degreeC or less (preferably Tg + 15 degreeC or less), for example.
[139] In addition, although the relationship with the thickness distribution is small, the stretching temperature is not less than the glass transition temperature (Tg) of -20 ° C (preferably Tg-5 ° C or more) and Tg + 40 ° C or less (preferably less than Tg + 15 ° C). It is desirable to. When extending | stretching temperature is too low, the thermal contraction rate of a film may run short, and transparency of a film may fall.
[140] (ii) suppression of internal fever following stretching
[141] By suppressing the internal heat generation of the film due to stretching, the temperature unevenness of the film in the stretching direction (width direction or the like) can be reduced, and the uniformity of the thickness of the film (heat-shrinkable film) after stretching can be increased.
[142] In order to suppress the said internal heat generation, it is preferable to control heating conditions suitably (for example, to speed up the supply of hot air), and to make it easy to heat a film. If there is a lack of heating, the internal heat generation due to the stretching orientation occurs, while if the film is sufficiently heated, the internal heat generation is difficult to occur because the molecular chain is likely to slip during stretching.
[143] The heating conditions are expressed by heat transfer coefficients. For example, the heat transfer coefficient is 0.OO38 J / cm ² · sec · ° C (O.OO09 calories / cm ² · sec · ° C) or more, preferably 0.0046 to 0.0071 J / cm ² Sec. 占 폚 (0.OO11 to O.OO17 calories / cm ² )
[144] (iii) control of preheating (preheating) conditions
[145] When controlling the preheating conditions, it is preferable to control the film to be heated slowly. When the film is gradually heated in the preheating step, the temperature distribution of the film can be made substantially uniform, so that the uniformity of the thickness of the film (heat shrinkable film) after stretching can be increased.
[146] The above heating conditions are, for example, about 0.00544 J / cm ² · sec · ° C (O.OO13 calories / cm ² · sec · ° C) or less. Moreover, as preheating, it is preferable to heat until film surface temperature becomes the temperature within the range of Tg + 0 degreeC-Tg + 60 degreeC, and it is preferable that the temperature of a hot air is about Tg + 10 degreeC-Tg + 90 degreeC.
[147] As a method of achieving the said heat transfer coefficient, the method of slowing down the supply speed of hot air, etc. are mentioned, for example.
[148] (iv) Equalization of Film Surface Temperature During Stretching
[149] When extending | stretching a film, when the fluctuation | variation range of the surface temperature of a film is made small (it homogenizes), it can extend | stretch and heat-process at the same temperature over the whole film length, and can uniform thickness distribution value and heat shrinkage behavior.
[150] When the surface temperature of the film is measured at any point, the fluctuation range of the surface temperature is that the temperature at each point is, for example, about ± 1 ° C. or less, and the average temperature is within ± 0.5 ° C. It is more preferable.
[151] When the film is stretched, the film is stretched through various processes such as preheating process, stretching process, heat treatment process after stretching, relaxation treatment and re-stretching process before stretching. It is preferable to use equipment (homogenizing) which can make the fluctuation range of temperature small. In particular, in order to uniformize the thickness distribution over the entire length of the film, in the preheating step and the stretching step (and in the heat treatment step after stretching as necessary), a facility that can reduce the variation in the surface temperature of the film is used. It is preferable. Moreover, when making heat shrink rate behavior uniform, it is preferable to use the installation which can make small the fluctuation range of the surface temperature of a film in an extending process.
[152] As a facility which can make the fluctuation | variation of the film surface temperature small, for example, the installation provided with the wind speed control means (inverter, etc.) for controlling the supply rate of the hot wind for heating a film, and stably heats air, And a facility equipped with a heating means for producing [heating means such as low pressure steam of 500 kPa or less (5 kgf / cm ² or less) as a heat source].
[153] Any of the above (i) control of the stretching temperature, (ii) suppression of internal heat generation, (iii) control of preheating conditions, and (iv) homogenization of the film surface may be adopted, and a plurality (particularly all) may be employed. You can do it.
[154] [Thickness distribution value in the flow direction of the film]
[155] The maximum shrinkage direction is substantially coincident with the stretching direction (major stretching direction) of the film, and the stretching direction (major stretching direction) may be the longitudinal direction (flow direction) of the film as described above, or may be the width direction. . Therefore, the thickness distribution value of the said largest shrinkage direction may mean the thickness distribution value of the flow direction of a film, and may mean the thickness distribution value of the width direction of a film.
[156] When the thickness distribution value in the maximum shrinkage direction means a thickness distribution value in the width direction of the film, the thickness distribution value in the flow direction of the film can be defined separately from the thickness distribution value in the maximum shrinkage direction (width direction). It is preferable that the thickness distribution values in this case are as follows.
[157] Inside 2 of said end <A>, when the end of the last side which winds a film in the normal area | region where film property is stable in the flow direction of a film is called the end <A>, and the end of the side which starts winding is called the end <B>. The first sample takeout part is provided in the part within m, and the final takeout part is provided in the part within 2m inside the said end <B>, and the sample takeout part is installed every about 100m from the first takeout part, and each takeout is carried out. When a sample having a length of 50 m and a width of 5 cm in the flow direction of the film was taken out from the part and the displacement of the thickness in the flow direction of the film was measured with respect to the sample of each part, The thickness distribution value displayed is 10% or less, Preferably it is 9% or less, More preferably, it is 8% or less, especially 5% or less.
[158] When the thickness distribution value in the flow direction is reduced, wrinkles can be prevented from entering into the film when the film is to be printed and when the solvent is bonded by the center seal or the like. In addition, when the film is printed and then processed into a form that can be attached to a container, tension fluctuation of the film can be prevented, and printing can be prevented or breakage can be prevented.
[159] As a method of equalizing the thickness distribution value of the flow direction of each part, the same method as the case of equalizing the thickness distribution value of the maximum shrinkage direction of each part mentioned above, ie, a method of lowering the melt resistivity value, a method using a specific electrode, during film production The method of homogenizing a polyester raw material (method of reducing raw material segregation), the method of stabilizing a film manufacturing process, the method of stabilizing the extending process of a film, etc. are mentioned.
[160] [Thermal shrinkage rate fluctuation]
[161] In the heat-shrinkable polyester film roll of the present invention, an end portion <A> is an end portion on the last side of the winding of the film in the normal region where the film properties are stable in the flow direction of the film, and an end portion <B> is called an end portion <B>. When called, the first sample extracting section is provided within 2 m of the inside of the end <A>, and the final extracting section is provided in the portion of 2 m inside of the end <B>. A sample takeout part is provided every 100 m, and each sample cut out in a square shape of 10 cm × 10 cm from this takeout part is immersed in hot water at 85 ° C. for 10 seconds and pulled up, followed by 10 seconds in water at 25 ° C. When the heat shrinkage in the maximum shrinkage direction when immersed and pulled up was measured and its average value was obtained (average heat shrinkage rate), the measured heat shrinkage rate of each sample was within ± 3% of the above average value (mean heat shrinkage rate). The crab is preferably in the range of ± 2%).
[162] That is, the absolute value (| X-Yn |) of the difference between the thermal contraction rate Yn (%) of each sample taken out from the said extraction part and the average thermal contraction rate X (%) of all the samples is 3 (%) or less [referably 2 (%) Or less] is preferable. In other words, the above requirement is satisfied if both the difference between the maximum value Ymax and X of Yn and the difference between the minimum value Ymin and X are within ± 3% (or within ± 2%).
[163] As described above, if the fluctuation of the heat shrinkage rate in one heat shrinkable film roll is reduced, the heat shrinkage fluctuation of one, one container mounting body (label, bag, etc.) can be reduced. This can reduce and reduce the defective rate of the product.
[164] As a method of reducing the fluctuation of the thermal contraction rate between each sample, the same method as the case where the fluctuation of the thickness distribution value in the maximum shrinkage direction between the respective samples described above is reduced, that is, the method of lowering the melt resistivity value, and using a specific electrode The method of making it, the method of homogenizing the polyester raw material in film manufacture (method of reducing raw material segregation), the method of stabilizing a film manufacturing process, the method of stabilizing the extending process of a film, etc. are mentioned.
[165] [Intrinsic viscosity]
[166] It is preferable that the film roll of this invention is 0.66 dl / g or more of intrinsic viscosity. If the intrinsic viscosity of the heat-shrink film is too small, the molecular weight of the polyester constituting the film decreases, so the durability of the shrinkage stress at the time of heat shrinkage decreases, and defects such as shrink whitening and shrinkage staining are likely to occur. It falls to the castle. Moreover, when the molecular weight of polyester falls, the mechanical strength and burst resistance of a film will fall.
[167] The intrinsic viscosity is preferably 0.67 dl / g or more, more preferably 0.68 dl / g or more. The intrinsic viscosity is usually about 1.30 dl / g or less (particularly about 0.8 d l / g or less).
[168] As a method of increasing the intrinsic viscosity of a film, for example, (1) the method of using a high molecular weight polyester for polyester which is a raw material of a film (for example, an intrinsic viscosity is 0.7 dl / g or more, Preferably it is 0.76 dl / g or more, more preferably 0.80 dl / g or more of a polyester), (2) a method of inhibiting thermal decomposition or hydrolysis when the polyester is extruded (for example, preliminarily drying the raw polyester) To a water content of 100 ppm or less, preferably about 50 ppm or less), (3) a method of using a hydrolyzable polyester as the polyester (for example, an acid value of 25 eq / ton or less). The method of using polyester), (4) The method of containing antioxidant (for example, about 0.01-1 mass%) in an polyester, etc. are mentioned.
[169] [Heat shrinkage stress value]
[170] It is preferable that the heat shrinkable polyester film roll of the present invention has a higher heat shrinkage stress value (maximum heat shrinkage stress value) in the maximum shrinkage direction. When the heat shrinkage stress value is high, the softness of the film (label or the like) can be prevented after coating the container, and the deterioration of the burst resistance due to the lack of mechanical strength of the film can be prevented.
[171] The maximum heat shrinkage stress value of the heat-shrinkable polyester film roll of the present invention is usually 3 MPa or more, preferably when the heat shrinkage test is performed under conditions of a test piece width of 20 mm and a distance of 100 mm between chucks in hot air at 90 ° C. 3.5 MPa or more, more preferably 4 MPa or more, in particular 7 MPa or more.
[172] The maximum heat shrinkage stress value is measured as follows.
[173] (1) From the heat-shrinkable film roll, the length of a maximum shrinkage direction is 200 mm, and the test piece of width 20mm is taken out.
[174] (2) In the heating furnace of a single tension tester (for example, "Tenshiron" manufactured by Toyo Seiki Co., Ltd.) equipped with a hot air heating furnace, hot air (wind velocity = 5) from three directions on the inside, left and right sides, respectively. m / sec) to heat the heating furnace to 90 ° C.
[175] (3) Stop the blowing and set the specimen in the heating furnace. The distance between the chuck is 100 mm (constant)
[176] (4) The door of the heating furnace is quickly closed, and the same blower as in (2) is resumed to detect and measure the heat shrinkage stress.
[177] (5) Read the maximum value from the chart and set this as the maximum heat shrinkage stress value (MPa).
[178] When controlling the maximum heat shrinkage stress value within the predetermined range, it is effective to adjust the composition of the polyester-based film. For example, as a polyhydric alcohol component, the 2nd alcohol component with which a base material is preferable in the said [heat-shrinkage rate] column, ie, a cyclic alcohol component (1, 4- cyclohexane dimethanol component), and a C3-C6 diol component ( Propanediol component, butanediol component, hexanediol component and the like) may be included in the film. The ratio of these preferable 2nd alcohol components may be as described in the column of said [thermal contraction rate].
[179] The polyester used by this invention can be obtained by melt polymerization method, another polymerization method, etc. As the melt polymerization method, for example, a method of polycondensing an oligomer obtained from a direct reaction of dicarboxylic acid and glycols (direct polymerization method), a method of polycondensation after a transesterification reaction of a dimethyl ester of dicarboxylic acid and glycol ( Transesterification method) and other arbitrary manufacturing methods can be applied. The degree of polymerization of the polyester is intrinsic viscosity and preferably about 0.5 to 1.3 dL / g.
[180] As the polymerization catalyst, various conventional catalysts can be used. For example, titanium catalysts, antimony catalysts, germanium catalysts, tin catalysts, cobalt catalysts, manganese catalysts, and the like, preferably titanium catalysts (titanium catalysts) Tetrabutoxide, etc.), an antimony catalyst (antimony trioxide etc.), a germanium catalyst (germanium dioxide etc.), a cobalt catalyst (cobalt acetate etc.), etc. are mentioned.
[181] The addition time of the compound (alkali metal compound, alkaline earth metal compound, phosphorus containing compound, etc.) for lowering the melt specific resistance value described above is not particularly limited, and from the end of the esterification to the start of the polymerization process before the esterification reaction, It may be any step during and after polymerization. Preferably it is any step after the esterification process, more preferably from the end of esterification to the start of the polymerization process. If an alkaline earth metal compound and a phosphorus-containing compound (and an alkali metal compound, if necessary) are added after the esterification step, the amount of foreign matter produced can be reduced as compared with the case where the alkaline earth metal compound and the phosphorus-containing compound are added.
[182] In addition, fine particles, such as silica, titanium dioxide, kaolin, and calcium carbonate, may be added to the film raw material as necessary, and antioxidants, ultraviolet absorbers, antistatic agents, colorants, antibacterial agents, and the like may be added.
[183] A heat shrinkable polyester film can be manufactured in accordance with a conventional method. Particularly in the heat-shrinkable polyester film, in the case of producing the second alcohol component in a specific range, as a production method, a method of using copolyester (copolyester) alone, or a method of mixing a plurality of polyesters [ For example, the method of mixing several mutually different homo polyester; A method of mixing homo polyesters (polyethylene terephthalate and the like) and copolyesters; The method of mixing several mutually different copolyester, etc. are mentioned.
[184] As a method of using copolyester independently, the copolyester containing the polyhydric alcohol component (2nd alcohol component etc.) of a specific composition can be used. On the other hand, the method of mixing a plurality of polyesters can be suitably employed because the characteristics of the film can be easily changed only by changing the mixing ratio, and the industrial production of films of various kinds can be supported.
[185] Specifically as a method for producing a film, a method of drying a raw polyester chip using a dryer (hopper dryer, paddle dryer, vacuum dryer, etc.) and extruding it into a film at a temperature of 200 to 300 ° C. using an extruder Can be mentioned. Alternatively, the method may be a method in which an undried polyester raw material chip is similarly extruded into a film while removing moisture in a vented extruder. In extrusion, various conventional methods, such as a T-die method and a tubular method, can be employ | adopted. After extrusion, it is preferable to obtain an unstretched film by quenching with a cooling roll such as a casting roll.
[186] Although the thickness of a heat shrinkable polyester film is not specifically limited, For example, when used for a label use, it is about 10-200 micrometers, Preferably it is about 20-100 micrometers.
[187] The heat shrinkable polyester film roll of this invention is obtained by winding the said heat shrinkable polyester film in a winding core. It is preferable that the film wound on a film roll is 200 mm or more in width and 300 m or more in length. The reason why the width is 200 mm or more is to increase the industrial utilization value of the film roll. The length of the film to be 300 m or more is because the thickness distribution value over the entire length of the film tends to fluctuate as the length of the film is wound longer, and in this case, the present invention which suppresses the variation of the thickness distribution value can be improved. .
[188] The width of the heat-shrinkable film wound on the roll is preferably 300 mm or more, more preferably 40 mm or more. Moreover, the length of the heat shrinkable film wound by a roll becomes like this. Preferably it is 400 m or more, More preferably, it is 500 m or more.
[189] Although the upper limit of the width | variety of the said film is not specifically limited, For ease of handling, it is generally 1500 mm or less in width. Moreover, although the upper limit of the length of the said film is not specifically limited, either, An upper limit can be determined according to film thickness from the ease of handling, for example, when the film thickness is 45 micrometers, the film length is preferably 6000 m or less.
[190] As a winding core, a plastic core or a metal core can be used normally. The diameter of these cores is, for example, about 2 to 10 inches (for example, 3 inches, 6 inches, 8 inches, etc.).
[191] According to this invention, since the film with a small melt specific resistance is used, it is excellent in the uniformity of film thickness, and is excellent in stable workability and printability. Moreover, the film roll of this invention is excellent in the uniformity of thickness over the whole film (normal region) wound up in roll shape. Therefore, the container coating film excellent in the stable workability and printability can be taken out in a good yield.
[12] Therefore, by applying the method developed in PET (Japanese Patent Laid-Open No. 3-54129) to a heat-shrinkable polyester film, Mg or P is added to the heat-shrinkable film to increase melt adhesion and uniformity of the film thickness. It is conceivable to increase the stable processability and printability of the film by increasing the ratio. However, since the raw materials and properties of the polymer are different from those of the PET and the heat-shrinkable polyester film, even if the method developed in PET is applied as it is, the effectiveness thereof is questionable. That is, a heat shrinkable polyester film (for example, a polyester film copolymerized with CHDM) has a large difference in thermal properties (melting point, crystallization temperature, glass transition temperature, etc.) and low heat resistance compared to PET. Therefore, as a heat-shrinkable polyester film, it is common to think that adding an additive greatly changes the thermal properties and also lowers the heat resistance, causing the film to be colored or to cause a viscosity decrease (molecular weight decrease) to occur, and to lower the melt specific resistance. It is common to think that the same problem occurs when adding an additive such as Mg or P.
[13] In addition, since a plurality of container coating films are taken out from one roll in a long heat-shrinkable polyester film (film roll etc.), it is important that it is excellent in stable workability and printability throughout the film roll. By the way, when manufacturing a film roll by the method of the said Unexamined-Japanese-Patent No. 3-54129, the part which lacks the uniformity of thickness may generate | occur | produce, and the part which the stability workability and printability may fall may arise. have. Therefore, it is required to further improve the yield of the film.
[14] The heat shrinkable polyester film roll of this invention is a film roll formed by winding a heat shrinkable polyester film. And this film roll,
[15] (1) The thermal contraction rate in the maximum shrinkage direction when a sample taken out of a 10 cm × 10 cm square shape was immersed in a hot water at 85 ° C. for 10 seconds and pulled up and then immersed in a 25 ° C. water for 10 seconds and pulled up. 20% or more,
[16] (2) The melt specific resistance at a temperature of 275 ° C. of the sample taken out of the film roll is 0.77 × 10 ⁸ Ω · cm or less,
[17] (3) When the end of the end of the winding of the film in the normal region where the film properties are stable in the flow direction (length direction) of the film is referred to as the end <A> and the end of the winding start side is referred to as the end <B>. And a first sample extracting portion is provided at a portion within 2 m of the inside of the end portion <A>, a final extracting portion is provided at a portion within 2 m of the inside of the end portion <B>, and a sample is taken out about every 100 m from the first extracting portion. When the shape of the sample taken out at the same time as installing the part was made into a rectangular shape having a length of 20 cm and a width of 5 cm in the maximum shrinkage direction of the film, and the displacement of the thickness in the maximum shrinkage direction was measured for each sample. The point which makes the summary the thickness distribution value represented by the following formula in the sample of each part is 7% or less.
[18] Thickness distribution = (maximum thickness-minimum thickness) / average thickness * 100
[19] By using such a film roll, the container coating film excellent in stable workability and printability can be taken out in a favorable yield.
[20] When the maximum shrinkage direction of the film having a thickness distribution value of 7% or less is orthogonal to the flow direction of the film,
[21] The end <A> when the end of the winding side of the film in the normal region where the film physical properties are stably in the flow direction of the film is referred to as the end <A> and the end of the winding side is called the end <B>. The first sample take-out part is provided in a portion within 2 m of the inside, and the final take-out part is provided in a portion within 2 m of the inside of the end portion <B>, and a sample take-out is provided every 100 m from the first take-out part. The shape of the taken-out sample was set to a rectangle having a length of 20 cm and a width of 5 cm in the flow direction of the film, and when the displacement of the thickness in the flow direction was measured with respect to the sample of each part, the formula in each sample was It is preferable that the thickness distribution value shown by is 10% or less. When thickness distribution value of a flow direction is made small, wrinkles can be prevented from entering into a film at the time of printing process of a film, and at the time of solvent adhesion processing by a center seal etc. In addition, when the film is printed and then processed into a form that can be attached to the container, the tension of the film can be prevented, and printing can be prevented or breakage can be prevented.
[22] The film is preferable to contain the alkaline earth metal compound and a phosphorus compound, and the alkaline earth metal content of the atom M ² of the film from 20 to 400 ppm (mass basis), and the content of phosphorus atoms P 5 to 350 ppm (mass Reference). In addition, an alkaline earth metal atom M ^2, and a mass ratio between the phosphorus atom P in the film (M ² / P) is preferably from 1.2 to 5.0. Also preferably in the case that contains the alkaline earth metal compound and phosphorus compound in the film, also the content of the alkali metal atom M ¹ of preferably include alkali metal compounds, and the film in the film is from 0 to 100 ppm (mass basis) Do. When the alkaline earth metal compound or the phosphorus compound is included in the film, the melt specific resistance of the film can be lowered and the uniformity of the film thickness can be improved.
[23] When manufacturing the said film, it is preferable to manufacture according to the method including the following processes. That is, when the molten polyester is extruded from an extruder and cooled and filmed by an electroconductive cooling roll, an electrode is disposed between the extruder and the roll, and electricity is supplied to the film from the electrode to electrostatically transfer the film to the roll. It is preferable to manufacture by the method including the process of contact | adhering, and to use the electrode provided with the repelling apparatus of a contaminated surface, and the supply apparatus of a non-contaminated surface as said electrode. When a film is produced by this method, when the thickness distribution value of the sample taken out from a film roll for several parts is measured, the fluctuation | variation of the thickness distribution value between extraction parts can be suppressed.
[24] It is preferable that the said heat-shrinkable polyester film is a film of a polyethylene terephthalate base, and content of 2nd alcohol components other than the polyhydric alcohol component (ethylene glycol component) which comprises a base unit is in 100 mol% of polyhydric alcohol components. It is preferable that it is about 10-70 mol%. As said 2nd alcohol component, 1 or more types chosen from cyclic alcohol component (1, 4- cyclohexane dimethanol etc.) and the diol component of 3-6 carbon atoms are used. It is preferable that 1, 4- cyclohexane dimethanol component is 5 mol% or more in 100 mol% of polyhydric alcohol components. By using the 1,4-cyclohexyl methanol compound, since the degree of amorphousness of the film can be increased, the heat shrinkage rate can be further increased. In addition, shrinkage finish can be improved.
[25] As for the ratio of a 1, 4- cyclohexane dimethanol component, it is more preferable to set it as 10 mol% or more (usually 80 mol% or less) in 100 mol% of polyhydric alcohol components. When it is 10 mol% or more, shrinkage whitening and shrinkage staining can be suppressed remarkably.
[26] Inside 2 of said end <A>, when the end of the last side which winds up a film in the normal area | region where film property is stable in the flow direction of a film is called end <A>, and the end of the side which starts winding is called end <B>. The first sample takeout part is provided in the part within m, and the final takeout part is provided in the part within 2 m inside the said end part <B>, and a sample takeout part is provided every 100 m from the first takeout part, For each sample cut into a square shape of 10 cm × 10 cm at, the maximum shrinkage in the direction of maximum shrinkage when immersed in 85 ° C. hot water for 10 seconds and pulled up, and then immersed in 25 ° C. water for 10 seconds and pulled up. When measured and the average value was calculated | required, it is preferable that the measured value of the thermal contraction rate of each sample is a range within +/- 3% of the said average value. As described above, if the variation in the heat shrinkage rate in one heat-shrinkable film roll is reduced, the heat shrinkage variation of one and one container mounting body (label, bag, etc.) can be reduced. This reduction can reduce the defective rate of the product.
[27] It is preferable that the intrinsic viscosity is 0.66 dl / g or more of the said film roll. When the intrinsic viscosity is increased, the persistence of the heat shrinkage stress can be maintained, and defects such as shrink whitening and shrinkage staining can be prevented. Moreover, the mechanical strength and burst resistance of a film roll are not reduced.
[28] The film wound up on the said film roll is 200 mm or more in width, and 300 m or more in length normally.
[29] In addition, in this specification, the term "unstretched film" includes the film | membrane in which the tension | tensile_strength required for sending a film acted.
[192] Hereinafter, although an Example further demonstrates this invention, the following example does not restrict this invention and it is contained in this invention, when changing in the range which does not deviate from the meaning of this invention. In addition, the measuring method of the composition and the physical property of the polyester obtained by the Example and the comparative example, the Example, and the comparative example are as follows.
[193] (1) composition
[194] ① dicarboxylic acid component, polyhydric alcohol component
[195] A sample solution was prepared by dissolving a sample (chip or film) in a solvent in which chloroform D (manufactured by Glass Co., Ltd.) and trifluoroacetic acid D1 (manufactured by Glass Co., Ltd.) were mixed at 10: 1 (volume ratio) to prepare a sample solution, and NMR (“GEMINI -200 "; manufactured by Varian Co., Ltd.), and the proton NMR of the sample solution were measured under a measurement condition of temperature 23 deg. The structural ratio of the monomer which comprises a sample was computed based on the peak intensity of proton by NMR measurement.
[196] ② metal components
[197] Content of Na, Mg, and P contained in a sample (chip or film) was measured in accordance with the method shown below.
[198] [Na]
[199] 2 g of the sample was placed in a platinum crucible and decomposed to ash at a temperature of 500 to 800 ° C., and 5 ml of hydrochloric acid (concentration: 6 mol / L) was added and evaporated to dryness. The residue was dissolved in 10 ml of 1.2 mol / L hydrochloric acid, and Na concentration was measured using an atomic absorption spectrometer [AA-640-12]; Shimadzu Corporation make the measurement (calibration method).
[200] [Mg]
[201] 2 g of the sample was placed in a platinum crucible, and the product was digested at a temperature of 500 to 800 ° C., and 5 ml of hydrochloric acid (concentration: 6 mo1 / L) was added and evaporated to dryness. The residue was dissolved in 10 ml of 1.2 mol / L hydrochloric acid, and the Mg concentration was measured using an ICP luminescence analyzer [ICPS-200]. Shimadzu Corporation make the measurement (calibration method).
[202] [P]
[203] The phosphorus component in a sample was made into plus phosphoric acid by the method in any one of the following (A)-(C) using a sample. The positive phosphoric acid and molybdate were reacted in sulfuric acid (concentration: 1 mol / L) to form phosphorus molybdate, followed by reduction by addition of hydrazine sulfate. The concentration of the generated heteropoly blue was measured using an absorbance photometer ["UV-150-02"; (Manufactured by Shimadzu Seisakusho Co., Ltd.), and was obtained by measuring the absorbance at 830 nm (calibration curve method).
[204] (A) A sample and soda carbonate are put into a platinum crucible and the dry material is decomposed.
[205] (B) Wet Decomposition in Sulfuric Acid, Nitric Acid, and Perchloric Acid Systems
[206] (C) Wet Decomposition in Sulfuric Acid and Perchloric Acid Systems
[207] (2) ultimate viscosity
[208] 0.1 g of a sample (film or chip) was precisely weighed and dissolved in a mixed solvent of 25 m1 of phenol / tetrachloroethane = 3/2 (mass ratio), and then measured at 30 ± 0.1 ° C. with an Oswald viscometer. Intrinsic viscosity [η] is obtained by the following equation (Huggins equation).
[209]
[210] η _sp : specific viscosity
[211] t ₀ : Dropping time of solvent using Oswald viscometer
[212] t: Dropping time of film solution using Oswald viscometer
[213] C: concentration of film solution.
[214] In addition, as an actual measurement, intrinsic viscosity was computed by the following approximation formula which made k = 0.375 in the Huggins formula.
[215]
[216] η _r : relative viscosity
[217] (3) solids (foreign material) remaining amount
[218] 2 g of a sample (chip or film) was mixed with phenol and tetrachloroethane [volume 100 ml; Phenol / tetrachloroethane = 3/2 (mass ratio)], and then the solution was filtered through a membrane-made membrane made of Teflon (pore diameter 0.1 μm) to collect solids and the amount of solids remaining was evaluated according to the following criteria.
[219] None: Foreign matter remaining on the membrane filter after filtration cannot be visually confirmed.
[220] Miso: Foreign matter remaining on the membrane filter after filtration was visually confirmed, and the foreign matter was present locally.
[221] Too much: Remaining remains on the membrane filter after filtration were visually confirmed, and foreign materials were found on the entire surface of the filter.
[222] (4) melt resistivity
[223] A pair of electrode plates was inserted in the sample (chip or film) melt | dissolved at the temperature of 275 degreeC, and the voltage of 120V was applied. The current was measured and the melt specific resistance (Si; unit Cm) was obtained by the following equation.
[224] Si (Ωcm) = (A / I) × (V / io)
[225] [Wherein A represents the area (cm ² ) of the electrode, I represents the distance (cm) between the electrodes, V represents the voltage (V), and io represents the current (A).
[226] (5) castability
[227] An electrode made of tungsten wire was disposed between the T die of the extruder and the casting roll whose surface temperature was controlled at 30 ° C., and a voltage of 7 to 10 kV was applied between the electrode and the casting roll. The resin was extruded from the T die at a temperature of 280 ° C., the extruded film was brought into contact with the electrode, and then cooled with a casting roll to prepare a film having a thickness of 180 μm (casting rate = 30 m / min). It observed by visually confirming the pinner bubble which generate | occur | produced on the surface of the obtained film, and evaluated according to the following criteria.
[228] ○: no pinner bubbles
[229] (Triangle | delta): The generation | occurrence | production of pinner bubble is confirmed partially.
[230] ×: occurrence of pinner bubbles
[231] (6) heat shrinkage rate
[232] In the film rolls obtained in the present experimental example and the comparative example, the film production process and the stretching process were operated in the normal state over the entire region from the start of the film to the end of the winding. Thus, the entire film corresponds to the normal region.
[233] Then, the first sample is taken out from the end of winding the film (0 m from the end of the winding), and the second and subsequent samples are taken out every about 100 m from the first taking out portion, and the portion that starts winding the film (starting winding) The final sample was taken out from Om) from the part to be made. The shape of each sample is a square of 10 cm x 10 cm. As mentioned later, since the length of a film is 1000 m, the number of samples is all 11 pieces.
[234] Each sample was immersed in hot water at 85 ° C. ± 0.5 ° C. for 10 seconds under no load and thermally shrunk, and then immersed in water at 25 ° C. for 10 seconds at ± 0.5 ° C., and then the length of the sample was measured in the longitudinal and transverse directions. It calculates according to the following formula.
[235] Thermal contraction rate (%) = 100 x (length before contraction-length after contraction) ÷ (length before contraction)
[236] In Table 2 described later, the average value X is the average value of all the heat shrinkage rates of the 11 samples measured, the maximum value Ymax is the maximum value of the heat shrinkage rate in 11 samples, and the minimum value Ymin is the minimum heat shrinkage rate of the 11 samples. And the difference with the average value was also shown.
[237] (7) rupture resistance (break rate)
[238] In accordance with JIS K 7127, a tensile test is performed in a direction orthogonal to the maximum shrinkage direction of the film before heat shrinkage. The number of test pieces shall be 20. The test piece length is 200 mm, the distance between chucks is 100 mm, the test piece width is 15 mm, the temperature is 23 ° C, and the tensile speed is 200 mm / min. The number of test pieces broken to 5% or less in elongation is counted, and the percentage of all the test pieces (20 pieces) is obtained to determine the breaking rate (%).
[239] (8) Maximum heat shrinkage stress value
[240] Using a heating furnace-tension tester (Tensilon, manufactured by Toyo Seiki Co., Ltd.), a sample having a length of 200 mm in the maximum shrinkage direction and a width of 20 mm was taken out of the heat-shrinkable film roll, and heated to 90 ° C in advance. Stop blowing in the furnace, attach the sample to the chuck at a distance of 50 mm from each end of the sample and make the distance between the chucks 100 mm, then quickly close the door of the heating furnace to cut the inside, left and right sides Blowing air flow (wind velocity = 5 m / sec) from the above was resumed, and the detected shrinkage stress was measured, and the maximum value obtained from the chart was defined as the maximum heat shrinkage stress value (MPa).
[241] (9) Thickness distribution in the maximum shrinkage direction
[242] From the film roll, the sample 1 of 20 cm in length and the width of 5 cm of the width direction (it corresponds to the largest shrinkage direction in the following example and a comparative example) was taken out.
[243] In addition, when the sample 1 is taken out, the first sample is taken out from the winding end of the film (0 m from the winding end), and the second and subsequent samples are taken out every 100 m from the first taking out part to wind the film. Take the final part of the sample from the starting part (Om from the start of the winding). As will be described later, since the film had a length of 1000 m, the number of ejection portions of Sample 1 was all 11, and 10 samples 1 were taken out for each ejection portion.
[244] Contact thickness meter [KG60 / A] for samples of each part; Anritsu Co., Ltd.] was used to measure the thickness in the longitudinal direction (ie, the maximum shrinkage direction) of the sample, and the thickness distribution value was obtained by the following equation, and the average value was used as the thickness distribution value of the portion.
[245] Thickness distribution = (maximum thickness-minimum thickness) / average thickness * 100
[246] (10) Thickness distribution in the flow direction
[247] It carried out similarly to the measurement of the thickness distribution value of the said largest shrinkage direction except taking out the sample 2 of 20 cm in width and 5 cm in width of the flow direction of a film from the film roll instead of the sample 1.
[248] (11) print processability
[249] The film was taken out from the heat-shrinkable film roll, and the full-color ink manufactured by Toyo Ink Co., Ltd. was stretched and printed, and then printed in the order of gold and white using a gravure plate of grid shape (1 cm square grid). The part which generate | occur | produced the wrinkle which generate | occur | produced in printing the film 1000m was counted, and it evaluated according to the following criteria.
[250] ○: less than two wrinkles (printable amount)
[251] (Triangle | delta): The generation part of wrinkles is 3-6 pieces
[252] X: 7 or more occurrences of wrinkles
[253] (12) shrink finish
[254] The film was taken out from the film roll, this film was adhere | attached with the solvent, and the tube was manufactured. In addition, about the thing which could not carry out solvent adhesion, heat sealing was performed and the tube was manufactured. This tube was cut to prepare a heat shrinkable polyester film label. Also tubular labels were made from the same film roll.
[255] Subsequently, the label was attached to a 300 ml glass bottle, and the label was shrunk by passing the inside of a hot air heat shrink tunnel at 160 ° C. (wind speed 10 m / sec) for 13 seconds. Judging by the degree of shrinkage whitening and shrinkage staining with the naked eye, the shrinkage finish was evaluated in five steps according to the following criteria.
[256] 5: The best finish
[257] 4: good finish
[258] 3: shrink whitening or shrinkage stains a little (within 2 parts)
[259] 2: shrink whitening or shrinkage stain (3-5 parts)
[260] 1: shrinkage bleaching or shrinkage staining (more than 6 parts)
[261] Moreover, four or more pass and three or less pass.
[262] All the labels obtained from the same film roll were evaluated for the shrinkage finish, the number of tubular labels at the pass level and the number of the tubular labels at the defective level were counted, and the shrinkage finish was evaluated by the following equation.
[263] Shrink-Finish = (Number of Tubular Labels with Poor Levels) ÷ (Number of All Tubular Labels) × 100 (%)
[264] Synthesis Example 1 (Synthesis of Polyester)
[265] Into the esterification tube, 57036 parts by mass of terephthalic acid (TPA), 35801 parts by mass of ethylene glycol (EG) and 15843 parts by mass of 1,4-cyclohexanedimethanol (CHDM) were charged, and the pressure was adjusted to 0.25 MPa. The esterification reaction was performed by stirring at 120 degreeC for 120 minutes. The reaction tube was returned to normal pressure to obtain 6.34 parts by mass of cobalt acetate and 4 beards (polymerization catalyst), 8 parts by mass of titanium tetrabutoxide (polymerization catalyst) and 132.39 parts by mass of magnesium acetate and 4 beards (alkaline earth metal compound), 5.35 parts by mass. After adding negative acetic acid sodium (alkali metal compound) and 61.5 parts by mass of trimethylphosphate (phosphorus compound), the mixture was stirred at a temperature of 240 ° C. for 10 minutes, and the pressure was reduced to 0.5 hPa for 75 minutes, and the temperature was raised to 280 ° C. Stirring was continued (approximately 40 minutes) until melt viscosity became 7000 poise at temperature 280 degreeC, and it discharged in water onto strand. Polyester chip A was obtained by cutting a discharged object by strand cutting.
[266] <Synthesis Examples 2 to 6>
[267] Polyester chips B to F shown in Tables 1-2 were obtained by the method similar to the synthesis example 1.
[268] The composition and physical properties of each polyester chip are shown in Table 1 and Table 2.
[269]
[270]
[271] In addition, in table, content of an inorganic component (Na, Mg, P, Ti, Co, Sb) is shown by the density | concentration (unit: ppm; mass basis) of each atom. In addition, the origin of each inorganic component is as follows.
[272] Na: mainly derived from sodium acetate
[273] Mg: mainly derived from magnesium acetate tetrahydrate
[274] P: mainly derived from trimethylphosphate
[275] Ti: mainly derived from titanium tetrabutoxide
[276] Co: Mainly derived from cobalt acetate tetrahydrate
[277] Sb: mainly derived from antimony trioxide
[278] In addition, in a table | surface, the meaning of a weak symbol is as follows.
[279] TPA: terephthalic acid
[280] EG: ethylene glycol
[281] CHDM: 1,4-cyclohexanedimethanol
[282] BD: 1,4-butanediol
[283] DEG: diethylene glycol
[284] <Example 1>
[285] Each chip obtained in the above synthesis example was preliminarily dried separately. Chip A, Chip D and Chip E were mixed in this hopper while continuously feeding separately to the hopper directly above the extruder using a quantitative screw feeder (chip A: 52 mass%, chip D: 38 mass%, chip E: 10 mass%). This mixed chip was melt-extruded using an extruder at the temperature of 280 degreeC, and it quenched by the casting roll (chromium plating roll) which controlled the surface temperature to 30 degreeC +/- 1, and obtained the unstretched film with a thickness of 180 micrometers.
[286] In the extrusion, a tungsten wire (0.25 mm in diameter) is disposed to face the extruded unfixed film, and electricity is supplied to the film from the wire (applied voltage 9.5 kV, current value of 4 mmA), and the film is rolled. To electrostatically. In addition, the said wire was continuously supplied from one side at the speed | rate of 1.8 m / hr, and wound up by the other side.
[287] In addition, the hopper used above has a capacity of 150 kg of chips, and the discharge amount of the extruder is 450 kg per hour. In addition, the inclination angle of the hopper side wall is 70 degrees.
[288] This unstretched film was stretched continuously over 1000 m. As the stretching, after preheating at 91 ° C. for 10 seconds, a tenter was used, the film was drawn at a temperature of 72 ° C. in the transverse direction at 4.0 times, and then thermally treated at a temperature of 79 ° C. for 10 seconds to form a heat-shrinkable polyester film having a thickness of 45 μm. Got it. The fluctuation range of the film surface temperature when the heat-shrinkable film was continuously produced for 1000 m was in the range of an average temperature of ± 0.8 ° C in the preheating step, an average temperature of ± 0.6 ° C in the stretching step, and an average temperature of ± 0.5 ° C in the heat treatment step. The obtained film was slit to a width of 400 mm and a length of 1000 m and wound up in a 3 inch paper tube to obtain a heat shrinkable film. Table 3 shows the composition and physical properties of the obtained film roll.
[289] <Example 2>
[290] As the mixed chip, a chip consisting of Chip A (71 mass%), Chip D (4 mass%) and Chip E (25 mass%) was used, and the pre-stretched film was preheated at a temperature of 78 ° C. for 10 seconds, and then tenter was used. A thermally shrinkable film roll was obtained in the same manner as in Example 1 except that the film was stretched 4.0 times in the transverse direction at a temperature of 73 ° C and subsequently subjected to a heat treatment at a temperature of 80 ° C for 10 seconds. Table 3 shows the composition and physical properties of the obtained film roll.
[291] Comparative Example 1
[292] As a mixed chip, the heat shrinkable film roll was obtained like Example 2 except having used the chip which consists of chip B (71 mass%), chip D (4 mass%), and chip E (25 mass%). Table 3 shows the composition and physical properties of the obtained film roll.
[293] Comparative Example 2
[294] As a mixed chip, the heat shrinkable film roll was obtained like Example 2 except having used the chip which consists of chip C (71 mass%), the chip D (4 mass%), and the chip E (25 mass%). Table 3 shows the composition and physical properties of the obtained film roll.
[295] <Example 3>
[296] As a mixed chip, after preheating an unstretched film for 10 second at the temperature of 78 degreeC using the chip which consists of chip A (10 mass%), chip D (64 mass%), and chip E (26 mass%), a tenter is A thermally shrinkable film roll was obtained in the same manner as in Example 2 except that the film was stretched 4.0 times in the transverse direction at a temperature of 73 deg. Table 3 shows the composition and physical properties of the obtained film roll.
[297] Comparative Example 3
[298] Each chip obtained in the above synthesis example was preliminarily dried separately. Chip F, Chip D and Chip E were mixed in this hopper while feeding continuously to the hopper directly above the extruder using a quantitative screw feeder (Chip F: 71 mass%, Chip D: 4 mass%, Chip E : 25 mass%). This mixed chip was melt-extruded at a temperature of 280 ° C. using an extruder and quenched with a casting roll to obtain an unoriented film having a thickness of 180 μm. The hopper used above has a capacity of 400 kg of chips, and the ejection amount of the extruder is 450 kg per hour. The angle of inclination of the hopper side wall is 60 °.
[299] This unstretched film was stretched continuously over 1000 m. As stretching, after preheating for 10 seconds at 78 ° C., the film was stretched 4.0 times in the transverse direction at a temperature of 73 ° C. using a tenter, and then thermally treated for 10 seconds at a temperature of 80 ° C. to form a heat-shrinkable polyester film having a thickness of 45 μm. Got it. The fluctuation range of the film surface temperature when the heat-shrinkable film was continuously manufactured for 1000 m was in the range of an average temperature of ± 1.0 ° C in the preheating step, an average temperature of ± 2.5 ° C in the stretching step, and an average temperature of ± 2.0 ° C in the heat treatment step. . The obtained film was slit to a width of 400 mm and a length of 1000 m, and wound around a 3 inch paper tube to obtain a heat shrinkable film roll. Table 3 shows the composition and physical properties of the obtained film roll.
[300]
[301] The heat shrinkable polyester film roll of this invention is excellent in the uniformity of film thickness, and is excellent in stable workability and printability. And the film for container coating can be taken out with a good yield. Therefore, it is useful for producing a label for modifying a container.

权利要求:
Claims (15)
[1" claim-type="Currently amended] A film roll formed by winding a heat shrinkable polyester film, wherein the heat shrinkable polyester film roll
(1) The thermal contraction rate in the maximum shrinkage direction when a sample taken out of a 10 cm × 10 cm square shape was immersed in a hot water at 85 ° C. for 10 seconds and pulled up, and then immersed in a 25 ° C. water for 10 seconds and pulled up. 20% or more,
(2) The melt specific resistance value at a temperature of 275 ° C. of the sample taken out from the film roll is 0.77 × 10 ⁸ Ω · cm or less,
(3) When the end of the last side of winding the film in the normal region where the film properties are stable in the flow direction of the film is called the end <A> and the end of the winding start side is called the end <B>, the end <A> The first sample take-out part is provided in a portion within 2 m of the inner side, and the final take-out part is provided in a part within 2 m of the inner side of the end portion <B>, and a sample take-out part is provided every 100 m from the first take-out part. At the same time, the shape of the sample taken out was set to a rectangle having a length of 20 cm and a width of 5 cm in the maximum shrinkage direction of the film, and each portion of the sample was measured for displacement of the thickness in the maximum shrinkage direction. The thickness distribution value represented by the following formula in the sample of is 7% or less, The heat shrinkable polyester film roll characterized by the above-mentioned.
Thickness distribution = (maximum thickness-minimum thickness) / average thickness * 100
[2" claim-type="Currently amended] The case where the maximum shrinkage direction of the film having a thickness distribution value of 7% or less is a direction orthogonal to the flow direction of the film, according to claim 1,
2 m inside of the end portion <A>, when the end of the last side to wind the film in the normal region where the film properties are stable in the flow direction of the film is called the end <A> and the end of the winding side is called the end <B>. The first sample extracting portion is provided in the portion within the portion, and the final extracting portion is provided in the portion within 2 m inside the end portion <B>, and the sample extracting portion is provided every 100 m from the first extracting portion, The shape is made into a rectangle having a length of 20 cm and a width of 5 cm in the flow direction of the film, and when the displacement of the thickness in the flow direction with respect to the sample of each part is measured, The heat shrinkable polyester film roll whose thickness distribution value is 10% or less.
[3" claim-type="Currently amended] The film of claim 1, wherein the film contains an alkaline earth metal compound and a phosphorus compound, the alkali earth metal atom M ^{2 in} the film is 20 to 400 ppm (by mass), and the content of phosphorus atom P is 5 to 350. Polyester film roll which is ppm (mass reference | standard).
[4" claim-type="Currently amended] The heat-shrinkable polyester according to claim 1, wherein the film contains an alkaline earth metal compound and a phosphorus compound, and the mass ratio (M ² / P) of the alkaline earth metal atoms M ² and the phosphorus atoms P in the film is 1.2 to 5.0. Based film rolls.
[5" claim-type="Currently amended] Claim 3 or claim 4, wherein the film will contain the alkali metal compound, (by weight) the content of the alkali metal atom M ¹ of the film from 0 to 100 ppm of the heat-shrinkable polyester film roll.
[6" claim-type="Currently amended] The method of claim 1, wherein when the molten polyester is extruded from an extruder and cooled to form a film by cooling, an electrode is disposed between the extruder and the roll and an electricity is supplied from the electrode to the film, thereby electrostatically forming the film. A heat-shrinkable polyester film roll manufactured by a method comprising the step of bringing the adhesive into close contact with the roll, wherein the electrode comprises a repellent device for contaminated surfaces and a supply device for non-contaminated surfaces. Based film rolls.
[7" claim-type="Currently amended] The heat-shrinkable polyester film roll according to claim 1, wherein the heat-shrinkable polyester film is a film of polyethylene terephthalate base.
[8" claim-type="Currently amended] The said heat-shrinkable polyester film of Claim 7 contains the 2nd alcohol components other than the ethylene glycol component which is the polyhydric alcohol component which comprises the said base unit, and this 2nd alcohol component contains a polyhydric alcohol component. The heat shrinkable polyester film roll which is 10-70 mol% in 100 mol%.
[9" claim-type="Currently amended] The heat-shrinkable polyester film roll according to claim 8, wherein the second alcohol component is at least one selected from a cyclic alcohol component and a diol component having 3 to 6 carbon atoms.
[10" claim-type="Currently amended] The heat-shrinkable polyester film roll according to claim 9, wherein the cyclic alcohol component is a 1,4-cyclohexanedimethanol component.
[11" claim-type="Currently amended] The said heat-shrinkable polyester film of Claim 10 WHEREIN: The heat shrinkable polyester film roll whose 1, 4- cyclohexane dimethanol component is 5 mol% or more in 100 mol% of polyhydric alcohol components.
[12" claim-type="Currently amended] The said heat-shrinkable polyester film of Claim 10 WHEREIN: The heat shrinkable polyester film roll whose 1, 4- cyclohexane dimethanol component is 10-80 mol% in 100 mol% of polyhydric alcohol components.
[13" claim-type="Currently amended] The end portion <A> according to claim 1, wherein the end portion <A> of the last side on which the film is wound in the normal region in which the film properties are stable in the flow direction of the film is referred to as the end portion <A>, and the end portion <B> is the end portion <A>. The first sample take-out part is provided in the part within 2 m inside of>, and the final take-out part is installed in the part within 2 m inside the said end <B>, and a sample take-out part is installed every 100 m from the first take-out part, For each sample cut out in a square shape of 10 cm × 10 cm from this outlet, the maximum shrinkage when soaked for 10 seconds in hot water at 85 ° C. and then pulled up for 10 seconds in water at 25 ° C. The heat shrinkable polyester film roll whose measured value of the heat shrinkage rate of each sample is the range within +/- 3% of the said average value when the heat shrinkage rate of the direction was measured and the average value was calculated | required.
[14" claim-type="Currently amended] The heat-shrinkable polyester film roll of Claim 1 whose intrinsic viscosity is 0.66 dl / g or more.
[15" claim-type="Currently amended] The heat-shrinkable polyester film roll according to claim 1, wherein the heat-shrinkable film has a width of 200 mm or more and a length of 30 Om or more.

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同族专利:

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公开号 | 公开日

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DE60237694D1|2010-10-28|

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JP2003113257A|2003-04-18|

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CN1537046A|2004-10-13|

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WO2003039841A1|2003-05-15|

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PT1424188E|2010-11-04|

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US6958178B2|2005-10-25|

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CN1308133C|2007-04-04|

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AT481229T|2010-10-15|

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US20040191493A1|2004-09-30|

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JP3678186B2|2005-08-03|

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EP1424188B1|2010-09-15|

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EP1424188A4|2005-12-14|

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KR101182884B1|2012-09-13|

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EP1424188A1|2004-06-02|

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:
2001-08-01|Priority to JPJP-P-2001-00233971

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2001-08-01|Priority to JP2001233971

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2001-09-28|Priority to JP2001300424A

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2001-09-28|Priority to JPJP-P-2001-00300424

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2002-07-30|Application filed by 토요 보세키 가부시기가이샤

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2002-07-30|Priority to PCT/JP2002/007746

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2004-04-03|Publication of KR20040028967A

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2012-09-13|Application granted

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2012-09-13|Publication of KR101182884B1

优先权:

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申请号 | 申请日 | 专利标题

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JPJP-P-2001-00233971|2001-08-01|

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JP2001233971|2001-08-01|

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JP2001300424A|JP3678186B2|2001-08-01|2001-09-28|Heat-shrinkable polyester film roll|

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JPJP-P-2001-00300424|2001-09-28|

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PCT/JP2002/007746|WO2003039841A1|2001-08-01|2002-07-30|Heat shrinking polyester film roll|