JP4791021B2 - Hydrogenated copolymer and composition thereof - Google Patents

Description

  The present invention relates to a hydrogenated copolymer excellent in a balance of physical properties such as solvent resistance, natural shrinkage, low temperature shrinkage, rigidity, transparency, low temperature elongation and impact resistance suitable for heat shrinkable films, and a composition thereof. About. In addition, the present invention is excellent in a balance of physical properties such as solvent resistance, natural shrinkage, low temperature shrinkage, rigidity, blocking resistance, hot water fusion resistance, low temperature elongation, and impact resistance, and fish eye (FE Relates to a sheet film, a heat-shrinkable film, and a heat-shrinkable multilayer film.

A block copolymer composed of a vinyl aromatic hydrocarbon and a conjugated diene, which has a relatively high vinyl aromatic hydrocarbon content, is used for injection molding applications, sheets, films, etc. by utilizing characteristics such as transparency and impact resistance. It is used for extrusion molding applications. In particular, heat-shrinkable films using block copolymer resins composed of vinyl aromatic hydrocarbons and conjugated dienes are the residual monomers and plasticizers of vinyl chloride resins used in the past, and the generation of hydrogen chloride during incineration. Since there is no problem, it is used for food packaging, cap seals, labels, etc. Properties required for heat-shrinkable films include natural shrinkage, low-temperature shrinkage, transparency, mechanical strength, suitability for packaging machines, and the like. So far, various studies have been made to improve these characteristics and obtain a good balance of physical properties.
For example, in order to obtain a composition having excellent mechanical properties, optical properties, stretching properties, crack resistance properties, etc., vinyl having an aliphatic unsaturated carboxylic acid derivative content of 5 to 80% by weight and a Vicat softening point not exceeding 90 ° C. A composition of an aromatic hydrocarbon-aliphatic unsaturated carboxylic acid derivative copolymer and a copolymer composed of a block of vinyl aromatic hydrocarbon and conjugated diene is disclosed (for example, see Patent Document 1).

  In addition, in order to obtain a heat-shrinkable film having excellent shrinkage characteristics and environmental destruction resistance, a heat-shrinkable film having a specific Tg in a segment of a block copolymer composed of a vinyl aromatic hydrocarbon and a conjugated diene is disclosed. (For example, refer to Patent Document 2). In order to obtain a heat-shrinkable film having excellent shrinkage characteristics and environmental destruction resistance, a heat-shrinkable film comprising a block copolymer composition comprising a vinyl aromatic hydrocarbon having a specific structure and a conjugated diene is disclosed ( For example, see Patent Document 3). In order to obtain a shrink film excellent in low-temperature shrinkage, optical properties, crack resistance properties, dimensional stability, etc., vinyl aromatics with a vinyl aromatic hydrocarbon content of 95 to 20% by weight and a Vicat softening point not exceeding 90 ° C. A low-temperature shrinkable film obtained by stretching a composition of a hydrocarbon-aliphatic unsaturated carboxylic acid derivative copolymer and a copolymer composed of a block of a vinyl aromatic hydrocarbon and a conjugated diene is disclosed (for example, a patent) Reference 4).

  In order to improve the natural shrinkability at room temperature, polystyrene-based heat shrinkage comprising a composition of a block copolymer comprising a styrene hydrocarbon and a conjugated diene hydrocarbon and a random copolymer having a specific Tg containing a styrene hydrocarbon. A film is disclosed (for example, see Patent Document 5). Vinyl aromatic hydrocarbon-aliphatic unsaturated carboxylic acid derivative copolymer and vinyl whose Vicat softening point does not exceed 105 ° C in order to obtain a transparent heat-shrinkable film excellent in stability over time and impact resistance of the film A heat-shrinkable hard film characterized by a specific heat-shrinking force is disclosed as a composition of an aromatic hydrocarbon and a copolymer comprising a block of a conjugated diene (see, for example, Patent Document 6). In order to obtain a composition that balances transparency, rigidity, and low-temperature impact, a copolymer composed of a block of vinyl aromatic hydrocarbon and conjugated diene having a specific structure and molecular weight distribution and vinyl aromatic hydrocarbon- (meta ) A composition with an acrylate copolymer resin is disclosed (for example, see Patent Document 7).

In order to obtain a resin composition having excellent transparency and impact resistance, a vinyl aromatic hydrocarbon block having a specific structure and a block copolymer having a vinyl aromatic hydrocarbon / conjugated diene copolymer block and a vinyl aromatic hydrocarbon are used. And a transparent high-strength resin composition containing a copolymer of (meth) acrylic acid ester (see, for example, Patent Document 8). In order to obtain a shrink film excellent in low-temperature shrinkage, optical properties, crack resistance properties, dimensional stability, etc., vinyl aromatics with a vinyl aromatic hydrocarbon content of 95 to 20% by weight and a Vicat softening point not exceeding 90 ° C. A multilayer low-temperature shrinkable film having at least one composition of a hydrocarbon-aliphatic unsaturated carboxylic acid derivative copolymer and a copolymer of a vinyl aromatic hydrocarbon and a conjugated diene block is disclosed ( For example, see Patent Document 9).
In order to obtain a shrink film excellent in natural shrinkage, strength, surface characteristics, waist strength, low-temperature shrinkage, etc., both outer layers are composed of a styrene-butadiene-styrene block copolymer having a specific butadiene unit content and styrene-butyl acrylate. A multilayer polystyrene-based heat-shrinkable film having at least three layers comprising a mixture of a styrene-butadiene-styrene block copolymer having a specific butadiene unit content and a mixture of styrene-butyl acrylate is disclosed (for example, Patent Document 10). reference).

  In order to obtain a heat-shrinkable film excellent in any of the properties of natural shrinkage, heat-resistant fusing, transparency, and shrinkage finish, a block copolymer of vinyl aromatic hydrocarbon and conjugated diene hydrocarbon and vinyl Mixing with a block copolymer consisting of vinyl aromatic hydrocarbon and conjugated diene hydrocarbon as the main component, blended with a combination of aromatic hydrocarbon and aliphatic unsaturated carboxylic acid ester copolymer A heat-shrinkable polystyrene-based laminated film having polymers as front and back layers is disclosed (for example, see Patent Document 11). Styrene- (meth) acrylic acid ester with a specific Vicat softening point in order to obtain a heat-shrinkable film that does not cause blocking between films when heat-shrinkable at low temperatures, shrinkable finish, natural shrinkage, and heat A multilayer heat-shrinkable polystyrene-based film having a specific heat shrinkage ratio, the main component of which is a copolymer and the inner and outer layers of which are styrene-conjugated diene block copolymers having a specific Vicat softening point, is disclosed ( For example, see Patent Document 12).

  Styrenic monomer characterized by specific molecular weight distribution and residual monomer amount to obtain resin composition and film and multilayer film with less processing characteristics, storage stability, odor, and excellent rigidity and impact resistance And a (multi-layer) heat-shrinkable film having a layer mainly composed of a copolymer resin comprising a (meth) acrylic acid ester monomer, a block copolymer resin comprising styrene and a conjugated diene, and a high impact polystyrene resin composition Is disclosed (for example, see Patent Document 13). In order to obtain a hydrogenated copolymer rich in flexibility, excellent in resilience and scratch resistance, and easy to handle, the content of vinyl aromatic hydrocarbon, the content of vinyl aromatic hydrocarbon polymer block, A hydrogenated copolymer having a weight average molecular weight and a hydrogenation rate of a double bond of a conjugated diene in a specific range is disclosed (for example, see Patent Document 14). In order to obtain a hydrogenated copolymer having excellent flexibility, tensile strength, abrasion resistance, dent resistance and good crosslinkability, the content of vinyl aromatic hydrocarbons, vinyl aromatic hydrocarbon polymer block A hydrogenated copolymer in which the content, the weight average molecular weight, the hydrogenation rate of the double bond of the conjugated diene, and the peak temperature of tan δ are in a specific range is disclosed (for example, see Patent Document 15).

  However, the composition of these block copolymer of vinyl aromatic hydrocarbon and conjugated diene or the block copolymer and vinyl aromatic hydrocarbon-aliphatic unsaturated carboxylic acid derivative copolymer is solvent resistant. , Natural shrinkage, low temperature shrinkage, rigidity, transparency, blocking resistance, hot water fusion resistance and impact resistance balance and gel-induced fisheye (FE) are not enough, There is no disclosure on how to improve the system, and problems in the market are still pointed out.

JP 59-221348 A JP-A-60-224520 JP 60-224522 A JP-A-61-25819 JP-A-4-52129 JP-A-5-104630 JP-A-6-220278 JP 7-216187 A JP 61-41544 A JP 2000-185373 A JP 2000-6329 A JP 2002-46231 A JP 2002-201324 A WO03 / 035705 publication WO04 / 003027 Publication

  The present invention provides a hydrogenated copolymer suitable for a heat shrinkable film excellent in a balance of physical properties such as solvent resistance, natural shrinkage, low temperature shrinkage, rigidity, transparency and impact resistance, and a composition thereof. Objective.

As a result of intensive studies, the present inventors have found that the above object can be achieved by a specific hydrogenated copolymer, and have reached the present invention. That is, the present invention
[1] Obtained by hydrogenating a non-hydrogenated copolymer comprising a vinyl aromatic hydrocarbon and a conjugated diene, and containing at least one polymer block (A) comprising a vinyl aromatic hydrocarbon, the vinyl aromatic hydrocarbon A hydrogenated copolymer (I) containing at least one copolymer block (B) consisting of a conjugated diene and having the following characteristics (1) to (7) Copolymer (I),
(1) The vinyl aromatic hydrocarbon content is in the range of more than 80% by weight and less than 90% by weight with respect to the weight of the hydrogenated copolymer (I).
(2) The content of the polymer (A) is in the range of more than 25% by weight and less than 60% by weight based on the weight of the non-hydrogenated copolymer.
(3) The vinyl aromatic hydrocarbon content in the copolymer block (B) is in the range of 80 wt% or more and less than 95 wt%,
(4) The weight average molecular weight is in the range of 50,000 to 1,000,000,
(5) The hydrogenation rate of the double bond of the conjugated diene unit is 60% by weight or more,
(6) The Vicat softening temperature of the hydrogenated copolymer (I) is in the range of 65 to 85 ° C.
(7) At least one peak of the function tan δ of dynamic viscoelasticity measurement of the hydrogenated copolymer (I) is present in the range of more than 80 ° C. and 110 ° C. or less.

[2] (1) The vinyl aromatic hydrocarbon content is in the range of 82 to 89% by weight with respect to the weight of the hydrogenated copolymer (I),
(2) The content of the polymer block (A) is in the range of 28 to 55% by weight with respect to the weight of the non-hydrogenated copolymer (I),
(3) The vinyl aromatic hydrocarbon content in the copolymer block (B) is in the range of 83% by weight or more and less than 92% by weight,
(4) The weight average molecular weight is in the range of 100,000 to 800,000,
(5) The hydrogenation rate of the double bond of the conjugated diene unit is 70% by weight or more,
(6) The Vicat softening temperature of the hydrogenated copolymer (I) is in the range of 68 to 80 ° C.,
(7) At least one peak of the dynamic viscoelasticity function tan δ of the hydrogenated copolymer (I) exceeds 83 ° C. and 105 ° C. or less.
The hydrogenated copolymer (I) as described in 1 above, wherein

[3] The hydrogenated copolymer (I) according to claim 1 or 2 , comprising at least one plastic polymer segment A and at least one elastomeric polymer segment B, Block copolymer having a weight ratio of aromatic hydrocarbon to conjugated diene of 65/35 to 82/18, and the peak of the dynamic viscoelasticity function tan δ of the block copolymer is at least −95 to −10 ° C. A composition comprising one block copolymer (II), wherein the Vicat softening temperature of the composition is in the range of 60 to 83 ° C, and the hydrogenated copolymer (I) and the block copolymer (II) The polymer composition whose weight ratio is 10 / 90-90 / 10.
[4] The hydrogenated copolymer (I) according to claim 1 or 2, the block copolymer (II) according to claim 3, and a styrene content of 70 to 90% by weight; A composition comprising an aliphatic unsaturated carboxylic acid ester-styrene copolymer (III) having a saturated carboxylic acid ester content of 30 to 10% by weight, wherein the Vicat softening temperature of the composition is in the range of 60 to 83 ° C. The weight ratio of the copolymer (I), the block copolymer (II) and the aliphatic unsaturated carboxylic acid ester-styrene copolymer (III) is 100% by weight, and (I) is A polymer composition comprising 10 to 80% by weight, (II) 10 to 80% by weight, and (III) 5 to 50% by weight.

  [5] The polymer composition as described in 3 or 4 above, wherein the hydrogenation rate of the double bond of the conjugated diene unit in the block copolymer (II) is in the range of 1 to 100% by weight. .

[6] 0.01 to 5 parts by weight of at least one lubricant selected from fatty acid amides, paraffins, hydrocarbon resins and fatty acids is added to 100 parts by weight of the hydrogenated copolymer (I). The hydrogenated copolymer (I) according to 1 or 2 above.
[7] At least one lubricant selected from fatty acid amide, paraffin, hydrocarbon-based resin and fatty acid is added in an amount of 0.01 to 5 with respect to 100 parts by weight of the hydrogenated copolymer (I) described in 1 or 2 above. 6. The polymer composition as described in any one of 3 to 5 above, which is added by weight part.
[8] 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-to 100 parts by weight of the hydrogenated copolymer (I) Pentylphenyl acrylate, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-bis [(octylthio) methyl] -o-cresol The hydrogenated copolymer (I) according to any one of 1, 2, 6 above, wherein 0.05 to 3 parts by weight of at least one stabilizer selected from the group consisting of:
[9] 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) with respect to 100 parts by weight of the hydrogenated copolymer (I) according to either 1 or 2 above Ethyl] -4,6-di-t-pentylphenyl acrylate, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4- The polymer composition as described in any one of 3 to 5 and 7 above, wherein 0.05 to 3 parts by weight of at least one stabilizer selected from bis [(octylthio) methyl] -o-cresol is added. object.
[10] At least one ultraviolet absorber or light selected from a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, and a hindered amine light stabilizer with respect to 100 parts by weight of the hydrogenated copolymer (I) The hydrogenated copolymer (I) according to any one of the above 1, 2, 6 and 8, wherein a stabilizer is added in an amount of 0.05 to 3 parts by weight .
[11] From 100 parts by weight of the hydrogenated copolymer (I) described in 1 or 2 above, from a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, and a hindered amine light stabilizer. The polymer composition as described in any one of 3 to 5, 7 and 9, wherein 0.05 to 3 parts by weight of at least one selected ultraviolet absorber or light stabilizer is added.

[12] The hydrogenated copolymer (I) according to any one of the above 1, 2, 2, 6, 8, or 10, or the above 3-5, 7, 7, 9, or 11 above. A sheet / film comprising the polymer composition.
[13] The hydrogenated copolymer (I) according to any one of 1, 2, 2, 6, or 10, or any of 3 to 5, 7, 9, or 11 above. A heat-shrinkable film obtained by stretching the polymer composition, wherein the heat shrinkage rate at 80 ° C. in the stretching direction is 5 to 60% and the tensile elastic modulus in the stretching direction is 700 to 3000 MPa.
[14] The hydrogenated copolymer (I) according to any one of the above 1, 2, 2, 6, 8, or 10, or the above 3-5, 7, 7, 9, or 11. A heat-shrinkable multilayer film characterized in that a layer made of the polymer composition is at least one layer of a multilayer film, and the heat shrinkage rate at 80 ° C. in the stretching direction is 5 to 60%.
[15] The heat-shrinkable multilayer film as described in 14 above, wherein the tensile elastic modulus in the stretching direction is 700 to 3000 MPa.

  The heat shrinkable film using the hydrogenated block copolymer of the present invention is excellent in the balance of physical properties such as solvent resistance, natural shrinkage, low temperature shrinkage, rigidity, transparency, low temperature elongation and impact resistance.

  Hereinafter, the present invention will be described in detail. In the hydrogenated copolymer (I) of the present invention, the vinyl aromatic hydrocarbon content of the non-hydrogenated polymer is more than 80% by weight, less than 90% by weight, preferably 82-89% by weight, more preferably It is in the range of 84 to 89% by weight. When the vinyl aromatic hydrocarbon content is in the range of more than 80% by weight and less than 90% by weight, a heat shrinkable film having an excellent balance between rigidity and low temperature elongation can be obtained.

The content of the polymer (A) of the hydrogenated copolymer (I) of the present invention is more than 25% by weight and less than 60% by weight, preferably 28 to 55% by weight based on the weight of the non-hydrogenated polymer. %, More preferably in the range of 30 to 50% by weight. When the content of the polymer (A) exceeds 25% by weight, a hot water fusion property is excellent, and when it is less than 60% by weight, a heat-shrinkable film having excellent low-temperature shrinkability can be obtained. The content of the polymer (A) is determined by a method of oxidatively decomposing a non-hydrogenated copolymer with tertiary butyl hydroperoxide using osmium tetroxide as a catalyst (IM KOLTHOFF, et al., J. Polym. Sci. 1). , 429 (1946)), and the weight of the vinyl aromatic hydrocarbon polymer block component obtained by this method (excluding vinyl aromatic hydrocarbon polymer components having an average degree of polymerization of about 30 or less). Is the value obtained from the following equation.
Polymer block (A) (% by weight) = (weight of vinyl aromatic hydrocarbon polymer block (A) in non-hydrogenated copolymer / weight in non-hydrogenated copolymer) × 100
In the case where the content of the polymer block (A) with respect to the hydrogenated copolymer (I) is directly measured from the hydrogenated copolymer (I), the method described in WO 04/003027 (pages 27 to 28). May be used.

The vinyl aromatic hydrocarbon content in the copolymer block (B) of the hydrogenated copolymer (I) of the present invention is in the range of 80 wt% or more and less than 95 wt%, preferably in the range of 83 to 92 wt%. More preferably, it is in the range of 86 to 92% by weight. When the vinyl aromatic hydrocarbon content in the copolymer block (B) is 80% by weight or more, the rigidity is excellent, and when it is less than 95% by weight, the hot water fusion resistance is excellent.
The weight average molecular weight of the hydrogenated copolymer (I) of the present invention is in the range of 50,000 to 1,000,000, preferably in the range of 100,000 to 800,000, and more preferably in the range of 130,000 to 600,000. When the weight average molecular weight is in the range of 50,000 to 1,000,000, the moldability is excellent. In the present invention, the preferred range of the molecular weight distribution (Mw / Mn, Mw is the weight average molecular weight, Mn is the number average molecular weight) is 10 or less, more preferably 1.05 to 6, particularly preferably 1.1 to 3 range. The weight average molecular weight of the hydrogenated copolymer specifies the molecular weight of the non-hydrogenated copolymer by gel permeation chromatography (GPC). The molecular weight of monodisperse polystyrene for gel permeation chromatography (GPC) is prepared by GPC and a calibration curve is created between the peak count and the number average molecular weight of the monodisperse polystyrene. >"Kodansha").

A preferred melt flow rate of the hydrogenated copolymer (I) of the present invention (measured according to JIS K6870. Conditions are G conditions, temperature 200 ° C., load 5 kg) is 0.01 to 100 g / 10 min from the viewpoint of molding processability. It is recommended to be 0.05 to 50 g / 10 min, more preferably 0.5 to 30 g / 10 min. The weight average molecular weight and the melt flow rate (hereinafter sometimes abbreviated as MFR) can be arbitrarily adjusted depending on the amount of catalyst used for the polymerization.
The Vicat softening point of the hydrogenated copolymer (I) of the present invention is recommended to be in the range of 65 to 85 ° C, preferably in the range of 68 to 80 ° C, and more preferably in the range of 68 to 77 ° C. The Vicat softening temperature is a value measured according to ASTM D-1525 (load: 1 Kg, heating rate: 2 ° C./min) using a test piece compression-molded to a thickness of 3 mm.
When the Vicat softening temperature is in the range of 65 to 85 ° C., the natural shrinkage and the low temperature shrinkability are excellent. The adjustment of the Vicat softening temperature increases, for example, when the weight average molecular weight is increased, increases when the vinyl aromatic hydrocarbon content is increased, and increases when the content of the polymer (A) is increased. It can be increased by increasing the vinyl aromatic hydrocarbon content in (B).

The hydrogenated copolymer (I) of the present invention comprises at least one polymer block (A) comprising a vinyl aromatic hydrocarbon and at least a copolymer block (B) comprising a vinyl aromatic hydrocarbon and a conjugated diene. The hydrogenated copolymer (I) containing one, and the polymer structure before hydrogenation is not particularly limited.
(AB) n, A- (BA) n, B- (AB) n + 1
(C-A-B) n, A- (B-C--A) n, B- (C-A-B) n + 1
[(AB) k] m + 1-X, [(AB) k-A] m + 1-X
[(BA) k] m + 1-X, [(BA) k-B] m + 1-X
[(C-A-B) k] m + 1-X, [(A-B-C) k-A] m + 1-X
(In the above formula, A (polymer block (A)) is a polymer block made of vinyl aromatic hydrocarbon, and B (copolymer block (B)) is a copolymer made of vinyl aromatic hydrocarbon and conjugated diene. Although it is a block, it may contain a homopolymer block C composed of a conjugated diene, where X is, for example, silicon tetrachloride, tin tetrachloride, 1,3 bis (N, N-glycidylaminomethyl) cyclohexane, epoxidation large It represents a residue of a coupling agent such as soybean oil or a residue of an initiator such as a polyfunctional organolithium compound, where n, k and m are integers of 1 or more, generally 1 to 5. The structure of the polymer chain bonded to X may be the same or different.) A linear hydrogenated copolymer or a radial hydrogenated copolymer represented by (2) or any mixture of these polymer structures Can be used . In the radial hydrogenated copolymer represented by the above general formula, A and / or B may be further bonded to X.

The block copolymer (II) or hydrogenated polymer structure used in the present invention has the general formula:
(Ab-Bb) n, Ab- (Bb-Ab) n, Bb- (Ab-Bb) n + 1
(Wherein n is an integer of 1 or more, generally 1 to 5), or a linear block copolymer represented by the general formula:
[(Ab-Bb) k] m + 2-X, [(Ab-Bb) k-Ab] m + 2-X
[(Bb-Ab) k] m + 2-X, [(Bb-Ab) k-Bb] m + 2-X
(In the above formula, Ab (plastic polymer segment A) is a polymer block mainly composed of vinyl aromatic hydrocarbon, and Bb (elastomeric polymer segment B) is a polymer mainly composed of conjugated diene. The boundary between the Ab block and the Bb block need not necessarily be clearly distinguished, where X is, for example, silicon tetrachloride, tin tetrachloride, 1,3 bis (N, N-glycidylaminomethyl) cyclohexane, epoxidized soybean oil A residue of a coupling agent such as, or a residue of an initiator such as a polyfunctional organolithium compound, wherein k and m are integers of 1 to 5.), or these Mixtures of any polymer structure of the block copolymer can be used. The block copolymer (II) used in the present invention is a vinyl aromatic hydrocarbon having an organic lithium compound as an initiator in a hydrocarbon solvent, similarly to the non-hydrogenated copolymer of the hydrogenated copolymer (I). It can be obtained by polymerizing conjugated dienes, and the weight ratio of vinyl aromatic hydrocarbon to conjugated diene is in the range of 65/35 to 82/18, preferably in the range of 70/30 to 80/20.

The Vicat softening temperature of the composition comprising the hydrogenated copolymer (I) and the block copolymer (II) of the present invention is in the range of 60 to 83 ° C, preferably 63 to 81 ° C, more preferably 65 to 78 ° C. is there. When the Vicat softening temperature is in the range of 60 to 83 ° C., the natural shrinkage and the low temperature shrinkability are excellent.
In the present invention, the non-hydrogenated copolymer before hydrogenation can be obtained by polymerizing vinyl aromatic hydrocarbon and conjugated diene in a hydrocarbon solvent using an organolithium compound as an initiator. Examples of the vinyl aromatic hydrocarbon used in the present invention include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, 1, Examples include 1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene, and a particularly common one is styrene. These may be used alone or in combination of two or more.

The conjugated diene is a diolefin having a pair of conjugated double bonds, such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene. 1,3-pentadiene, 1,3-hexadiene, etc., and particularly common examples include 1,3-butadiene and isoprene. These may be used alone or in combination of two or more.
In the present invention, the non-hydrogenated copolymer before hydrogenation is obtained, for example, by anion living polymerization using an initiator such as an organic alkali metal compound in a hydrocarbon solvent. Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and cycloheptane. In addition, alicyclic hydrocarbons such as methylcycloheptane, and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene can be used. These may be used alone or in combination of two or more.

As the polymerization initiator, aliphatic hydrocarbon alkali metal compounds, aromatic hydrocarbon alkali metal compounds, organic amino alkali metal, which are generally known to have anionic polymerization activity for conjugated dienes and vinyl aromatic compounds. A compound or the like can be used. Examples of the alkali metal include lithium, sodium, potassium, and the like. Suitable organic alkali metal compounds are aliphatic and aromatic hydrocarbon lithium compounds having 1 to 20 carbon atoms, and one lithium per molecule. And dilithium compounds, trilithium compounds, and tetralithium compounds containing a plurality of lithium atoms in one molecule.
Specifically, n-propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, hexamethylene dilithium, butadienyl dilithium, isoprenyl dilithium, diisopropenylbenzene and sec-butyl lithium Examples of the reaction product include a reaction product of divinylbenzene, sec-butyllithium and a small amount of 1,3-butadiene. Furthermore, organic alkali metal compounds disclosed in US Pat. No. 5,708,092, British Patent 2,241,239, US Pat. No. 5,527,753, etc. are also used. be able to. These may be used alone or in combination of two or more.

In the present invention, the polymerization temperature for producing the non-hydrogenated copolymer before hydrogenation is generally -10 ° C to 150 ° C, preferably 40 ° C to 120 ° C. The time required for the polymerization varies depending on the conditions, but is usually within 10 hours, particularly preferably 0.5 to 5 hours. The polymerization atmosphere is preferably replaced with an inert gas such as nitrogen gas. The polymerization pressure is not particularly limited as long as it is carried out within a range of pressure sufficient to maintain the monomer and solvent in the liquid layer within the above polymerization temperature range. Furthermore, care must be taken not to mix impurities, such as water, oxygen, carbon dioxide, etc., that inactivate the catalyst and living polymer into the polymerization system.
The hydrogenated copolymer of the present invention can be obtained by hydrogenating the non-hydrogenated copolymer obtained above before hydrogenation. The hydrogenation catalyst is not particularly limited and is conventionally known (1) A supported heterogeneous hydrogenation in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like. A catalyst, (2) a so-called Ziegler-type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, Cr or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum, (3) Ti, Ru, A homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as Rh or Zr is used. Specific examples of the hydrogenation catalyst include Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-337970, Japanese Patent Publication No. 1-53851, The hydrogenation catalyst described in Japanese Utility Model Publication No. 2-9041 can be used. A preferred hydrogenation catalyst is a mixture with a titanocene compound and / or a reducing organometallic compound.

As the titanocene compound, compounds described in JP-A-8-109219 can be used. Specific examples thereof include (substitution) such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. Examples thereof include compounds having at least one ligand having a cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton. Examples of the reducing organometallic compound include organic alkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.
The hydrogenation reaction is generally carried out in a temperature range of 0 to 200 ° C, more preferably 30 to 150 ° C. The pressure of hydrogen used for the hydrogenation reaction is 0.1 to 15 MPa, preferably 0.2 to 10 MPa, and more preferably 0.3 to 7 MPa. The hydrogenation reaction time is usually 3 minutes to 10 hours, preferably 10 minutes to 5 hours. The hydrogenation reaction can be any of a batch process, a continuous process, or a combination thereof.

In the hydrogenated copolymer (I) of the present invention, the hydrogenation rate of the unsaturated double bond based on the conjugated diene is 60% by weight of the unsaturated double bond based on the conjugated diene compound in the non-hydrogenated copolymer. Above, preferably 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more. When the hydrogenation rate is 60% by weight or more, the solvent resistance is excellent.
In the hydrogenated block copolymer (II) used in the present invention, the total hydrogenation rate of unsaturated double bonds based on the conjugated diene compound can be arbitrarily selected according to the purpose and is not particularly limited. 70% or more, preferably 80% or more, more preferably 90% or more of the unsaturated double bond based on the conjugated diene compound in the block copolymer (II) may be hydrogenated, or only a part thereof. It may be hydrogenated. When only a part is hydrogenated, the hydrogenation rate is preferably 1% or more and less than 70%, or 10% or more and less than 65%, or 20% or less and less than 60% if desired. The hydrogenation rate can be known by a nuclear magnetic resonance apparatus (NMR).

In the present invention, the microstructure (ratio of cis, trans, vinyl) of the conjugated diene moiety in the hydrogenated copolymer (I) can be arbitrarily changed by using a polar compound or the like, and is not particularly limited. In general, the vinyl bond amount can be set in the range of 5 to 90%, preferably 10 to 80%, more preferably 15 to 75%. In the present invention, the amount of vinyl bonds means the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (however, when 1,3-butadiene is used as the conjugated diene, 1,2-vinyl bonds are used. Binding amount). The amount of vinyl bonds can be grasped by a nuclear magnetic resonance apparatus (NMR).
In the hydrogenated copolymer (I) of the present invention, the peak temperature of the function tan δ of dynamic viscoelasticity measurement exceeds 80 ° C. and is in the range of 110 ° C. or less, preferably 83 to 105 ° C., more preferably 83 to 100 ° C. Particularly preferably, it is necessary that at least one is present in the range of 83 to 95 ° C. In the hydrogenated copolymer of the present invention, it is necessary that the peak temperature of the function tan δ of dynamic viscoelasticity measurement does not exist between −10 ° C. and 80 ° C., and the peak temperature of tan δ exists within this temperature range. Then, since it is inferior to a natural contractility, it is not preferable.

The peak of the dynamic viscoelasticity function tan δ of the block copolymer (II) used in the present invention is in the range of −95 to −10 ° C., preferably in the range of −90 to −15 ° C., more preferably −85 to 85 ° C. At least one exists in the range of −20 ° C. The peak of the dynamic viscoelasticity function tan δ of the block copolymer (II) is excellent in low temperature elongation when it is in the range of −95 to −10 ° C.
The function tan δ in the dynamic viscoelasticity measurement is a value measured by, for example, a viscoelasticity measuring / analyzing apparatus DVE-V4 manufactured by Rheology Co., Ltd. or a Leo Vibron DDV-3 type manufactured by Toyo Baldwin, Inc. Measurement is performed using a test piece having a thickness of 0.5 to 2 mm under the condition of 3 ° C./min. The temperature showing the peak means a temperature at which the first derivative of the amount of change of the tan δ value with respect to the temperature becomes zero. The peak temperature of the tan δ is, for example, increasing the vinyl aromatic hydrocarbon content, increasing the molecular weight of the hydrogenated copolymer, and the content of the vinyl aromatic hydrocarbon polymer block (A) in the hydrogenated copolymer. The amount of vinyl aromatic hydrocarbon in the copolymer block (B) can be adjusted to be high.

The aliphatic unsaturated carboxylic acid ester of the aliphatic unsaturated carboxylic acid ester-styrene copolymer (III) used in the present invention is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, esters of the number of _C 1 _{-C 12} preferably carbon alcohol and acrylic acid _C 2 _{-C 12} hexyl acrylate, or methacrylic acid and the number of _C 1 _{-C 12} preferably carbon carbon number _C 2 _{-C 12} Esters of alcohol and acrylic acid, and α or β unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and the like and mono- or diesters of C ₁ -C ₁₂ , preferably C ₂ -C ₁₂ alcohols Is at least one selected from The content of the aliphatic unsaturated carboxylic acid ester in the aliphatic unsaturated carboxylic acid ester-styrene copolymer is 10 to 30% by weight, preferably 13 to 27% by weight, and more preferably 15 to 20% by weight. . A particularly preferred aliphatic unsaturated carboxylic acid ester-styrene copolymer is a copolymer mainly composed of n-butyl acrylate and styrene. A heat-shrinkable film using an aliphatic unsaturated carboxylic acid ester-styrene copolymer mainly composed of n-butyl acrylate and styrene has good shrinkage and natural shrinkage.

  The weight ratio of the hydrogenated copolymer (I) to the block copolymer (II) in the composition of the present invention is 10/90 to 90/10, preferably 20/80 to 80/20, more preferably 30/70. ~ 70/30. The weight ratio of the copolymer (I), the block copolymer (II) and the aliphatic unsaturated carboxylic acid ester-styrene copolymer (III) is such that the total amount is 100% by weight and (I) is 10 -80 wt%, (II) 10-80 wt%, and (III) 5-50 wt%, preferably (I) 15-75 wt%, (II) 15-75 wt%, And (III) in the range of 10 to 45% by weight, more preferably (I) in the range of 20 to 70% by weight, (II) in the range of 20 to 70% by weight, and (III) in the range of 15 to 40% by weight. . When the weight ratio of each component of the composition of the present invention is within the range specified in the present invention, it is excellent in a balance of physical properties such as solvent resistance, natural shrinkage, low temperature shrinkage, rigidity, transparency and impact resistance. .

  If necessary, a non-rubber modified styrene polymer and a rubber modified styrene polymer may be added to the composition of the present invention. The non-rubber-modified styrenic polymer is obtained by polymerizing styrene or a monomer copolymerizable therewith (except for the aliphatic unsaturated carboxylic acid ester-styrene copolymer (III)). Examples of the monomer copolymerizable with styrene include α-methylstyrene, acrylonitrile, maleic anhydride and the like. Examples of the styrenic polymer include polystyrene (including syndiotactic polystyrene), styrene-α-methylstyrene copolymer, acrylonitrile-styrene copolymer, styrene-maleic anhydride copolymer, and the like. An example of the styrenic polymer is polystyrene. A polymer having a weight average molecular weight of 50,000 to 500,000 can be generally used. These styrenic polymers can be used singly or as a mixture of two or more, and can be used as a rigidity improving agent. The rubber-modified styrenic polymer is obtained by polymerizing a mixture of a monomer copolymerizable with a vinyl aromatic hydrocarbon and an elastomer. The polymerization method is suspension polymerization, emulsion polymerization, bulk polymerization, bulk-suspension polymerization. Etc. are generally performed. Examples of the monomer copolymerizable with the vinyl aromatic hydrocarbon include α-methylstyrene, acrylonitrile, acrylic acid ester, methacrylic acid ester, maleic anhydride and the like. As the copolymerizable elastomer, natural rubber, synthetic isoprene rubber, butadiene rubber, styrene-butadiene rubber, high styrene rubber or the like is used.

  These elastomers are generally 3 to 50 parts by weight with respect to 100 parts by weight of vinyl aromatic hydrocarbon or a monomer copolymerizable therewith, or dissolved in latex or emulsion-like, bulk polymerization, bulk-suspension polymerization in latex form. Etc. A particularly preferable rubber-modified styrene polymer is an impact-resistant rubber-modified styrene polymer (HIPS). The rubber-modified styrenic polymer can be used as an agent for improving rigidity, impact resistance and slipperiness. A polymer having a weight average molecular weight of 50,000 to 500,000 can be used. The addition amount of the rubber-modified styrenic polymer is preferably 0.1 to 10 parts by weight in consideration of maintaining transparency.

In the hydrogenated copolymer (I) and the composition of the present invention, at least one selected from fatty acid amide, paraffin, hydrocarbon-based resin and fatty acid is used as a lubricant with respect to 100 parts by weight of the hydrogenated copolymer (I). Addition of 0.01 to 5 parts by weight, preferably 0.05 to 4 parts by weight, and more preferably 0.1 to 3 parts by weight improves the blocking resistance.
Examples of fatty acid amides include stearoamide, oleylamide, erucylamide, behenamide, mono- or bisamide of higher fatty acids, ethylene bisstearoamide, stearyl oleylamide, N-stearyl erucamide, and these may be used alone or in combination of two or more. Can be used. Examples of the paraffin and hydrocarbon resins include paraffin wax, microcrystalline wax, liquid paraffin, paraffin synthetic wax, polyethylene wax, composite wax, montan wax, hydrocarbon wax, silicone oil, etc. Two or more types can be mixed and used.

  Examples of fatty acids include saturated fatty acids and unsaturated fatty acids. That is, saturated fatty acids such as lauric acid, palmitic acid, stearic acid, behenic acid, hydroxystearic acid, unsaturated fatty acids such as oleic acid, erucic acid, ricinoleic acid, methylene bis stearic acid, ethylene biscapric acid, ethylene bis laurin Acid, ethylene bis stearic acid, ethylene bisisostearic acid, ethylene bishydroxystearic acid, ethylene bisbehenic acid, hexamethylene bishydroxystearic acid, m-xylylene bisstearic acid, etc., but these may be used alone or in combination of two or more. Can be used.

  The hydrogenated copolymer (I) and the composition of the present invention include at least one selected from a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, and a hindered amine light stabilizer as an ultraviolet absorber and a light stabilizer. UV absorber and light stabilizer of 0.05 to 3 parts by weight, preferably 0.05 to 2.5 parts by weight, more preferably 0.1 to 2 parts by weight based on 100 parts by weight of the block copolymer hydrogenated product. Addition of parts by weight improves light resistance. Examples of benzophenone ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone. 2-hydroxy-4-n-octoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 3,5-di-t-butyl-4-hydroxybenzoyl Acid, n-hexadecyl ester, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 1,4-bis (4-benzoyl-3-hydroxyphenoxy) butane, 1,6-bis (4- Benzoyl-3-hydroxyphenoxy) hexane and the like.

  Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl)- 5-chlorobenzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole, 2 -[2'-hydroxy-3 '-(3 ", 4", 5 ", 6"-[4H] tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotri Sol, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- [2′-hydroxy-3 ′ , 5′-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (2′-hydroxy-4′-octyloxyphenyl) -2H-benzotriazole, 2- (2H-benzotriazole- 2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol.

  Examples of the hindered amine light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,6,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- {3- (3,5-di-tert-butyl-4-hydroxydiphenyl) propionyloxy} ethyl] -4- {3- (3,5-di-tert-butyl-4-hydroxydiphenyl) propionyl Oxy} -2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triasaspiro [4.5] decane-2, 4-dione, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine succinate Emissions polycondensate thereof.

  Also, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl- 4-piperidyl) imino] -hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl) imino], poly [6-morpholino-s-triazine-2,4-diyl] [(2, 2,6,6-tetramethyl-4-piperidyl) imino] -hexamethylene [(2,2,6,6-tetramethyl-4-biperidyl) imino], 2- (3 ′, 5′-di-t -Butyl-4'-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), tetrakis (2,2,6,6-tetramethyl- 4-piperidyl) 1,2,3,4-butanetetracarboxyl Rate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2 , 2,6,6-pentamethyl-4-piperidinol and a condensate of tridecyl alcohol.

  Furthermore, a condensate of 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and tridecyl alcohol, 1,2,3,4-butanetetracarboxylic Acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β, β-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5.5] Undecane) condensate with diethanol, 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and β, β, β, β-tetramethyl-3,9 -Condensation with (2,4,8,10-tetraoxaspiro [5.5] undecane) diethanol, N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl- N- (1,2,2,6,6-pen Tamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, dibutylamine-1,3,5-triazine-N, N-bis (2,2,6,6-tetramethyl) -4-piperidyl-1,6-hexamethylenediamine · N- (2,2,6,6) -tetramethyl-4-piperidyl) butylamine polycondensate, 1,2,2,6,6-pentamethyl- 4-piperidyl-methacrylate, 2,2,6,6-tetramethyl-4-piperidyl-methacrylate and the like.

The hydrogenated copolymer (I) and composition of the present invention contain 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t as a stabilizer. -Gel suppression effect can be obtained by adding 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight of pentylphenyl acrylate with respect to 100 parts by weight of the hydrogenated copolymer (I). .
The hydrogenated copolymer (I) and the composition of the present invention include n-octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2-t-butyl-6- (3- t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-bis [(octylthio) methyl] -o-cresol, tetrakis [methylene-3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2,4-bis At least one phenolic stabilizer such as-(n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine is added to a hydrogenated copolymer (I 1) 0.05 to 3 parts by weight with respect to 0 part by weight, tris- (nonylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 2-[[2, 4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] -N, N-bis [2- [ [2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] -ethyl] -ethanamine, tris At least one organic phosphate-based or organic phosphite-based stabilizer such as (2,4-di-t-butylphenyl) phosphite is added in an amount of 0.05 to 3 per 100 parts by weight of the hydrogenated copolymer (I). Part by weight can be added That.

Various polymers and additives can be added to the hydrogenated copolymer (I) and the composition of the present invention depending on the purpose. Suitable polymers include vinyl aromatic hydrocarbon and conjugated diene block copolymer elastomers or hydrogenated products thereof, and vinyl aromatic hydrocarbons and conjugated dienes that are different from the hydrogenated copolymer (I) of the present invention. Block copolymers and / or hydrogenated products thereof.
In the present invention, a vinyl aromatic hydrocarbon / conjugated diene block copolymer elastomer or a hydrogenated product thereof may have a vinyl aromatic hydrocarbon content of less than 60% by weight, preferably 10 to 50% by weight. The impact resistance and elongation can be improved by blending 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight with respect to 100 parts by weight of the hydrogenated copolymer (I) of the present invention. .

In the hydrogenated block copolymer elastomer, the hydrogenation rate of the unsaturated double bond based on the conjugated diene can be arbitrarily selected according to the purpose and is not particularly limited. 70% or more, preferably 80% or more, more preferably 90% or more of the unsaturated double bonds based on the conjugated diene in the block copolymer elastomer may be hydrogenated, or only a part is hydrogenated. May be. When only a part is hydrogenated, the hydrogenation rate is preferably 10% or more and less than 70%, or 15% or more and less than 65%, and if desired, 20% or more and less than 60%.
The vinyl aromatic hydrocarbon and conjugated diene block copolymer different from the hydrogenated copolymer (I) of the present invention and / or its hydrogenated product has a vinyl aromatic hydrocarbon content of 60 to 95% by weight, Preferably, it is 65 to 90% by weight, and 5 to 90 parts by weight, preferably 10 to 80 parts by weight, based on 100 parts by weight of the hydrogenated copolymer (I) of the present invention, impact resistance and rigidity, Elongation etc. can be improved.

  Other suitable additives include softeners such as coumarone-indene resins, terpene resins, oils, and plasticizers. Various stabilizers, pigments, antiblocking agents, antistatic agents, lubricants and the like can also be added. In addition, as an antiblocking agent, an antistatic agent, a lubricant, for example, fatty acid amide, ethylene bisstearamide, sorbitan monostearate, saturated fatty acid ester of fatty acid alcohol, pentaerythritol fatty acid ester, etc., and as an ultraviolet absorber, p-t-butylphenyl salicylate, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chloro The compounds described in “Practical Handbook for Additives for Plastics and Rubber” (Chemical Industry Co., Ltd.) such as benzotriazole and 2,5-bis- [5′-t-butylbenzoxazolyl- (2)] thiophene are used. it can. These are generally used in the range of 0.01 to 5% by weight, preferably 0.05 to 3% by weight.

The hydrogenated copolymer (I) and the composition thereof of the present invention can be used for various molding materials such as sheets, films and injection molded articles.
The heat-shrinkable uniaxial or biaxially stretched film using the hydrogenated copolymer (I) and the composition of the present invention is obtained by converting the hydrogenated copolymer (I) into a flat shape from a normal T die or a cyclic die. The tube is extruded at 150 to 250 ° C., preferably 170 to 220 ° C., and the obtained unstretched product is substantially uniaxially or biaxially stretched.
For example, in the case of uniaxial stretching, in the case of a film or sheet, it is stretched in the extrusion direction with a calendar roll or the like, or in a direction perpendicular to the extrusion direction with a tenter or the like, and in the case of a tube, in the extrusion direction or circumferential direction of the tube. Stretch. In the case of biaxial stretching, in the case of a film or sheet, the extruded film or sheet is stretched in the longitudinal direction with a metal roll or the like and then stretched in the transverse direction with a tenter or the like. The tubes are stretched simultaneously or separately in the circumferential direction of the tube, that is, in a direction perpendicular to the tube axis.

  In the present invention, the stretching temperature is 60 to 160 ° C., preferably 70 to 150 ° C., more preferably 80 to 140 ° C., and the stretching ratio is 1.5 to 8 times, preferably 2 to 6 in the machine direction and / or the transverse direction. It is preferable to stretch it twice. The stretching temperature is 60 ° C. or higher from the viewpoint of breaking during stretching, and 110 ° C. or lower from the viewpoint of shrinkage characteristics. The draw ratio is 1.5 times or more from the viewpoint of heat shrinkage and 8 times or less from the viewpoint of stable production. In the case of biaxial stretching, the stretching ratios in the longitudinal direction and the transverse direction may be the same or different. The uniaxially stretched or biaxially stretched heat-shrinkable film is then subjected to heat treatment at 60 to 160 ° C., preferably 80 to 155 ° C. for a short time, for example, 3 to 60 seconds, preferably 10 to 40 seconds. It is also possible to implement means to prevent natural contraction below.

  In order to use the heat-shrinkable film thus obtained as a heat-shrinkable packaging material or a heat-shrinkable label material, the heat shrinkage rate at 80 ° C. in the stretching direction is 5 to 60%, preferably 10 It is -55%, More preferably, it is 15-50%. When the heat shrinkage ratio is within such a range, a heat shrinkable film having an excellent balance between the heat shrinkage ratio and the natural shrinkage ratio can be obtained. In the present invention, the heat shrinkage rate at 80 ° C. is a measure of low temperature shrinkage, and a uniaxially stretched film or a biaxially stretched film is a heat medium that does not impair the characteristics of molded products such as 80 ° C. hot water, silicone oil, and glycerin. It is the thermal shrinkage rate in each stretching direction of the molded product when immersed in the interior for 10 seconds. In the present invention, it is recommended that the natural shrinkage rate of the heat shrinkable film itself is 2.5% or less, preferably 2.0% or less, more preferably 1.5% or less within the range of the heat shrinkage rate. The Here, the natural shrinkage ratio of the heat shrinkable film itself is a value calculated by an equation described later after leaving the heat shrinkable film in the range of the above heat shrinkage ratio at 35 ° C. for 5 days.

Furthermore, the uniaxially stretched or biaxially stretched film of the present invention needs to have a tensile elastic modulus in the stretching direction of 700 to 3000 MPa, preferably 1000 to 2500 MPa as a heat shrink wrapping material. The tensile elastic modulus in the stretching direction is 700 MPa or more due to the problem of settling in the shrink wrapping process, and is 3000 MPa or less due to the problem of impact resistance of the film.
When the uniaxially stretched or biaxially stretched film of the present invention is used as a heat-shrinkable packaging material, a temperature of 130 to 300 ° C., preferably 150 to 250 ° C., is used for several seconds to several minutes in order to achieve the desired heat shrinkage rate. Preferably, the heat shrinkage can be performed by heating for 1 to 60 seconds.

  The heat-shrinkable film of the present invention may be a multilayer laminate having at least two layers, preferably at least three layers. Specific examples of the usage form as the multilayer laminate include those disclosed in Japanese Patent Publication No. 3-5306. You may use the hydrogenated copolymer (I) or composition of this invention for an intermediate | middle layer and both outer layers. When the hydrogenated copolymer (I) or composition of the present invention is used in a multilayer film, the layers other than the film layer using the hydrogenated copolymer (I) or composition of the present invention are not particularly limited. The hydrogenated copolymer (I) of the present invention having different constituents or composition, or a composition thereof, or a hydrogenated copolymer other than the present invention or a hydrogenated copolymer other than the present invention, and the above vinyl aromatic carbonization It may be a multilayer laminate in which a composition with a hydrogen polymer is combined. In addition, polypropylene, polyethylene, ethylene polymer (ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, etc.) ionomer resin, nylon resin, polyester resin, polymethyl Examples include at least one component selected from a methacrylate resin, an ABS resin, the above-mentioned vinyl aromatic hydrocarbon polymer, and the like. Preferably, a hydrogenated copolymer other than the present invention or a hydrogenated copolymer other than the present invention is used. A composition of a coalescence and the vinyl aromatic hydrocarbon polymer, and the vinyl aromatic hydrocarbon polymer.

The heat shrinkable multilayer film of the present invention has a heat shrinkage rate of 80 ° C. in the stretching direction of 5 to 60%, preferably 10 to 55%, more preferably 15 to 50%, and a tensile elastic modulus in the drawing direction of 700. It is also possible to obtain a heat-shrinkable multilayer film of ˜3000 MPa, preferably 1000 to 2500 MPa.
The thickness of the heat-shrinkable film and heat-shrinkable multilayer film of the present invention is 10 to 300 μm, preferably 20 to 200 μm, more preferably 30 to 100 μm, and the ratio of the thickness of both surface layers to the inner layer (sum of both surface layers / inner layer) ) Is recommended to be 5/95 to 50/50, preferably 10/90 to 35/65.

The heat-shrinkable film of the present invention can be used for various uses such as packaging of fresh foods, confectionery, clothing, stationery, etc. by making use of the characteristics. As a particularly preferred application, letters and designs are printed on a uniaxially stretched film of a block copolymer defined in the present invention, and then the surface of a packaged object such as a plastic molded product, a metal product, a glass container, or a porcelain is thermally contracted. It can be used as a material for so-called heat-shrinkable labels that are used in close contact.
In particular, the uniaxially stretched heat-shrinkable film of the present invention is excellent in solvent resistance, low-temperature shrinkage, rigidity and natural shrinkage. , Materials having extremely different coefficients of thermal expansion and water absorption from the block copolymer of the present invention, such as metals, porcelain, glass, paper, polyethylene, polypropylene, polybutene, and other polyolefin resins, polymethacrylate resins, polycarbonate It can be suitably used as a heat-shrinkable label material for containers using at least one selected from polyester resins such as polyethylene resins, polyethylene terephthalate, polybutylene terephthalate, and polyamide resins as constituent materials.

The material constituting the plastic container in which the heat-shrinkable film of the present invention can be used is polystyrene, rubber-modified impact-resistant polystyrene (HIPS), styrene-butyl acrylate copolymer, styrene-acrylonitrile in addition to the above resins. Copolymer, styrene-maleic anhydride copolymer, acrylonitrile-butadiene-styrene copolymer (ABS), methacrylic ester-butadiene-styrene copolymer (MBS), polyvinyl chloride resin, phenol resin, urea resin Melamine resin, epoxy resin, unsaturated polyester resin, silicone resin and the like. These plastic containers may be a mixture of two or more resins or a laminate.
When the heat-shrinkable film of the present invention is used as a heat-shrinkable label material, the heat shrinkage rate after 10 seconds at 80 ° C. in the direction perpendicular to the stretching direction is less than 20%, preferably 10% or less. . Therefore, in the present invention, uniaxial stretching for a heat-shrinkable label means that the heat shrinkage rate after 10 seconds at 80 ° C. in the drawing direction is 5 to 60% and the heat shrinkage rate in the direction orthogonal to the drawing direction is less than 20%. It is said that a stretching process is performed so that

Examples of the present invention will be described below, but these do not limit the scope of the present invention. Table 1 shows hydrogenated copolymers (I), and Table 2 shows block copolymers (II) and styrene-n-butyl acrylate copolymers and general-purpose polystyrene (GPPS) as vinyl aromatic hydrocarbon polymers. It was.
(Preparation of hydrogenated copolymer (I) A-1 to A-6)
The non-hydrogenated copolymer before hydrogenation was prepared by using n-butyllithium in a cyclohexane solvent as a catalyst, tetramethylethylenediamine as a randomizing agent, and the styrene content (% by weight) and styrene polymer block (weight) shown in Table 1. %), A block copolymer having a weight average molecular weight was produced. The styrene content was adjusted by adding styrene and butadiene, the styrene polymer block was adjusted by weight ratio of styrene alone and styrene and butadiene, and the weight average molecular weight was adjusted by catalytic amount. In the preparation of the copolymer, a monomer diluted with cyclohexane to a concentration of 20% by weight was used.
The hydrogenation catalyst was charged with 1 liter of dried and purified cyclohexane in a nitrogen-substituted reaction vessel, 100 mmol of bis (η ⁵ -cyclopentadienyl) titanium dichloride was added, and 200 mmol of trimethylaluminum with sufficient stirring. The hydrogenation catalyst which added the n-hexane solution containing this and made it react at room temperature for about 3 days was used.

1) Hydrogenated copolymer A-1
Using an autoclave with a stirrer, 0.055 parts by weight of n-butyllithium and 0.05 parts by weight of tetramethylethylenediamine are added to a cyclohexane solution containing 19 parts by weight of styrene under a nitrogen gas atmosphere, and polymerization is performed at 70 ° C. for 20 minutes. Hold for 5 minutes. Next, a cyclohexane solution containing 51 parts by weight of styrene and 11 parts by weight of 1,3-butadiene was continuously added for 70 minutes, polymerized at 70 ° C., and held for 5 minutes.
Next, a cyclohexane solution containing 19 parts by weight of styrene was added, polymerized at 70 ° C. for 20 minutes, and held for 5 minutes. Next, 100 ppm of a hydrogenation catalyst as titanium per 100 parts by weight of the polymer was added to the polymer solution obtained above, and a hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. Thereafter, methanol was added, and then 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by mass of the polymer. Removal of the solvent gave hydrogenated copolymer A-1. The hydrogenation rate of the hydrogenated copolymer A-1 was adjusted by the amount of hydrogen so that the hydrogenation rate was 96%.
2) Hydrogenated copolymers A-2 to A-5
Hydrogenated copolymers A-2 to A-5 were prepared in the same manner as in A-1 with the composition of styrene and butadiene shown in Table 1 (the addition rate of styrene and butadiene and the polymerization temperature were the same).

(Preparation of block copolymers B-1 and B-2)
In Table 2, at least one polymer block mainly composed of vinyl aromatic hydrocarbon and at least one polymer block composed of conjugated diene and at least one heavy composed of conjugated diene and vinyl aromatic hydrocarbon used in the examples are used. A block copolymer having a combined block is shown. The block copolymer was obtained by adding and polymerizing normal butyl lithium in cyclohexane as a polymerization initiator and, if necessary, tetramethylethylenediamine as a randomizing agent for adjusting the content of single-chain styrene. In preparing the block copolymer, a monomer diluted with cyclohexane to a concentration of 20% by weight was used.

1) Block copolymer B-1
Using an autoclave with a stirrer, 0.070 parts by weight of n-butyllithium and 0.02 parts by weight of tetramethylethylenediamine are added to a cyclohexane solution containing 24 parts by weight of styrene under a nitrogen gas atmosphere, and continuously supplied at 75 ° C. for 20 minutes. And polymerized. Next, a cyclohexane solution containing 14 parts by weight of styrene, 21 parts by weight of 1,3-butadiene and 5 parts by weight of isoprene was continuously fed at 75 ° C. for 50 minutes to polymerize. Next, a cyclohexane solution containing 36 parts by weight of styrene was continuously fed at 75 ° C. for 30 minutes for polymerization, and then held at 75 ° C. for 10 minutes. Then, the polymerization was stopped, and 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate was used as a block copolymer as a stabilizer. After adding 0.6 part by weight to 100 parts by weight of the composition, the solvent was removed to obtain a block copolymer.
2) Block copolymer B-2
Block copolymer B-2 was prepared in the same manner as B-1.

(Preparation of aliphatic unsaturated carboxylic acid ester-styrene copolymer)
Styrene-n-butyl acrylate copolymer B-3 and styrene-methyl methacrylate copolymer B-4 are ratios shown in Table 2 for 10 L autoclave with a stirrer and styrene and n-butyl acrylate or methyl methacrylate. In addition, 0.3 kg of ethylbenzene and a predetermined amount of 1,1 bis (t-butylperoxy) cyclohexane are charged in order to adjust the MFR, and after polymerization at 110 to 150 ° C. for 2 to 10 hours, using a vent extruder Unreacted styrene, n-butyl acrylate, methyl methacrylate and ethylbenzene were recovered and produced. The MFR of the obtained B-3 was 3.0 g / 10 min, and the MFR of B-4 was 2.6 g / 10 min.

(Measurement and evaluation method)
The measurement and evaluation described in Examples and Comparative Examples were performed by the following methods.
1) Styrene content The styrene content of the hydrogenated copolymer (I) was measured using an ultraviolet spectrophotometer (device name: UV-2450; manufactured by Shimadzu Corporation).
2) Polymer block (A)
A method of oxidatively decomposing a non-hydrogenated copolymer before hydrogenation with tertiary butyl hydroperoxide using osmium tetroxide as a catalyst (IM KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946). )). The polymer block (A) is obtained by using a vinyl aromatic hydrocarbon polymer block component obtained by the same method (however, a vinyl aromatic hydrocarbon polymer component having an average degree of polymerization of about 30 or less is excluded). It was obtained from the following formula.
Polymer block (A) (% by weight) = (weight of vinyl aromatic hydrocarbon polymer block (A) in non-hydrogenated copolymer / weight in non-hydrogenated copolymer) × 100

3) Weight average molecular weight The molecular weight of the hydrogenated copolymer (I) was measured using a GPC apparatus (manufactured by Waters, USA). Tetrahydrofuran was used as a solvent, and measurement was performed at 35 ° C. The weight average molecular weight was calculated | required using the analytical curve created using the commercially available standard polystyrene whose weight average molecular weight and number average molecular weight are known.
4) Hydrogenation rate Using a non-hydrogenated copolymer before hydrogenation of the hydrogenated copolymer (I) and a hydrogenated copolymer after hydrogenation, a nuclear magnetic resonance apparatus (device name: DPX-400; Germany) Measured by the country, manufactured by BRUKER).
5) Vicat softening temperature A hydrogenated copolymer (I) compression molded to a thickness of 3 mm was used as a test piece and measured according to ASTM D-1525 (load: 1 Kg, heating rate: 2 ° C./min). Value.

6) Dynamic viscoelasticity measurement Dynamic viscoelasticity measurement is performed using a viscoelasticity measuring device DVE-V4 (manufactured by Rheology Co., Ltd.), with a vibration frequency of 35 Hz, a heating rate of 3 ° C / min, and a measurement temperature of -100 ° C. In the range of 150 ° C., a 2.0 mm thick sheet obtained by hot press compression molding was measured as a sample. Hot press compression molding was performed at a temperature of 200 ° C., a pressure of 14.7 MPa, and a compression time of 5 minutes.
7) Shrinkage The 80 ° C shrinkage was calculated from the following equation by immersing the stretched film in 80 ° C silicone oil for 10 seconds.
Thermal contraction rate (%) = (L−L1) / L × 100,
L: Length before contraction, L1: Length after contraction.
8) Natural shrinkage rate This is a value calculated by the following formula after leaving a stretched film with a shrinkage rate of 40% at 80 ° C for 5 minutes at 35 ° C for 5 days.
Natural shrinkage (%) = (L2−L3) / L2 × 100,
L2: length before being left, L3: length after being left.
The smaller the natural shrinkage rate, the better the natural shrinkage.

9) Tensile elastic modulus and elongation at break Using a tensile tester, the film was measured in the MD direction at a tensile speed of 100 mm / min. The test piece was 15 mm wide and 30 mm between the marked lines. The measurement temperature was 23 ° C for tensile modulus and 5 ° C for elongation at break. The unit is MPa for tensile modulus and% for elongation.
10) Puncture impact strength Measured according to JIS P-8134. The unit is J.
11) Haze
Liquid paraffin was applied to the surface of the stretched film and measured according to ASTM D1003. Units%.

12) Solvent resistance Methyl ethyl ketone / isopropyl alcohol (ratio 7/3) was applied to a stretched film 15 cm in MD × 15 cm in TD with a brush and dried at 30 ° C. for 7 days. Judged by the retention rate of elongation.
<Criteria>
○: Retention rate of 50% or more X: Retention rate of less than 50% 13) Blocking property Two stretched multilayer films of 5 cm in MD direction × 5 cm in TD direction were overlaid, and a load of 98 Pa was applied and left at 40 ° C. for 7 days to form a film. The blocking state of was visually determined.
<Criteria>
○: Blocking is not recognized.
X: Blocking is recognized.

14) Warm water fusing property The stretched film was wound around a glass bottle having a diameter of about 8 cm, left in 70 ° C. warm water for 5 minutes, and the fused state of the film was visually determined.
<Criteria>
○: not fused x: not fused immediately after fusion.
15) FE
The hydrogenated copolymer (I) was continuously formed into a sheet having a thickness of 0.3 mm for 6 hours using a 40 mm sheet extruder at an extrusion temperature of 240 ° C., and the sheet area after 5 minutes and 6 hours from the start of operation. The number of FEs of 0.5 mm or more per 300 cm ² was counted and evaluated by the difference in the number of FEs.
<Criteria>
○: Difference is less than 100 ×: Difference exceeds 100

[Examples 1-6, Comparative Examples 1-3]
The measurement of heat-shrinkable film performance was performed by measuring the hydrogenated copolymers (I): A-1 to A-7, block copolymers (II): B-1 and B-2 shown in Tables 1 and 2. Styrene-n-butyl acrylate copolymer: B-3, styrene-methyl methacrylate copolymer: B-4 composition of type and amount, thickness of 0.25 mm at 200 ° C. using a 40 mm extruder. After that, the stretching temperature was 88 ° C. (Comparative Example 1 was stretched at 105 ° C. because it could not be stretched at 88 ° C.), and a tenter was used to uniaxially stretch the stretch ratio to 5 times on the horizontal axis Thus, a heat-shrinkable film having a thickness of about 60 μm was obtained.
Table 3 shows the film performance of the heat-shrinkable film. The performance of the heat shrinkable film of the present invention is as follows: rigidity represented by tensile modulus, low temperature shrinkage represented by 80 ° C. shrinkage, natural shrinkage, impact resistance represented by puncture impact strength, solvent resistance It can be seen that the transparency represented by Haze is excellent. In addition, the sheet | seat and film performance shown in Table 3 were performed by said method.
In addition, the peak temperature of the dynamic viscoelasticity function tan δ of the hydrogenated copolymers (I) A-1 to 4 used in the examples was not observed in the range of −10 to 80 ° C.

[Examples 7 and 8]
A three-layer sheet having the composition shown in Table 5 as an intermediate layer and front and back layers was extruded from a T-die, stretched 1.2 times in the longitudinal direction, and formed into a sheet having a thickness of 0.25 mm. Next, the film was stretched 5 times in the transverse direction at a stretching temperature of 95 ° C. by a tenter to obtain a heat-shrink film having a thickness of about 50 μm. The thickness ratio (%) between the middle layer and the surface layer / back layer was 15 (surface layer) / 70 (middle layer) / 15 (back layer). The performance of the obtained three-layer heat-shrinkable film is shown in Table 5. As an ultraviolet absorber, 0.2 part by weight of ADK STAB LA-32 (manufactured by Asahi Denka Kogyo Co., Ltd.) was added to 100 parts by weight of the front and back layers.

  The heat-shrinkable film using the hydrogenated copolymer of the present invention is transparent and excellent in solvent resistance, rigidity, natural shrinkage, low-temperature shrinkage, hot-water fusion, low-temperature elongation and impact resistance. Thinning of the film, dimensional stability and low-temperature shrinkage can be achieved at the same time, and it can be suitably used for beverage container packaging, cap seals and various labels.

Claims (15)

At least one polymer block (A) obtained by hydrogenating a non-hydrogenated copolymer comprising a vinyl aromatic hydrocarbon and a conjugated diene, comprising a vinyl aromatic hydrocarbon;
A hydrogenated copolymer (I) containing at least one copolymer block (B) comprising a vinyl aromatic hydrocarbon and a conjugated diene, and having the following characteristics (1) to (7): Characterized hydrogenated copolymer (I).
(1) The vinyl aromatic hydrocarbon content is in the range of more than 80% by weight and less than 90% by weight with respect to the weight of the hydrogenated copolymer (I).
(2) The content of the polymer block (A) is in the range of more than 25% by weight and less than 60% by weight based on the weight of the non-hydrogenated copolymer (I).
(3) The vinyl aromatic hydrocarbon content in the copolymer block (B) is in the range of 80 wt% or more and less than 95 wt%,
(4) The weight average molecular weight is in the range of 50,000 to 1,000,000,
(5) The hydrogenation rate of the double bond of the conjugated diene unit is 60% by weight or more,
(6) The Vicat softening temperature of the hydrogenated copolymer (I) is in the range of 65 to 85 ° C.
(7) The hydrogenated copolymer (I) has at least one peak of the function tan δ of dynamic viscoelasticity measurement exceeding 80 ° C. and 110 ° C. or less. (1) The vinyl aromatic hydrocarbon content is in the range of 82 to 89% by weight based on the weight of the hydrogenated copolymer (I),
(2) The content of the polymer block (A) is in the range of 28 to 55% by weight with respect to the weight of the non-hydrogenated copolymer (I),
(3) The vinyl aromatic hydrocarbon content in the copolymer block (B) is in the range of 83% by weight or more and less than 92% by weight,
(4) The weight average molecular weight is in the range of 100,000 to 800,000,
(5) The hydrogenation rate of the double bond of the conjugated diene unit is 70% by weight or more,
(6) The Vicat softening temperature of the hydrogenated copolymer (I) is in the range of 68 to 80 ° C.,
(7) At least one peak of the dynamic viscoelasticity function tan δ of the hydrogenated copolymer (I) exceeds 83 ° C. and 105 ° C. or less.
The hydrogenated copolymer (I) according to claim 1, characterized in that: A vinyl aromatic hydrocarbon comprising the hydrogenated copolymer (I) according to claim 1 or 2 , at least one plastic polymer segment A, and at least one elastomeric polymer segment B. Is a block copolymer having a weight ratio of 65/35 to 82/18 of conjugated diene, and has at least one peak of the dynamic viscoelasticity function tan δ of the block copolymer at −95 to −10 ° C. A composition comprising the block copolymer (II), wherein the Vicat softening temperature of the composition is in the range of 60 to 83 ° C., and the weight ratio of the hydrogenated copolymer (I) to the block copolymer (II) Is a polymer composition having a ratio of 10/90 to 90/10. The hydrogenated copolymer (I) according to claim 1 or 2, the block copolymer (II) according to claim 3, and a styrene content of 70 to 90% by weight, an aliphatic unsaturated carboxylic acid A composition comprising an aliphatic unsaturated carboxylic acid ester-styrene copolymer (III) having an ester content of 30 to 10% by weight, wherein the Vicat softening temperature of the composition is in the range of 60 to 83 ° C, The weight ratio of the copolymer (I), the block copolymer (II), and the aliphatic unsaturated carboxylic acid ester-styrene copolymer (III) is 100% by weight, and (I) is 10 to 80%. A polymer composition comprising: wt%, (II) 10-80 wt%, and (III) 5-50 wt%. The polymer composition according to claim 3 or 4, wherein the hydrogenation rate of the double bond of the conjugated diene unit in the block copolymer (II) is in the range of 1 to 100% by weight. 0.01 to 5 parts by weight of at least one lubricant selected from fatty acid amides, paraffins, hydrocarbon resins and fatty acids is added to 100 parts by weight of the hydrogenated copolymer (I). Item 3. The hydrogenated copolymer (I) according to item 1 or 2. 0.01 to 5 parts by weight of at least one lubricant selected from fatty acid amides, paraffins, hydrocarbon resins and fatty acids with respect to 100 parts by weight of the hydrogenated copolymer (I) according to claim 1 or 2. The polymer composition according to any one of claims 3 to 5, which is added. 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate with respect to 100 parts by weight of the hydrogenated copolymer (I) , 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-bis [(octylthio) methyl] -o-cresol The hydrogenated copolymer (I) according to any one of claims 1, 2, and 6, wherein 0.05 to 3 parts by weight of at least one stabilizer is added . 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl with respect to 100 parts by weight of the hydrogenated copolymer (I) according to claim 1 or 2. ] -4,6-di-t-pentylphenyl acrylate, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-bis The polymer composition according to any one of claims 3 to 5, wherein 0.05 to 3 parts by weight of at least one stabilizer selected from [(octylthio) methyl] -o-cresol is added. object. At least one UV absorber or light stabilizer selected from a benzophenone UV absorber, a benzotriazole UV absorber, and a hindered amine light stabilizer is added to 100 parts by weight of the hydrogenated copolymer (I). The hydrogenated copolymer (I) according to any one of claims 1, 2, 6, and 8, which is added in an amount of 0.05 to 3 parts by weight . A benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, or a hindered amine light stabilizer is selected based on 100 parts by weight of the hydrogenated copolymer (I) according to claim 1 or 2. The polymer composition according to claim 3, wherein 0.05 to 3 parts by weight of at least one ultraviolet absorber or light stabilizer is added. The hydrogenated copolymer (I) according to any one of claims 1, 2, 6, 8, and 10, or 3 to 5, 7, 9, and 10. A sheet / film comprising the polymer composition according to any one of 11 above. The hydrogenated copolymer (I) according to any one of claims 1, 2, 6, 8, and 10, or 3 to 5, 7, 9, and 10. A heat-shrinkable film obtained by stretching the polymer composition according to any one of 11 and having a heat shrinkage rate of 5 to 60% at 80 ° C. in the stretching direction and a tensile elastic modulus in the stretching direction of 700 to 3000 MPa. The hydrogenated copolymer (I) according to any one of claims 1, 2, 6, 8, and 10, or 3 to 5, 7, 9, and 10. 11. A heat-shrinkable multilayer film, wherein the layer made of the polymer composition according to any one of 11 is at least one layer of a multilayer film, and the heat shrinkage rate at 80 ° C. in the stretching direction is 5 to 60%. . The heat-shrinkable multilayer film according to claim 14, which has a tensile elastic modulus in the stretching direction of 700 to 3000 MPa.