JP4919713B2 - Hydrogenated block copolymer composition, sheet and film thereof, and heat-shrinkable film - Google Patents

Description

  The present invention is a sheet film excellent in solvent resistance, rigidity, elongation and transparency, and physical properties such as solvent resistance, natural shrinkage, low temperature shrinkage, rigidity, transparency and elongation suitable for heat shrinkable films. The present invention relates to a hydrogenated block copolymer composition having an excellent balance.

  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.

  In the following document 1, in order to improve the natural shrinkage at room temperature, 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 is disclosed. A polystyrene-based heat-shrinkable film is disclosed.

  Reference 2 below discloses a vinyl aromatic hydrocarbon-aliphatic unsaturated carboxylic acid derivative whose Vicat softening point does not exceed 105 ° C. in order to obtain a transparent heat-shrinkable film having excellent temporal stability and impact resistance of the film. A heat-shrinkable hard film characterized by a specific heat-shrinking force is disclosed in a composition of a copolymer and a copolymer comprising a block of vinyl aromatic hydrocarbon and conjugated diene.

  Reference 3 below provides a copolymer comprising a vinyl aromatic hydrocarbon and conjugated diene block having a specific structure and molecular weight distribution and a vinyl aromatic in order to obtain a composition that balances transparency, rigidity and low-temperature impact. Compositions with hydrocarbon- (meth) acrylic ester copolymer resins are disclosed.

  Reference 4 below discloses a block copolymer having a vinyl aromatic hydrocarbon block vinyl aromatic hydrocarbon and a conjugated diene copolymer block having a specific structure in order to obtain a resin composition having excellent transparency and impact resistance. A transparent high-strength resin composition containing a copolymer of vinyl aromatic hydrocarbon and (meth) acrylic acid ester is disclosed.

  In Patent Document 5 below, in order to obtain a shrink film excellent in low-temperature shrinkage, optical properties, crack resistance properties, dimensional stability, etc., the vinyl aromatic hydrocarbon content is 95 to 20% by weight, and the Vicat softening point is 90. Multilayer low temperature shrinkage having at least one composition of vinyl aromatic hydrocarbon-aliphatic unsaturated carboxylic acid derivative copolymer and copolymer comprising vinyl aromatic hydrocarbon and conjugated diene block not exceeding ℃ A film is disclosed.

  In Patent Document 6 below, in order to obtain a shrink film excellent in natural shrinkage, strength, surface characteristics, waist strength, low-temperature shrinkage, etc., both outer layers have a specific butadiene unit content in styrene-butadiene-styrene type block copolymer. Disclosed is a multilayer polystyrene-based heat-shrinkable film having at least three layers comprising a mixture of a polymer and a styrene-butyl acrylate, and an intermediate layer comprising a mixture of a styrene-butadiene-styrene block copolymer having a specific butadiene unit content and a styrene-butyl acrylate. Yes.

  In Patent Document 7 listed below, in order to obtain a heat-shrinkable film excellent in any of the properties of natural shrinkage, heat-resistant fusion, transparency, and shrink finish, a vinyl aromatic hydrocarbon and a conjugated diene hydrocarbon are used. A block copolymer consisting of a vinyl aromatic hydrocarbon and a conjugated diene hydrocarbon, with a blend comprising a block copolymer, a copolymer of vinyl aromatic hydrocarbon and an aliphatic unsaturated carboxylic acid ester as an intermediate layer A heat-shrinkable polystyrene-based laminated film is disclosed in which a mixed polymer containing a coalescence as a main component is used as front and back layers.

  Patent Document 8 listed below discloses a styrene having a specific Vicat softening point in order to obtain a heat-shrinkable film having no heat-shrinkability at low temperature, shrinkage finish, natural shrinkage, heat, and no blocking between films. -Multi-layer heat-shrinkable polystyrene based on (meth) acrylic acid ester copolymer and having specific heat shrinkage ratio with inner and outer layers mainly composed of styrene-conjugated diene block copolymer with specific Vicat softening point A film is disclosed.

  The following Patent Document 9 is characterized by a specific molecular weight distribution and a residual monomer amount in order to obtain a resin composition and film having a low processing property, storage stability, odor, and excellent rigidity and impact resistance, and a multilayer film. A copolymer resin composed of a styrene monomer and a (meth) acrylic acid ester monomer, a block copolymer resin composed of styrene and a conjugated diene, and a layer mainly composed of a high-impact polystyrene resin composition A (multilayer) heat shrinkable film is disclosed.

  In Patent Document 10 below, a specific conjugated diene monomer and a vinyl aroma are used to obtain a hydrogenated copolymer that is flexible, has excellent resilience and scratch resistance, and has good handling properties (blocking resistance). There is disclosed a hydrogenated copolymer characterized by the absence of crystallization of the DSC chart in the weight ratio of the aromatic hydrocarbon monomer, the amount of the vinyl aromatic hydrocarbon monomer block, and the specific temperature range . Patent Document 11 listed below discloses a hydrogenated block copolymer having a specific structure in order to obtain a composition having a good puncture impact value, strength, transparency, and the like.

However, a block copolymer comprising these vinyl aromatic hydrocarbons and a conjugated diene, or a composition of the block copolymer and a vinyl aromatic hydrocarbon-aliphatic unsaturated carboxylic acid derivative copolymer or a vinyl aromatic carbonization. Hydrogenated copolymer consisting of hydrogen and conjugated diene and its composition is a sheet excellent in impact resistance, solvent resistance, rigidity and transparency, and solvent resistance and natural shrinkage suitable for heat shrinkable film. However, the balance of physical properties such as low temperature shrinkage, rigidity, transparency and impact resistance is not sufficient, and these literatures do not disclose how to improve them, and problems in the market are still pointed out. .
JP-A-4-52129 JP-A-5-104630 JP-A-6-220278 Japanese Patent Laid-Open No. 7-216187 JP 61-41544 A JP 2000-185373 A JP 2000-6329 A JP 2002-46231 A JP 2002-201324 A WO03 / 035705 publication WO03 / 066667

  Compositions of polypropylene resins, ethylene polymers, etc. and styrene block copolymers are suitable for sheet applications and heat-shrinkable film fields where rigidity and transparency are required, as transparency deteriorates and rigidity decreases. There was no.

One of the problems to be solved by the present invention is the above problem.
Accordingly, the present invention is suitable for sheets and films, heat-shrinkable films and the like, and is a composition comprising a block copolymer hydrogenated product and a polyolefin polymer such as a polypropylene resin or an ethylene polymer, and has a solvent resistance. It is an object of the present invention to provide a hydrogenated block copolymer composition having excellent properties, natural shrinkage, low-temperature shrinkage, and transparency and having a good balance between rigidity and elongation.

  Another object of the present invention is to provide a sheet film and a heat shrinkable film excellent in solvent resistance, rigidity, elongation and transparency.

  As a result of intensive studies, the inventors of the present invention achieved the object by a composition comprising a specific hydrogenated hydrogenated block copolymer and at least one polymer selected from a polypropylene resin, an ethylene polymer, and the like. I got the knowledge that I can do it.

The present invention has been made on the basis of the above findings. ~ 13. This invention is provided.
1. Hydrogenated block copolymer having a weight ratio of vinyl aromatic hydrocarbon to conjugated diene of 60/40 to 95/5 and a number average molecular weight of 30,000 to 500,000 as measured by gel permeation chromatography (GPC) Composition (I) and polyolefin polymer (II), wherein the composition has a storage elastic modulus (E ′) at 30 ° C. of 1 × 10 ⁹ Pa or more and a loss elastic modulus. (E ″) at least one peak temperature of 60 ° C. or more and 110 ° C. or less, and a block co-weight with a weight ratio of the component (I) to the component (II) of 1/99 to 99/1 Combined hydrogenated composition.

  2. 2. The block copolymer hydrogenated composition according to 1 above, wherein the block ratio of the vinyl aromatic hydrocarbon incorporated in the block copolymer hydrogenated component (I) is 20 to 95% by weight.

  3. 3. The peak temperature of the function tan δ of dynamic viscoelasticity measurement of the block copolymer hydrogenated component (I) is at least one in the range of more than −70 ° C. and not more than 10 ° C. Block copolymer hydrogenated composition.

  4). Furthermore, 0.01-5 weight part is contained with respect to a total of 100 weight part of said component (I) and (II) at least 1 sort (s) of lubricant chosen from fatty acid amide, paraffin, a hydrocarbon-type resin, and a fatty acid. 4. The block copolymer hydrogenated composition according to any one of 1 to 3 above.

  5. Furthermore, at least one ultraviolet absorber or light stabilizer selected from benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and hindered amine-based light stabilizers is added to a total of 100 components (I) and (II). The block copolymer hydrogenated composition according to any one of 1 to 4 above, containing 0.05 to 3 parts by weight with respect to parts by weight.

  6). In addition to the components (I) and (II), the composition further comprises (III) a vinyl aromatic hydrocarbon polymer, and the weight ratio of the sum of the components (I) and (II) to the component (III) is 99.99. 4. The block copolymer hydrogenated composition according to any one of 1 to 3, which is 9 / 0.1 to 20/80.

7). 7. The block copolymer hydrogenated composition as described in 6 above, wherein the vinyl aromatic hydrocarbon polymer of component (III) is at least one selected from the following a) to c).
a) Styrene polymer b) At least one aliphatic unsaturated carboxylic acid selected from vinyl aromatic hydrocarbons and aliphatic unsaturated carboxylic acids, aliphatic unsaturated carboxylic acid anhydrides and aliphatic unsaturated carboxylic acid esters Copolymer with acid or derivative thereof c) Rubber-modified styrene polymer

  8). Further, at least one lubricant selected from fatty acid amides, paraffins, hydrocarbon resins and fatty acids is added in an amount of 0.01 to 5 with respect to 100 parts by weight of the total of the components (I), (II) and (III). 8. The block copolymer hydrogenated composition as described in 6 or 7 above, which is contained in parts by weight.

  9. Furthermore, at least one ultraviolet absorber or light stabilizer selected from benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, and hindered amine light stabilizers is added to the components (I), (II) and (III). The block copolymer hydrogenated composition according to any one of 6 to 8 above, which is contained in an amount of 0.05 to 3 parts by weight per 100 parts by weight in total.

  10. A sheet / film comprising the block copolymer hydrogenated composition according to any one of 1 to 9 above.

  11. The heat-shrinkable film which is a single layer film of the layer which consists of a block copolymer hydrogenated composition in any one of said 1-9, or is a multilayer film containing the said layer at least.

  12 12. The heat shrinkable film as described in 11 above, wherein the heat shrinkage rate at 80 ° C. in the stretching direction is from 10 to 65%.

13. 13. The heat-shrinkable film as described in 11 or 12 above, wherein the tensile elastic modulus in the stretching direction is from 7000 to 30000 Kg / cm ² .

The block copolymer hydrogenated composition of the present invention is excellent in a balance of physical properties such as solvent resistance, natural shrinkage, low temperature shrinkage, rigidity, transparency and elongation.
The sheet film and heat-shrinkable film of the present invention are excellent in transparency, have a good balance between rigidity and elongation, and are excellent in solvent resistance.

Hereinafter, the present invention will be described in detail based on preferred embodiments thereof.
[Block copolymer hydrogenated composition]
As described above, the block copolymer hydrogenated composition of the present invention has a weight ratio of vinyl aromatic hydrocarbon to conjugated diene of 60/40 to 95/5, and gel permeation chromatography (GPC). A composition comprising a block copolymer hydrogenated product (I) having a number average molecular weight of 30,000 to 500,000 by measurement and a polyolefin polymer (II), wherein the composition is stored at 30 ° C. The elastic modulus (E ′) is 1 × 10 ⁹ Pa or more, and at least one peak temperature of loss elastic modulus (E ″) is 60 ° C. or more and 110 ° C. or less, and the component (I) and the component ( The weight ratio with respect to II) is 1/99 to 99/1 Since the block copolymer hydrogenated product of the present invention has such a structure, it has solvent resistance, natural shrinkage, low temperature shrinkage, rigidity, and transparency. Excellent balance of physical properties such as property and elongation.

  The block copolymer hydrogenated component (I) used in the composition of the present invention has a weight ratio of vinyl aromatic hydrocarbon to conjugated diene of 60/40 to 95/5, preferably 64/36 or more. , Less than 90/10, more preferably 68/32 to 85/15. When the weight ratio between the vinyl aromatic hydrocarbon and the conjugated diene is in the range of 60/40 to 95/5, a sheet and a heat-shrinkable film with improved rigidity and elongation can be obtained. The vinyl aromatic hydrocarbon content of the block copolymer hydrogenated product may be grasped by the vinyl aromatic compound content of the block copolymer before hydrogenation. The weight ratio here refers to the weight ratio of the constituent units derived from the vinyl aromatic hydrocarbon and conjugated diene as monomers in the block copolymer hydrogenated component (I).

  The block ratio of the vinyl aromatic hydrocarbon incorporated in the hydrogenated block copolymer (I) is preferably 20 to 95% by weight, more preferably 25 to 92% by weight, still more preferably 30 to 90% by weight. %. When the block ratio is in the range of 20 to 95% by weight, the balance between rigidity and elongation is excellent.

  The block ratio of the above-mentioned vinyl aromatic hydrocarbon incorporated in the hydrogenated block copolymer (I) is, for example, tertiary butyl hydroperoxide using osmium tetroxide as a catalyst for the block copolymer before hydrogenation. By oxidative decomposition (method described in IM KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946)). In the present invention, the above “block ratio of vinyl aromatic hydrocarbon” means the vinyl aromatic hydrocarbon polymer block component obtained by the above method (however, the vinyl aromatic hydrocarbon polymer component having an average degree of polymerization of about 30 or less). Is the value obtained from the following equation.

  Block ratio (% by weight) = (weight of vinyl aromatic hydrocarbon polymer block in block copolymer / weight of total vinyl aromatic hydrocarbon in block copolymer) × 100

  The block copolymer hydrogenated product (I) used in the present invention preferably has a molecular weight of 5000 to 30000, more preferably 8000 to 25000, and particularly preferably a vinyl aromatic hydrocarbon having a peak molecular weight in the range of 10,000 to 20000. At least one polymer block is incorporated.

  The block copolymer hydrogenated product (I) used in the present invention has a peak temperature of the function tan δ of the hydrogenated dynamic viscoelasticity measurement exceeding −70 ° C., preferably in the range of 10 ° C. or less, preferably −65. It is desirable that at least one is present in the range exceeding 5 ° C., more preferably in the range −60 to 0 ° C., particularly preferably in the range exceeding −55 ° C. and less than −10 ° C. In the case where at least one peak temperature of the function tan δ of the dynamic viscoelasticity measurement exceeds −70 ° C. and is 10 ° C. or less, the elongation is excellent.

  The function tan δ in the dynamic viscoelasticity measurement is a value measured by, for example, a rheological viscoelasticity measurement / analysis apparatus DVE-V4 manufactured by Rheology Co., Ltd. or a Leo Vibron DDV-3 model 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 with respect to the temperature of the value of tan δ becomes zero. The tan δ peak temperature is the weight ratio of vinyl aromatic hydrocarbon and conjugated diene, the molecular weight of the block copolymer hydrogenated product, the content of the vinyl aromatic hydrocarbon polymer block in the block copolymer hydrogenated product, the block It is adjusted by the content of the short-chain vinyl aromatic hydrocarbon polymerized moiety having 1 to 3 vinyl aromatic hydrocarbon units in the copolymer hydrogenated product, the microstructure of the conjugated diene, and the like. More specifically, at least one of the copolymer parts composed of a vinyl aromatic hydrocarbon and a conjugated diene has a vinyl aromatic hydrocarbon content of 50% by weight or less, and is composed of a vinyl aromatic hydrocarbon and a conjugated diene. In order to minimize the number of conjugated diene chains in the copolymer part, it is necessary to adjust the addition amount of the polar solvent to an optimum amount.

  The block copolymer hydrogenated product (I) used in the present invention has a number average molecular weight (polystyrene equivalent molecular weight) of 30,000 to 500,000, preferably 50,000 to 500,000 as measured by gel permeation chromatography (GPC). More preferably, it is in the range of 70,000 to 300,000, and may be a mixture of a plurality of block copolymer hydrogenated products having different molecular weights. The preferred melt flow rate of the block copolymer hydrogenated product (I) (measured according to JISK-6870. Conditions are G conditions, temperature 200 ° C., load 5 kg) is 0.1 to 100 g / 10 min from the viewpoint of molding processability. In particular, it is recommended to be 0.5 to 50 g / 10 min, more preferably 1 to 30 g / 10 min. The number average molecular weight and the melt flow rate (hereinafter sometimes abbreviated as MFR) can be arbitrarily adjusted by the amount of catalyst used for polymerization.

  The block ratio of the block copolymer hydrogenated product (I) used in the present invention is determined by the vinyl aromatic carbonization in the process of copolymerizing the vinyl aromatic hydrocarbon and the conjugated diene during the production of the block copolymer hydrogenated product. It can be controlled by changing the weight, weight ratio, polymerization reactivity ratio, etc. of hydrogen and conjugated diene. As a specific method, a mixture of a vinyl aromatic hydrocarbon and a conjugated diene is continuously supplied to a polymerization system for polymerization, and / or a vinyl aromatic hydrocarbon and a polar compound or a randomizing agent are used. A method such as copolymerization of a conjugated diene can be employed. Examples of polar compounds and randomizing agents include ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol dibutyl ether, amines such as triethylamine and tetramethylethylenediamine, thioethers, phosphines, phosphoramides, alkylbenzene sulfonates, potassium and sodium. An alkoxide etc. are mentioned. The microstructure of the conjugated diene monomer unit in the block copolymer described later can be adjusted by adding a predetermined amount of a polar compound or the like.

  The block copolymer hydrogenated product (I) used in the present invention is preferably a segment composed of a vinyl aromatic hydrocarbon homopolymer and / or a copolymer composed of a vinyl aromatic hydrocarbon and a conjugated diene. It has at least one segment composed of at least one and a conjugated diene homopolymer and / or a copolymer of vinyl aromatic hydrocarbon and conjugated diene.

The polymer structure before hydrogenation of the block copolymer hydrogenated product (I) is not particularly limited.
(AB) n, A- (BA) n, B- (AB) n + 1
[(AB) k] m + 1-X, [(AB) kA] m + 1-X
[(BA) k] m + 1-X, [(BA) kB] m + 1-X
(In the above formula, segment A is a vinyl aromatic hydrocarbon homopolymer and / or a copolymer comprising vinyl aromatic hydrocarbon and conjugated diene, and segment B is a conjugated diene homopolymer and / or vinyl aromatic hydrocarbon. X is a copolymer of a conjugated diene, for example, X is a residue of a coupling agent such as silicon tetrachloride, tin tetrachloride, 1,3 bis (N, N-glycidylaminomethyl) cyclohexane, epoxidized soybean oil or the like. It represents a residue of an initiator such as a functional organolithium compound, where n, k, and m are integers of 1 or more, generally an integer of 1 to 5. In addition, the structure of a polymer chain that is bonded to X by a plurality May be the same or different.), A linear block copolymer hydrogenated product, a radial block copolymer hydrogenated product, or any mixture of these polymer structures may be used. Further, in the hydrogenated radial block copolymer represented by the above general formula, at least one A and / or B may be bonded to X.

  In the present invention, the vinyl aromatic hydrocarbon in the copolymer of vinyl aromatic hydrocarbon and conjugated diene in segment A and segment B may be distributed uniformly or in a tapered (gradual decrease) form. Good. Further, in the copolymer hydrogenated product (I), a plurality of portions where vinyl aromatic hydrocarbons are uniformly distributed and / or portions where taper distribution is present coexist in the segment. Good. Vinyl aromatic hydrocarbon content in segment A ({vinyl aromatic hydrocarbon in segment A / (vinyl aromatic hydrocarbon in segment A + conjugated diene)} × 100) and vinyl aromatic carbon in segment B The relationship between the hydrogen content ({vinyl aromatic hydrocarbon in segment B / (vinyl aromatic hydrocarbon in segment B + conjugated diene)} × 100) is greater with the vinyl aromatic hydrocarbon content in segment A. , Greater than the vinyl aromatic hydrocarbon content in segment B. The difference in the preferred vinyl aromatic hydrocarbon content between segment A and segment B is preferably 5% by weight or more.

  In the present invention, the block copolymer before hydrogenation of the block copolymer hydrogenated product (I) is, for example, an organic alkali metal compound (for example, an organic lithium compound) in a hydrocarbon solvent, as a polymerization initiator. It can be obtained by polymerizing a vinyl aromatic hydrocarbon and a conjugated diene (for example, anionic living polymerization).

  Examples of the vinyl aromatic hydrocarbon constituting the hydrogenated block copolymer (I) include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methyl. Examples include styrene, vinyl naphthalene, vinyl anthracene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethyl styrene, N, N-diethyl-p-aminoethyl styrene, Styrene is mentioned. These may be used alone or in combination of two or more.

  The conjugated diene constituting the block copolymer hydrogenated product (I) may be 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 and the like, and particularly common ones include 1,3-butadiene, isoprene and the like. These may be used alone or in combination of two or more.

  In the present invention, examples of the hydrocarbon solvent that can be used to obtain the block copolymer before hydrogenation of the block copolymer hydrogenated product (I) include n-butane, isobutane, n-pentane, n -Aliphatic hydrocarbons such as hexane, n-heptane, n-octane, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cycloheptane, methylcycloheptane, benzene, toluene Aromatic hydrocarbons such as xylene and ethylbenzene can be used. These may be used alone or in combination of two or more.

  In addition, as polymerization initiators, aliphatic hydrocarbon alkali metal compounds, aromatic hydrocarbon alkali metal compounds, organic amino alkalis generally known to have anionic polymerization activity for conjugated dienes and vinyl aromatic compounds. A metal 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 In addition, a reaction product of divinylbenzene, sec-butyllithium and a small amount of 1,3-butadiene can be used. 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 block copolymer before hydrogenation of the block copolymer hydrogenated product (I) 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 block copolymer hydrogenated product (I) can be obtained by hydrogenating the block copolymer before hydrogenation obtained as described above. 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. 1-39770, Japanese Patent Publication No. 1-53851, The hydrogenation catalyst described in Japanese Patent 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, a compound 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 performed 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 block copolymer (I) used in the present invention, the hydrogenation rate (hydrogenation rate) of unsaturated double bonds based on the conjugated diene in the block copolymer before hydrogenation is It is desirable that 60% or more, preferably 75% or more, more preferably 85% or more, particularly preferably 90% or more of the unsaturated double bond based on the conjugated diene compound in the coalescence is hydrogenated. When the hydrogenation rate is 60% or more, the solvent resistance is further improved. The hydrogenation rate can be known by a nuclear magnetic resonance apparatus (NMR).

  In the present invention, the block copolymer hydrogenated product (I) can change the microstructure (cis, trans, vinyl ratio) of the conjugated diene moiety arbitrarily by using the above-mentioned polar compound, etc. There is no limit. 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 present invention, when obtaining the block copolymer hydrogenated product (I) having particularly excellent rigidity, it is 0 ° C. or higher, preferably 5 ° C. in the differential scanning calorimetry (DSC) chart of the block copolymer hydrogenated product. More preferably, a hydrogenated block copolymer having a crystallization peak in a temperature range of 10 to 60 ° C. is preferred. The crystallization peak heat quantity is 3 J / g or more, preferably 6 J / g or more, more preferably 10 J / g or more. The hydrogenated block copolymer having a crystallization peak has a vinyl bond content in the block copolymer before hydrogenation of less than 30%, preferably 8 to 25%, more preferably 10 to 25%, particularly preferably. It can be obtained by setting to 12 to 20%. In particular, the block copolymer before hydrogenation may contain at least one conjugated diene polymer segment having a vinyl bond content of 8 to 25%, preferably 10 to 20%, more preferably 10 to 18%. Recommended.

  The polyolefin polymer of component (II) used in the composition of the present invention is at least one polymer selected from polypropylene resins, polyethylene polymers and the like, for example, polyethylene, ethylene copolymers ( Ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-methacrylic acid copolymer, etc. or other ethylene and unsaturated fatty acids System copolymer derivatives, ethylene ionomer resins, ethylene-α olefin copolymers, etc.), modified polymers having carboxylic acid groups added thereto, polybutene-1 copolymers, etc. The main component is at least one selected component. Among them, a polypropylene resin (lander) is preferable. Copolymers, these alicyclic saturated hydrocarbon resins, petroleum resins, tempen resins, and those modified with rosins), high-density polyethylene, linear-low density polyethylene (L / LDPE), ultra-low density Polyethylene, ionomer resin (for example, ethylene), and the like.

  In the composition of the present invention, the weight ratio of the component (I) to the component (II) is 1/99 to 99/1, preferably 3/97 to 97/3, more preferably 5/95. ~ 95/5. When the weight ratio of component (I) to component (II) is in the range of 1/99 to 99/1, the solvent resistance is excellent.

The storage elastic modulus (E ′) at 30 ° C. of the hydrogenated block copolymer composition of the present invention is 1 × 10 ⁹ Pa or more, preferably 1.2 × 10 ⁹ Pa or more. When the storage elastic modulus (E ′) at 30 ° C. is 1 × 10 ⁹ Pa or more, the rigidity is excellent.

  The peak temperature of the loss elastic modulus (E ″) of the block copolymer hydrogenated composition of the present invention is in the range of 60 ° C. or higher and 110 ° C. or lower, preferably 65 to 105 ° C., more preferably 70 to 100 ° C. It is necessary that at least one, ie, one or two or more exist. The peak temperature of the loss modulus (E ″) is at least one at 60 ° C. or more and 110 ° C. or less, so that low temperature shrinkage and natural shrinkage are present. Excellent in properties.

  The block copolymer hydrogenated composition of the present invention comprises (III) a vinyl aromatic hydrocarbon polymer (hereinafter also referred to as component (III)) together with the components (I) and (II). Can be used as a composition comprising The weight ratio of the sum of components (I) and (II) to component (III) is 99.9 / 0.1-20 / 80, preferably 99.7 / 0.3-25 / 75, more preferably It is desirable that it is 99 / 1-30 / 70. By combining the components (I), (II) and (III) at such a weight ratio, a block copolymer hydrogenated composition having excellent rigidity, blocking resistance and natural shrinkage can be obtained.

As the vinyl aromatic hydrocarbon polymer of the component (III), at least one selected from the following a) to c) can be used.
a) Styrenic polymer b) At least one aliphatic unsaturated carboxylic acid selected from vinyl aromatic hydrocarbons and aliphatic unsaturated carboxylic acids, aliphatic unsaturated carboxylic acid anhydrides and aliphatic unsaturated carboxylic acid esters Copolymer with acid or derivative thereof c) Rubber-modified styrene polymer

  Of the component (III) that can be used in the present invention, the a) styrenic polymer is obtained by polymerizing styrene or a monomer copolymerizable therewith (except for b). Examples of the monomer copolymerizable with styrene include α-methylstyrene, acrylonitrile, maleic anhydride and the like. Examples of the styrenic polymer include polystyrene, styrene-α-methylstyrene copolymer, acrylonitrile-styrene copolymer, styrene-maleic anhydride copolymer, and the like. Particularly preferred styrenic polymer is polystyrene. I can give you. A polymer having a weight average molecular weight of 50,000 to 500,000 can be generally used. These styrenic polymers can be used alone or as a mixture of two or more, and can be used as a rigidity improver.

  In addition, a block copolymer composed of a vinyl aromatic hydrocarbon having a vinyl aromatic hydrocarbon content of 85 to 98% by weight and a conjugated diene, and a hydrogenated product thereof, excluding the block copolymer hydrogenated product of the present invention. The number average molecular weight is 30,000 to 300,000, preferably 50,000 to 250,000, more preferably 70,000 to 200,000, and the tan δ peak temperature is 80 to 110 ° C., preferably 83 to 105 ° C., more preferably It is 85-100 degreeC, Vicat softening temperature is 60-85 degreeC, Preferably it is 65-83 degreeC, More preferably, 68-80 degreeC is preferable, and it can be used as a rigidity and shrinkage | contraction improvement agent.

Among the component (III) that can be used in the present invention, b) vinyl aromatic hydrocarbon and aliphatic unsaturated carboxylic acid, aliphatic unsaturated carboxylic acid anhydride, aliphatic unsaturated carboxylic acid ester are selected. Examples of the aliphatic unsaturated carboxylic acid used in the copolymer with at least one aliphatic unsaturated carboxylic acid or derivative thereof include acrylic acid, methacrylic acid, fumaric acid, itaconic acid and maleic acid. In addition, examples of the aliphatic unsaturated carboxylic acid anhydride include fumaric anhydride, itaconic anhydride, maleic anhydride, and the like, and examples of the aliphatic unsaturated carboxylic acid ester include the above aliphatic unsaturated carboxylic acid and carbon number. C ₁ -C _12, preferably include mono- or diesters of alcohols of C ₂ -C _12. The content of the aliphatic unsaturated carboxylic acid and / or aliphatic unsaturated carboxylic acid derivative in component (III) is generally 5 to 50% by weight, preferably 8 to 30% by weight, more preferably 10 to 25% by weight. is there. As the production method of component b), a known method for producing a styrene resin, for example, a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method or the like can be used. In general, a polymer having a weight average molecular weight of component b) of 50,000 to 500,000 can be used.

For example, aliphatic unsaturated carboxylic acid ester of aliphatic unsaturated carboxylic acid ester-styrene copolymer is carbon such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, etc. number C ₁ -C ₁₂ preferably C ₂ -C esters of alcohols and acrylic acid _12, or methacrylic acid with a carbon number C ₁ -C ₁₂ preferably with carbon number C ₂ -C ₁₂ alcohol and acrylic · BR> Selected from mono- or diesters of α and β unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and the like and alcohols having C _{1 to} C ₁₂ , preferably C _{2 to} C _12. At least one. The content of the aliphatic unsaturated carboxylic acid ester in the aliphatic unsaturated carboxylic acid ester-styrene copolymer is generally 5 to 50% by weight, preferably 8 to 30% by weight, and more preferably 10 to 25% by weight. is there.

  Moreover, the Vicat softening point in the aliphatic unsaturated carboxylic acid ester-styrene copolymer used for improving the low temperature shrinkage is 50 to 95 ° C, preferably 60 to 90 ° C, more preferably 65 to 85 ° C. It is recommended that 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.

  Particularly preferred aliphatic unsaturated carboxylic acid ester-styrene copolymer is a copolymer mainly composed of n-butyl acrylate and styrene, and the total amount of n-butyl acrylate and styrene is 50% by weight or more, more preferably. Is an aliphatic unsaturated carboxylic acid ester-styrene copolymer in which the total amount of n-butyl acrylate and styrene is 60% by weight or more. 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.

  Among the components (III) that can be used in the present invention, the c) rubber-modified styrenic polymer is obtained, for example, by polymerizing a mixture of a monomer copolymerizable with a vinyl aromatic hydrocarbon and an elastomer. As the polymerization method, suspension polymerization, emulsion polymerization, bulk polymerization, bulk-suspension polymerization and the like 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 are dissolved in the monomer or in latex form, emulsion polymerization, bulk polymerization, bulk-suspension polymerization. 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 20 parts by weight or less, particularly 0.1 to 10 parts with respect to 100 parts by weight of the total of the components (I), (II) and (III), considering transparency maintenance Part by weight is preferred.

  As the vinyl aromatic hydrocarbon polymer of component (III) that can be used in the present invention, in particular, MFR (temperature of 200 ° C. under G condition, load of 5 kg) is 0.1 to 100 g / It is recommended that it be 10 min, preferably 0.5 to 50 g / 10 min, 1 to 30 g / 10 min.

  The block copolymer hydrogenated composition of the present invention may contain at least one selected from fatty acid amides, paraffins, hydrocarbon resins and fatty acids as a lubricant. The content of the lubricant is preferably based on 100 parts by weight of the sum of the components (I) and (II) (the sum of the components (I), (II) and (III) when the component (III) is used). Is 0.01 to 5 parts by weight, more preferably 0.05 to 4 parts by weight, and still more preferably 0.1 to 3 parts by weight. By adding a lubricant, blocking resistance is improved.

  Examples of fatty acid amides include stearoamide, oleyl amide, erucyl amide, behen amide, mono- or bisamide of higher fatty acids, ethylene bis stearoamide, stearyl oleylamide, N-stearyl erucamide, etc. Two or more types can be mixed and used. 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. It can be used alone or in combination of two or more. Examples of fatty acids include saturated fatty acids and unsaturated fatty acids. That is, examples include saturated fatty acids such as lauric acid, palmitic acid, stearic acid, behenic acid, hydroxystearic acid, and unsaturated fatty acids such as oleic acid, erucic acid, and ricinoleic acid. These may be used alone or in combination of two or more. Can be used.

  The block copolymer hydrogenated composition of the present invention contains at least one selected from benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, and hindered amine light stabilizers as ultraviolet absorbers and light stabilizers. An ultraviolet absorber and a light stabilizer can be contained. The content of the ultraviolet absorber and the light stabilizer is the sum of components (I) and (II) (the sum of components (I), (II) and (III) when component (III) is used) 100 Preferably it is 0.05-3 weight part with respect to a weight part, More preferably, it is 0.05-2.5 weight part, More preferably, it is 0.1-2 weight part, Thereby, light resistance improves. .

  Examples of the benzophenone ultraviolet absorber include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4 '. -Dimethoxy benzophenone, 2-hydroxy-4-n-octoxy benzophenone, 2,2 ', 4,4'-tetrahydroxy benzophenone, 4-dodecyloxy-2-hydroxy benzophenone, 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) hexa Etc. The.

  As the benzotriazole UV absorber, 2- (2′-hydroxy-5′-methyl-phenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butyl-phenyl) benzo Triazole, 2- (2′-hydroxy-3′-t-butyl-5′-methyl-phenyl) -5-chloro-benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t- Butyl-phenyl) -5-chloro-benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amyl) Phenyl) benzotriazole, 2- [2′-hydroxy-3 ′-(3 ′, 4 ′, 5 ′, 6′-tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole, 2-2′-methylenebis [4- (1,1,3,3-tetramethylbuty ) -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-benzotriazol-2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol, etc. Is mentioned.

  Examples of hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) separate, bis (1,2,6,6,6, -pentmethyl-4-piperidyl) separate, 1- [2- {3- (3,5-di-tert-butyl-4-hydroxydiphenyl) propionyloxy} ethyl] -4- {3- (3,5-di-tert-butyl-4-hydroxydiphenyl) ) Propionyloxy} -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) succinate) -4-hydroxy-2,2,6,6- Examples include tetramethylpiperidine polycondensate.

  Also, poly [[6- (1,1,3,3-tetramethylbutyl) imino-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-tert-butyl- 4-Hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), tetraxy (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetraxy (1,2,2,6,6, -pentamethyl-4-piperidi L) 1,2,3,4, -butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and tridecyl alcohol These condensates can be mentioned.

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 -Condensate 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-Pendamethyl-4-piperidyl) amino] -6-chloro-1 3,5-triazine condensate, dibutylamine, 1,3,5-triazine, N, N-bis (2,2,6,6-tetramethyl-4-piperyl-1,6-hexamethylenediamine, N- 2,2,6,6-tetramethy-4-piperidyl) butylamine polycondensate, 1,2,2,6,6-tetramethyl-4-piperyl-methacrylate, 2,2,6,6-tetramethyl- Examples include 4-piperyl-methacrylate.

  The block copolymer hydrogenated composition and composition of the present invention include 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t as a stabilizer. -Pentylphenyl acrylate was added to the total of components (I) and (II) (in the case where component (III) was used, the total of components (I), (II) and (III)) was 0.1. It is possible to add from 0.5 to 3 parts by weight, more preferably from 0.1 to 2 parts by weight, whereby a gel suppressing effect can be obtained.

  Further, the hydrogenated block copolymer composition of the present invention includes 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- At least one phenol-based stabilizer such as bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine is used as the block copolymer water. 0.05 to 3 parts by weight per 100 parts by weight of the additive, Tris- (noni Phenyl) 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) Organic phosphates such as dibenzo [d, f] [1,3,2] dioxaphosphine-6-yl] oxy] -ethyl] -ethanamine, tris (2,4-di-t-butylphenyl) phosphite The total of components (I) and (II) (if component (III) is used, the sum of components (I), (II) and (III)) 0.05 to 3 parts by weight can be added to 100 parts by weight.

  Various polymers and additives can be added to the block copolymer hydrogenated 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 aromatics different from the component (I) block copolymer hydrogenated products used in the present invention. A block copolymer of a hydrocarbon and a conjugated diene and / or a hydrogenated product thereof (that does not satisfy at least a part (for example, weight ratio, etc.) of the specific matters of the component (I) according to the present invention).

  The vinyl aromatic hydrocarbon and conjugated diene block copolymer elastomer or its hydrogenated product has a vinyl aromatic hydrocarbon content of less than 60% by weight, preferably 10 to 50% by weight, and is used in the present invention. Those having the same structure as the block copolymer hydrogenated product of (I) can be used, and 0.5 to 30 parts per 100 parts by weight of the block copolymer hydrogenated component (I) used in the present invention. By blending parts by weight, preferably 1 to 20 parts by weight, impact resistance, elongation and the like can be improved.

  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 and / or its hydrogenated product, which is different from the component (I) block copolymer hydrogenated product used in the present invention, has a vinyl aromatic hydrocarbon content. 60 to 95% by weight, preferably 65 to 90% by weight, and a structure similar to that of the block copolymer hydrogenated component (I) used in the present invention (for example, the general formula (AB) exemplified above) n, A- (BA) n, B- (AB) n + 1, [(AB) k] m + 1-X, [(AB) k-A] m + 1-. X, [(BA) k] m + 1-X, [(BA) k-B] m + 1-X, etc .: those having the same definitions of the characters in the formula as above It can be used, and by blending 5 to 90 parts by weight, preferably 10 to 80 parts by weight with respect to 100 parts by weight of the block copolymer hydrogenated component (I) used in the present invention, impact resistance and rigidity, To improve growth, etc. Kill.

  Other suitable additives include softeners such as coumarone-indene resins, terpene resins, oils, and plasticizers.

  In addition, various stabilizers, pigments, antiblocking agents, antistatic agents, lubricants and the like can be added to the block copolymer hydrogenated composition of the present invention. Examples of the antiblocking agent, antistatic agent and lubricant include fatty acid amide, ethylene bis-stearamide, sorbitan monostearate, saturated fatty acid ester of fatty acid alcohol, pentaerythritol fatty acid ester, etc. -t-Butylphenyl salicylate, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzo Triazole, 2,5-bis- [5′-t-butylbenzoxazolyl- (2)] thiophene, and the like, compounds described in “Practical Handbook for Additives for Plastics and Rubber” (Chemical Industry Co., Ltd.) can be used. . These are generally used in the composition of the present invention in an amount of 0.01 to 5% by weight, preferably 0.05 to 3% by weight.

  The block copolymer hydrogenated composition of the present invention can be used for various molding materials such as sheets, films and injection molded articles.

[Sheet Film]
The sheet / film of the present invention comprises the above-mentioned block copolymer hydrogenated composition. The sheet / film of the present invention is excellent in solvent resistance, rigidity, elongation and transparency due to such a structure.

[Heat shrinkable film]
The heat-shrinkable film of the present invention is composed of the aforementioned block copolymer hydrogenated composition. The heat-shrinkable film of the present invention is excellent in solvent resistance, rigidity, elongation and transparency due to such a configuration. The heat-shrinkable film of the present invention may be a single layer film composed of the copolymer hydrogenated composition or a multilayer film including at least the layer.

  The heat-shrinkable film of the present invention is a heat-shrinkable uniaxial or biaxially stretched film using the block copolymer hydrogenated composition. For example, the block copolymer hydrogenated composition is usually used as the heat-shrinkable film. Obtained by extruding from a T-die or an annular die into a flat shape or a tube shape at 150 to 250 ° C., preferably 170 to 220 ° C., and substantially unaxially or biaxially stretching the obtained unstretched product. Is.

  When the heat-shrinkable film of the present invention is, for example, a uniaxially stretched film, it can be obtained as follows. That is, in the case of a film or sheet, it is stretched in the extrusion direction with a calender 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, it is stretched in the extrusion direction or circumferential direction of the tube. When the heat-shrinkable film of the present invention is a biaxially stretched film, it is obtained as follows. That is, 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. In the case of a tube, the extrusion direction of the tube and the circumference of the tube Each is stretched simultaneously or separately in the direction, that is, the direction perpendicular to the tube axis.

  The heat shrinkable film of the present invention has a stretching temperature of 60 to 160 ° C., preferably 80 to 155 ° C., more preferably 85 to 150 ° C., and a stretching ratio of 1.5 to 8 times in the machine direction and / or the transverse direction. What was obtained by extending | stretching 2-6 times preferably is desirable. 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.

  When the heat-shrinkable film of the present invention obtained as described above is used as a heat-shrinkable packaging material or a heat-shrinkable label material, the heat shrinkage rate at 80 ° C. in the stretching direction is preferably 5 to 5. It is 60%, more preferably 10 to 55%, still more preferably 15 to 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 heat shrinkage rate in each stretching direction of the molded product when immersed in the interior for 5 minutes. 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.

Further, when the heat-shrinkable film of the present invention is used as a uniaxially stretched film or a biaxially stretched film, the tensile elastic modulus in the stretched direction is preferably 7000 to 30000 Kg / cm ² , more preferably 10,000 to 25000 Kg / cm ^2. It is necessary as a heat shrink wrapping material. The tensile modulus in the stretching direction is 7000 Kg / cm ² or more due to the problem of settling in the shrink wrapping process, and is 30000 Kg / cm ² or less due to the impact resistance of the film.

  When the heat-shrinkable film of the present invention is used as a heat-shrinkable packaging material as a uniaxially stretched or biaxially stretched film, it is 130 to 300 ° C, preferably 150 to 250 ° C in order to achieve the desired heat shrinkage rate. The heat shrinkage can be performed by heating at a temperature of several seconds to several minutes, preferably 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. In the heat-shrinkable film of the present invention, the block copolymer hydrogenated composition described above may be used for the intermediate layer and both outer layers. When the heat-shrinkable film of the present invention is a multilayer film, the layers other than the film layer using the above-described block copolymer hydrogenated composition are not particularly limited, and the present invention differs in the components and compositions. The block copolymer hydrogenated composition, or the block copolymer other than the block copolymer hydrogenated component (I) used in the composition and / or the hydrogenated product or the block copolymer weight thereof It may be a multilayer laminate obtained by combining a composition and / or a hydrogenated product thereof and a composition of the vinyl aromatic hydrocarbon polymer. 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, poly Examples thereof include at least one component selected from methyl methacrylate resin, ABS resin, the above-mentioned vinyl aromatic hydrocarbon polymer, and the like.

  The multilayer heat-shrinkable film preferred in the present invention has at least one layer of the multilayer film as the above-mentioned block copolymer hydrogenated composition, and preferably has a heat shrinkage rate of 80 ° C. in the stretching direction of 10 to 10. It is a heat-shrinkable multilayer film that is 65%, preferably 15-62%, more preferably 20-60%.

  The thickness of the heat-shrinkable film of the present invention is 10 to 300 μm, preferably 20 to 200 μm, more preferably 30 to 100 μm, and the thickness ratio between the inner layer and both surface layers is 5/95 to 45/55, preferably 10/90 to 35/65 are recommended.

  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, after letters and designs are printed on a uniaxially stretched film of the block copolymer hydrogenated composition defined in the present invention, plastic molded products, metal products, glass containers, porcelain, etc. Use as a material for a so-called heat-shrinkable label, which is used in close contact with the surface by heat shrinkage, can be mentioned.

  In particular, the heat-shrinkable film of the present invention is excellent in solvent resistance, low-temperature shrinkage, rigidity and natural shrinkage as a uniaxially stretched film. In addition to the label material, the material of which the coefficient of thermal expansion and water absorption are very different from those of the block copolymer hydrogenated composition according to the present invention, for example, polyolefin such as metal, porcelain, glass, paper, polyethylene, polypropylene, polybutene, etc. Suitable as heat-shrinkable label material for containers using at least one selected from polyester resins, polymethacrylate resins, polycarbonate resins, polyethylene terephthalate, polyester resins such as polybutylene terephthalate, and polyamide resins as constituent materials Available to:

  The material constituting the plastic container in which the heat-shrinkable film of the present invention can be used includes polystyrene, rubber-modified high impact polystyrene (HIPS), styrene-butyl acrylate copolymer, styrene-acrylonitrile in addition to the above-mentioned resins. Copolymer, Styrene-maleic anhydride copolymer, Acrylonitrile-butadiene-styrene copolymer (ABS), Methacrylate-butadiene-styrene copolymer (MBS), Polyvinyl chloride resin, 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 at 80 ° C. in the direction orthogonal to the stretching direction is less than 20%, preferably 10% or less. Therefore, uniaxial stretching as a heat-shrinkable label in the present invention means that the heat shrinkage rate 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%. This refers to performing a stretching process.
〔Example〕

  Examples of the present invention will be described below, but these do not limit the scope of the present invention. Table 1 shows hydrogenated block copolymer hydrogenated components (I), Table 2 shows component (II) polyolefin polymers, and Table 3 shows component (III) vinyl aromatic hydrocarbons and aliphatic unsaturated carboxylic acids. Copolymers composed of a series derivative were shown.

(Preparation of hydrogenated block copolymer and block copolymers A-1 to A-7)
The block copolymer before hydrogenation uses n-butyllithium in a cyclohexane solvent as a catalyst, tetramethylethylenediamine as a randomizing agent, the structure of the hydrogenated block copolymer shown in Table 1, and the styrene content (% by weight) A hydrogenated block copolymer having an average molecular weight, a block ratio, a Tan δ peak temperature and a predetermined hydrogenation ratio was produced. The styrene content was the addition amount of styrene and butadiene, the number average molecular weight was the catalyst amount, the block ratio was the styrene content and the structure of the block copolymer, and the Tan δ peak temperature was adjusted by the structure of the block copolymer. In the preparation of the hydrogenated block 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 (η5-cyclopentadienyl) titanium dichloride was added, and 200 mmol of trimethylaluminum was added while stirring sufficiently. The hydrogenation catalyst which added the n-hexane solution containing and made it react at room temperature for about 3 days was used.

1) Block copolymer A-1
Using an autoclave with a stirrer, 0.065 parts by weight of n-butyllithium and 0.03 parts by weight of tetramethylethylenediamine were added to a cyclohexane solution containing 20 parts by weight of styrene under a nitrogen gas atmosphere, and polymerization was performed at 70 ° C. for 20 minutes. . Next, a cyclohexane solution containing 16 parts by weight of styrene and 29 parts by weight of 1,3-butadiene was continuously added for 45 minutes to polymerize at 70 ° C.

  Next, a cyclohexane solution containing 35 parts by weight of styrene was added and polymerized at 70 ° C. for 40 minutes. Thereafter, a hydrogenation catalyst was added at 100 ppm as titanium per 100 parts by weight of the block copolymer, and a hydrogenation reaction was carried out 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 block copolymer. Thereafter, the solvent was removed to obtain a hydrogenated block copolymer. The hydrogenation rate was adjusted with the amount of hydrogen.

2) Block copolymer hydrogenated product A-2 to A-7
Block copolymer hydrogenated products A-2 to A-7 were prepared in the same manner as A-1, except that the structure and number average molecular weight, block rate, Tanδ peak temperature and hydrogenated rate of the block copolymer were adjusted. did.

(Preparation of copolymers consisting of vinyl aromatic hydrocarbons and aliphatic unsaturated carboxylic acid derivatives)
C-1 and C-2 were added 5 kg of styrene, methyl methacrylate, n-butyl acrylate, acrylic acid and ethyl methacrylate to a 10 L autoclave with a stirrer in the ratio shown in Table 2, and simultaneously 0.3 kg of ethylbenzene, In order to adjust the MFR, a predetermined amount of 1,1 bis (t-butylperoxy) cyclohexane was charged, and after polymerization at 110 to 150 ° C. for 2 to 10 hours, the unreacted monomer and ethylbenzene were recovered with a vent extruder.

(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 was measured using an ultraviolet spectrophotometer (device name: UV-2450; manufactured by Shimadzu Corporation).

2) Number average molecular weight The number molecular weight was measured using a GPC apparatus (HLC8220GPC; manufactured by Tosoh Corporation). Tetrahydrofuran was used as a solvent, and measurement was performed at 40 ° C. The number average molecular weight was calculated | required using the calibration curve created using the commercially available standard polystyrene whose weight average molecular weight and number average molecular weight are known.

3) Hydrogenation rate The hydrogenation rate was measured with a nuclear magnetic resonance apparatus (device name: DPX-400; manufactured by BRUKER, Germany).

4) Block ratio A method of oxidatively decomposing a block copolymer before hydrogenation with tertiary butyl hydroperoxide using osmium tetroxide as a catalyst (IM KOLTHOFF, et al., J. Polym. Sci. 1, 429). (Method described in (1946)), and the block styrene content was measured. Further, the block ratio is calculated by the following formula using the vinyl aromatic hydrocarbon polymer block component obtained by the same method (however, the vinyl aromatic hydrocarbon polymer component having an average degree of polymerization of about 30 or less is excluded). I asked for it.
Block ratio (% by weight) = (weight of vinyl aromatic hydrocarbon polymer block in block copolymer / weight of total vinyl aromatic hydrocarbon in block copolymer) × 100

5) Peak temperature of Tanδ peak temperature, storage elastic modulus (E ′) and loss elastic modulus (E ″) at 30 ° C., using a rheology viscoelasticity measuring / analyzing apparatus DVE-V4, with a vibration frequency of 35 Hz and a temperature rise Using a test piece having a thickness of 2 mm under the condition of a speed of 3 ° C./min, the temperature was measured in the range of −50 ° C. to 150 ° C.

6) 80 ° C. Shrinkage The 80 ° C. shrinkage is a value calculated by the following equation by immersing a 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.

7) Natural shrinkage rate This is a value calculated by the following formula after leaving the stretched film 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.

8) Tensile elastic modulus Based on JIS K-6732, it measured about the extending | stretching direction (MD direction in the case of a sheet | seat) of the film at the tensile speed of 5 mm / min. The test piece had a width of 12.7 mm and a gap between marked lines of 50 mm. The measurement temperature was 23 ° C. The unit is Kg / cm ² .

9) Elongation Based on JIS K-6732, it measured about the extending | stretching direction of the film at the tension speed of 10 mm / min. The test piece had a width of 12.7 mm and a gap between marked lines of 50 mm. The measurement temperature was 23 ° C.

10) Haze
Liquid paraffin was applied to the surface of the stretched film or sheet and measured according to ASTM D1003.

11) Solvent resistance Methyl ethyl ketone / isopropyl alcohol (ratio 7/3) is applied to a stretched film or sheet 15 cm in MD × 15 cm in TD with a brush, dried at 30 ° C. for 7 days, and then 10 ° C. film MD before and after coating. Judgment was based on the retention of elongation in the direction.
<Criteria>
○: Retention rate 65% or more ×: Retention rate less than 65% [Examples 1 to 5, Comparative Examples 1 to 4]

Measurement of heat-shrinkable film performance was carried out by mixing the composition (components previously kneaded with a 30 mm twin screw extruder) of the types and amounts of component (I), component (II) and component (III) shown in Table 4. The tenter was formed into a sheet having a thickness of 0.2 mm using a 40 mm single screw extruder, and then the stretching temperature was 85 ° C. (Comparative Example 4 was stretched at 107 ° C. because it could not be stretched at 85 ° C.). Was used to obtain a heat-shrinkable film having a thickness of about 40 μm. Table 4 shows the film performance of this heat-shrinkable film. The performance of the heat-shrinkable film of the present invention is excellent in rigidity represented by tensile modulus, low-temperature shrinkage represented by 80 ° C. shrinkage, natural shrinkage, elongation, transparency represented by Haze, and solvent resistance. Is good. In addition, the sheet | seat and film performance shown in Table 4 were performed by said method. In addition, 0.2 parts by weight of Adeka Stub LA-32 (manufactured by Adeka Co., Ltd.) is added as an ultraviolet absorber to 100 parts by weight of the composition, and 0.2 parts by weight of stearoamide is added as a lubricant to 100 parts by weight of the composition. did.
[Example 6]

A pre-kneaded composition of 95% by weight of component (I) A-3, 4% by weight of component (II) B-1 and 1% by weight of component (III) C-3 (E at 30 ° C. 'Value: 1.04 × 10 ⁹ Pa, peak temperature of E ″: 105 ° C.) was formed into a sheet having a thickness of 0.3 mm using a 40 mm single screw extruder, and the physical properties thereof were measured. The sheet had good sheet properties with a tensile modulus of 1250 MPa, an elongation of 350%, a haze of 3.2%, and a solvent resistance of ○. As a result of molding into a beverage cup having a diameter of 7 cm, it was possible to obtain a good cup having a good appearance with little cloudiness and no cracking even when crushed.

  The heat-shrinkable film using the block copolymer hydrogenated composition of the present invention is transparent and excellent in solvent resistance, rigidity, natural shrinkage, low-temperature shrinkage, hot-water fusion, and low-temperature elongation. Therefore, 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, various labels, and the like.

Claims (11)

A block copolymer having a weight ratio of vinyl aromatic hydrocarbon to conjugated diene of 68/32 or more and less than 90/10 , and a number average molecular weight of 30,000 to 500,000 as measured by gel permeation chromatography (GPC) A composition comprising a hydrogenated product (I) and a polyolefin polymer (II), wherein the composition has a storage elastic modulus (E ′) at 30 ° C. of 1 × 10 ⁹ Pa or more and a loss modulus (E ") peak temperature 60 ° C. or more, and at least one present in the 110 ° C. or less, the weight ratio of the component (I) and the component (II) is Ri 1 / 99-99 / 1 der ,
The block ratio of the vinyl aromatic hydrocarbon incorporated in the hydrogenated block copolymer of component (I) is 30 to 90% by weight,
Hydrogenation of the block copolymer in which at least one peak temperature of the function tan δ of the dynamic viscoelasticity measurement of the block copolymer hydrogenated component (I) is more than −70 ° C. and less than −10 ° C. Composition. Furthermore, 0.01-5 weight part is contained with respect to a total of 100 weight part of said component (I) and (II) at least 1 sort (s) of lubricant chosen from fatty acid amide, paraffin, a hydrocarbon-type resin, and a fatty acid. The block copolymer hydrogenated composition according to claim 1 . Furthermore, at least one ultraviolet absorber or light stabilizer selected from benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and hindered amine-based light stabilizers is added to a total of 100 components (I) and (II). The block copolymer hydrogenated composition according to claim 1, which contains 0.05 to 3 parts by weight with respect to parts by weight. In addition to the components (I) and (II), the composition further comprises (III) a vinyl aromatic hydrocarbon polymer, and the weight ratio of the sum of the components (I) and (II) to the component (III) is 99.99. The block copolymer hydrogenated composition according to claim 1 , which is 9 / 0.1 to 20/80. The block copolymer hydrogenated composition according to claim 4 , wherein the vinyl aromatic hydrocarbon polymer of component (III) is at least one selected from the following a) to c).
a) Styrene polymer b) At least one aliphatic unsaturated carboxylic acid selected from vinyl aromatic hydrocarbons and aliphatic unsaturated carboxylic acids, aliphatic unsaturated carboxylic acid anhydrides and aliphatic unsaturated carboxylic acid esters Copolymer with acid or derivative thereof c) Rubber-modified styrene polymer Further, at least one lubricant selected from fatty acid amides, paraffins, hydrocarbon resins and fatty acids is added in an amount of 0.01 to 5 with respect to 100 parts by weight of the total of the components (I), (II) and (III). The block copolymer hydrogenated composition according to claim 4 or 5, which contains parts by weight. Furthermore, at least one ultraviolet absorber or light stabilizer selected from benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, and hindered amine light stabilizers is added to the components (I), (II) and (III). The block copolymer hydrogenated composition according to any one of claims 4 to 6 , which is contained in an amount of 0.05 to 3 parts by weight based on a total of 100 parts by weight of The sheet | seat film which consists of a block copolymer hydrogenated composition in any one of Claims 1-7 . A heat-shrinkable film which is a single-layer film comprising a block copolymer hydrogenated composition according to any one of claims 1 to 7 , or a multilayer film comprising at least the layer. The heat-shrinkable film according to claim 9, wherein the heat-shrinkage rate at 80 ° C. in the stretching direction is 10 to 65%. Heat-shrinkable film according to claim 9 or 10 tensile modulus in the stretching direction is 7000~30000Kg / cm ^2.