JP6027378B2 - Laminated sheet and film - Google Patents

Description

  The present invention relates to a laminated sheet and a film.

  A block copolymer composed of a vinyl aromatic hydrocarbon and a conjugated diene having a relatively high vinyl aromatic hydrocarbon content is used for injection molding applications, sheets, and the like, utilizing properties such as transparency and impact resistance. It is used for extrusion molding applications such as films. In addition, attempts have been made to improve the mutual characteristics by combining such block copolymers with various thermoplastic resins. In this case, since the mutual compatibility is insufficient, for example, block copolymers and Even when a thermoplastic resin is laminated to form a sheet and a film, there are problems such as insufficient peel strength.

Thus, various studies have been made to improve mechanical properties and / or peel strength as a laminated sheet and film of a block copolymer and a thermoplastic resin.
In Patent Document 1, a styrene-butadiene block copolymer having a lamellar structure is used as a surface layer in order to obtain a laminated resin sheet for molding having excellent transparency, rigidity, and impact strength, and the styrene-butadiene block copolymer is styrene-based. A laminated resin sheet for molding has been disclosed in which a resin obtained by graft copolymerization of a monomer and an alkyl (meth) acrylate is used as an inner layer.
Patent Document 2 discloses a multilayer laminate of a polyolefin resin and a hydrogenated diene copolymer having a specific structure in order to obtain a multilayer laminate excellent in transparency, flexibility, cold resistance, heat seal strength, and the like. Yes.
In Patent Document 3, in order to obtain a multilayer laminate having excellent transparency, flexibility, heat resistance, impact strength and the like, a polyolefin resin and a hydrogenated diene copolymer having a specific structure are used as a base layer, A multilayer laminate having a surface layer of -4-methyl-1-pentene resin is disclosed. In Patent Document 4, in order to obtain a multilayer resin sheet having excellent physical property balance such as rigidity and impact resistance and satisfying peeling resistance, oil resistance and chemical resistance, a specific material composed of vinyl aromatic hydrocarbon and conjugated diene is specified. A multilayer resin sheet obtained by laminating a surface layer made of a substantially amorphous polyester polymer on a base material layer containing a block copolymer having a structure is disclosed.
In Patent Document 5, as a shrink label that is excellent in heat resistance, low-temperature shrinkage, and solvent resistance and is less likely to cause delamination of the base film, the outer surface layer is made of a polyester-based resin, and the intermediate layer is a styrene-based label. A laminated film made of a resin and a polyester resin is disclosed.

Japanese Patent Laid-Open No. 7-314611 JP-A-9-327893 Japanese Patent Laid-Open No. 10-34849 JP 2001-121664 A JP 2004-170715 A

However, any of the conventionally disclosed laminated sheets and films as described above still have room for improvement in transparency, rigidity, impact resistance, and peel strength. I don't have it.
The problem to be solved by the present invention is to provide a laminated sheet and a film excellent in transparency, rigidity, impact resistance and peel strength.

  As a result of intensive studies in order to solve the problems of the related art related to the laminated sheet and film as described above, the present inventors use a thermoplastic resin as the surface layer of the laminated sheet and film, and the laminated sheet. And it discovered that the said subject could be solved by using a specific block copolymer mixture and a specific block copolymer as an intermediate | middle layer of a film, and completed this invention.

That is, the present invention is as follows.
[1] A laminated sheet or film comprising a surface layer and an intermediate layer,
The surface layer comprises at least one thermoplastic resin;
1 to 60% by mass of the intermediate layer, a block copolymer (A) composed of a vinyl aromatic hydrocarbon and a conjugated diene, a block copolymer (B) composed of a vinyl aromatic hydrocarbon and a conjugated diene, And a block copolymer mixture (C) comprising 40 to 99% by mass of a vinyl aromatic hydrocarbon and a conjugated diene,
The block copolymer mixture includes 50 to 80% by mass of the block copolymer (A) and 20 to 50% by mass of the block copolymer (B),
The block copolymer (A) has a vinyl aromatic hydrocarbon content of 30 to 50 mass% and a conjugated diene content of 50 to 70 mass%, has a peak molecular weight of 30,000 to 70,000 as measured by GPC, Having at least one peak molecular weight of the aromatic hydrocarbon polymer block in the range of 10,000 to 30,000,
The block copolymer (B) has a vinyl aromatic hydrocarbon content of 30 to 50% by mass and a conjugated diene content of 50 to 70% by mass, and has a peak molecular weight of more than 70,000 and not more than 130,000 by GPC measurement. , Having at least one peak molecular weight of the vinyl aromatic hydrocarbon polymer block in the range of 10,000 to 30,000,
The block copolymer (C) has a vinyl aromatic hydrocarbon content of 60 to 95% by mass and a conjugated diene of 5 to 40% by mass, has a peak molecular weight of 30,000 to 500,000 by GPC measurement, and is vinyl aromatic. A laminated sheet or film having at least one peak molecular weight of the hydrocarbon polymer block in the range of 10,000 to 100,000.
[2] The block copolymer mixture includes 55 to 75% by mass of the block copolymer (A) and 25 to 45% by mass of the block copolymer (B). The laminated sheet or film described.
[3] The laminate according to [1] or [2], wherein the block copolymer (B) is a block copolymer obtained from the block copolymer (A) using a non-halogen coupling agent. Sheet or film.
[4] The thermoplastic resin is a polyolefin resin, AS resin, ABS resin, PMMA resin, styrene-butadiene-methyl methacrylate terpolymer resin (MBS resin), polyester resin, polyamide resin, polycarbonate resin, The laminated sheet or film according to any one of [1] to [3], which is at least one selected from polyurethane resins and polyphenylene ether resins.
[5] The intermediate layer further includes 0.1 to 80% by mass of at least one vinyl aromatic hydrocarbon polymer selected from the group consisting of the following (a) to (c): [1] Thru | or the laminated sheet or film in any one of [4].
(A) Styrenic polymer (b) At least one kind of aliphatic hydrocarbon selected from vinyl aromatic hydrocarbons and aliphatic unsaturated carboxylic acids, aliphatic unsaturated carboxylic acid anhydrides and aliphatic unsaturated carboxylic acid esters Copolymer with saturated carboxylic acid or derivative thereof (c) Rubber-modified styrenic polymer [6] The thickness ratio of the intermediate layer to the surface layer is 2/1 to 30/1, [1] to The laminated sheet or film according to any one of [5].

  According to the present invention, a laminated sheet and a film excellent in transparency, rigidity, impact resistance and peel strength can be obtained.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described.
The present invention is not limited to the following description, and various modifications can be made within the scope of the gist thereof.

[Laminated sheet and film]
The laminated sheet and film of this embodiment include a surface layer containing at least one thermoplastic resin, and an intermediate layer containing a block copolymer mixture and a block copolymer (C). It is.
In this embodiment, a thickness of 0.25 mm or more is referred to as a sheet, and a thickness of less than 0.25 mm is referred to as a film.
The laminated sheet and film of the present embodiment are excellent in transparency, rigidity, and impact resistance, and particularly have high peel strength between the intermediate layer and the surface layer.

(Surface layer)
The surface layer which comprises the lamination sheet and film of this embodiment contains at least 1 type of thermoplastic resin.

The thermoplastic resin used for the surface layer is not particularly limited, and examples thereof include “II. Thermoplastic resin” described in “2010 edition plastic molding material commerce manual (revised 26th edition); It is done.
Preferred thermoplastic resins used for the surface layer include polyolefin resin, AS resin, ABS resin, PMMA resin, styrene-butadiene-methyl methacrylate terpolymer resin (MBS resin), polyester resin, polyamide resin, Polycarbonate resins, polyurethane resins, and polyphenylene ether resins.
As the thermoplastic resin, at least one kind may be used, or two or more kinds may be mixed and used.

Examples of the polyolefin-based resin include polypropylene-based resins, polyethylene-based polymers, polybutene-1-based copolymers, etc., and modified polymers to which carboxylic acid groups are further added, and are selected from these polymers (resins). At least one kind may be a main component (preferably, 50% by mass in all components).
Examples of the polyethylene polymer include polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-methacrylic acid. Examples thereof include copolymers, other copolymers of ethylene and unsaturated fatty acids, ethylene ionomer resins, ethylene copolymers such as ethylene-α olefin copolymers, and the like.
Preferred polyolefin resins include polypropylene resins (including random copolymers and random copolymers modified with alicyclic saturated hydrocarbon resins, petroleum resins, tempen resins, rosins), high density polyethylene, Examples thereof include linear low density polyethylene (L / LDPE), ultra low density polyethylene, and ionomer resin (for example, ethylene).

  The AS resin is preferably a resin having a monomer composition of 10 to 50% by mass of acrylonitrile and 50 to 90% by mass of styrene, and the production method of the AS resin is not particularly limited. For example, emulsion polymerization of acrylonitrile and styrene , Suspension polymerization, continuous bulk polymerization, and the like.

  The ABS resin is preferably a resin having a monomer structure of 10 to 20% by mass of acrylonitrile, 40 to 70% by mass of butadiene, and 20 to 40% by mass of styrene, and the production method of the ABS resin is not particularly limited. (1) A method in which butadiene is first emulsion polymerized to form a polybutadiene rubber latex, and styrene and acrylonitrile are emulsified in the presence of this latex and graft polymerization is performed. Examples include a bulk / suspension polymerization method in which polymerization is performed in a dissolved state, the rubber phase is phase-inverted to form rubber particles, and then dispersed in water to complete graft polymerization.

Examples of the PMMA resin include a transparent polymer containing 80% by mass or more of methyl methacrylate. In addition to the methyl methacrylate single polymer, the PMMA resin contains 1 to 20% by mass of methyl methacrylate and methyl acrylate, ethyl acrylate, butyl acrylate, or the like. A copolymer may also be used.
In addition, the PMMA resin can contain an acrylic elastomer, but since the acrylic elastomer may whiten the laminated film, it is preferable to avoid the use of the PMMA resin containing the acrylic elastomer. A preferable blending ratio is 0 to 30 parts by mass with respect to a transparent polymer containing 80 to 100% by mass of 70 to 100 parts by mass of methyl methacrylate. A commercially available grade of PMMA resin called “impact resistant” PMMA containing acrylic elastomer in the form of multilayer particles can be used.

Styrene-butadiene-methyl methacrylate terpolymer resin (MBS resin) is a copolymer of methyl methacrylate, butadiene and styrene as raw materials, and a copolymer of butadiene and styrene (SBR) which is a rubber layer. A core-shell type thermoplastic resin having a core and a copolymer (MS) of methyl methacrylate and styrene as a shell.
Other than butadiene and styrene copolymer (SBR), an MBS resin having a polybutadiene rubber or polyacrylate rubber as a core may be used.
The preferable content of the rubber-like polymer as the rubber layer in the MBS resin is 5 to 30% by mass.

The polyester-based resin is a linear polymer in which structural units are bonded by repeating ester bonds.
Examples of the polyester-based resin include dibasic acids such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, p, p′-dicarboxydiphenyl, 2,6-naphthalene dicarboxylic acid, and derivatives thereof, ethylene glycol, Polypropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, p-xylene glycol, polycondensation with glycols (or diols) such as bisphenol A, pivalolactone, β-propio Examples thereof include ring-opening polymers such as lactone and ε-caprolactone.

The polyamide-based resin is a linear polymer in which structural units are bonded by repeating amide bonds.
Examples of the polyamide-based resin include ring-opening polymers and copolymers such as ε-aminocaprolactam and ω-aminolaurolactam, condensation polymers of ε-aminoundecanoic acid, hexamethylenediamine and adipic acid, sebacic acid, and the like. Examples thereof include condensation polymers with dibasic acids, such as nylon-46, nylon-6, nylon-66, nylon-610, nylon-11, nylon-12, and nylon-6-nylon-12. A copolymer etc. are mentioned.

The polycarbonate-based resin is a linear polymer in which structural units are bonded by repeating carbonate ester bonds.
Examples of the polycarbonate resin include a polymer obtained by a reaction of a dihydroxy compound such as 4,4′-dihydroxydiphenylalkane and 4,4′-dihydroxydiphenyl sulfide with phosgene, and the dihydroxy compound and diphenyl carbonate. Examples include polymers obtained by transesterification, and specific examples include poly-4,4′-dioxydiphenyl-2,2′-propane carbonate.

  Polyurethane-based resins are structural units such as poly (1,4-butylene adipate), poly (1,6-hexane adipate), polyester diols such as polycaprolactone, polyethers such as polyethylene glycol, polypropylene glycol, and polyoxytetramethylene glycol. A glycol component selected from glycols such as diol, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and aromatic, alicyclic and aliphatic diisocyanates, such as tolylene diisocyanate, 4 , 4,4'-Diphenylmethane diisocyanate, hexamethylene diisocyanate, and other diisocyanate components are polymer units in which structural units obtained by polyaddition reaction are bonded by repeating urethane bonds, Polyurethane.

Examples of polyphenylene ether resins include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2, 6-diethyl-1,4-phenylene) ether, poly (2-methyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-phenylene) ether, poly ( 2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-methyl-6-isobutyl-1,4-phenylene) ether, poly (2-methyl-4-chloro-phenylene) ether, Homogeneous such as poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether Coalescence and the like, preferably, poly (2,6-dimethyl-1,4-phenylene) ether.
The structural unit may be a copolymer partially containing an alkyl trisubstituted phenol, for example, 2,3,6-trimethylphenol, and may contain other known phenylene ether units as a partial structure. Good. Examples of other known phenylene ether units include 2- (dialkylaminomethyl) -6-methylphenylene ether units and 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether units. Can be mentioned. Further, a graft copolymer obtained by grafting styrene, α-methylstyrene, chlorostyrene, vinyltoluene, or the like as the styrene compound to the polyphenylene ether resin described above may be used.

The method for producing the composition constituting the surface layer is not particularly limited, and a known method can be used.
For example, a melt kneading method using a general mixer such as an open roll, a Banbury mixer, a single screw extruder, a twin screw extruder, a kneader, a multi-screw extruder, etc., after dissolving or dispersing and mixing each component, A method of removing the solvent by heating can be applied.
In particular, a melt kneading method using an extruder is preferable from the viewpoints of productivity and good kneading properties.

(Middle layer)
The laminated sheet and film of this embodiment are films laminated in the order of the intermediate layer and the surface layer.
The intermediate layer constituting the laminated sheet and film of the present embodiment includes a block copolymer (A) composed of vinyl aromatic hydrocarbon and conjugated diene, and a block copolymer (B) composed of vinyl aromatic hydrocarbon and conjugated diene. ), And a block copolymer (C) composed of a vinyl aromatic hydrocarbon and a conjugated diene.
1 to 60% by mass of the block copolymer mixture, 40 to 99% by mass of the block copolymer (C), preferably 3 to 55% by mass of the block copolymer mixture, and 45 to 45% of the block copolymer (C). 97% by mass, more preferably 5 to 50% by mass of the block copolymer mixture and 50 to 95% by mass of the block copolymer (C).
By including the block copolymer mixture constituting the intermediate layer and the block copolymer (C) in such an amount in the intermediate layer, a laminate sheet excellent in balance of physical properties such as transparency, rigidity, impact resistance and peel strength, and It can be a film.

In a block copolymer mixture, 50-80 mass% of block copolymers (A) and 20-50 mass% of block copolymers (B) are included.
Preferably, the block copolymer mixture contains 55 to 75% by mass of the block copolymer (A) and 25 to 45% by mass of the block copolymer (B).
By including the block copolymer (A) and the block copolymer (B) in such an amount in the intermediate layer, a laminated sheet and a film having excellent peel strength between the surface layer and the intermediate layer can be obtained.

The block copolymer (A) is a polymer having a vinyl aromatic hydrocarbon content of 30 to 50% by mass and a conjugated diene content of 50 to 70% by mass.
Preferably, the vinyl aromatic hydrocarbon content is 32 to 48 mass%, the conjugated diene content is 52 to 68 mass%, and the vinyl aromatic hydrocarbon content and the conjugated diene content are within such ranges. The laminate sheet and film can be excellent in peel strength and impact resistance between the surface layer and the intermediate layer.

  The peak molecular weight of the block copolymer (A) by GPC measurement is 30,000 to 70,000, preferably 35,000 to 65,000. The peak molecular weight of the vinyl aromatic hydrocarbon polymer block is 10,000. ˜30,000, preferably 10,000 to 27,000, more preferably 12,000 to 25,000.

The block copolymer (B) is a polymer having a vinyl aromatic hydrocarbon content of 30 to 50% by mass and a conjugated diene content of 50 to 70% by mass.
Preferably, the vinyl aromatic hydrocarbon content is 32 to 48 mass%, the conjugated diene content is 52 to 68 mass%, and the vinyl aromatic hydrocarbon content and the conjugated diene content are within such ranges. The laminate sheet and film can be excellent in peel strength and impact resistance between the surface layer and the intermediate layer.

  The peak molecular weight by GPC measurement of the block copolymer (B) is more than 70,000 and not more than 130,000, preferably 75,000 to 125,000, and the peak molecular weight of the vinyl aromatic hydrocarbon polymer block is It has at least one in the range of 10,000 to 30,000, preferably 10,000 to 27,000, more preferably 12,000 to 25,000.

  The block copolymer (A) has a peak molecular weight of 30,000 to 70,000 as measured by GPC, and the vinyl aromatic hydrocarbon polymer block has at least one peak molecular weight in the range of 10,000 to 30,000. A block copolymer having a peak molecular weight of more than 70,000 and not more than 130,000 according to GPC measurement of the polymer (B), and a vinyl aromatic hydrocarbon polymer block having a peak molecular weight in the range of 10,000 to 30,000. By setting it as a mixture, it can be set as the lamination sheet and film which are excellent in the film formability of a sheet | seat and a film, and the peeling strength of a surface layer and an intermediate | middle layer.

The peak molecular weights of the block copolymer (A) and the block copolymer (B) can be determined by GPC measurement.
Specifically, after obtaining the GPC curve by applying the block copolymer (A) or the block copolymer (B) to GPC, using a calibration curve prepared from the peak count number and molecular weight of the monodisperse polystyrene by GPC. The peak molecular weight can be determined by calculation according to a conventional method (“gel permeation chromatography”, pages 81 to 85 (1976, issued by Maruzen, Japan).
The peak molecular weight means the molecular weight at which the first derivative of the amount of change in the height of the vertical axis when the horizontal axis in the molecular weight distribution curve is the molecular weight is zero.
The peak molecular weight of the vinyl aromatic hydrocarbon polymer block of the block copolymer (A) and the block copolymer (B) is obtained by di-tertiary butyl hydroperoxide using osmium tetroxide as a catalyst. Method of oxidative decomposition [I. M.M. KOLTHOFF, et al. , J .; Polym. Sci. 1, 429 (1946)] can be obtained by analysis by gel permeation chromatography (GPC) in the same manner as described above except that the vinyl aromatic hydrocarbon polymer block component obtained by the method is used as a sample. .

The block copolymer (A) and the block copolymer (B) were each obtained by polymerizing vinyl aromatic hydrocarbons using an organic lithium compound as an anionic polymerization initiator in a hydrocarbon solvent, for example. The polymer and butadiene can be polymerized, and further optionally produced by repeating these operations.
The peak molecular weight of the block copolymer can be adjusted by controlling the amount of the organolithium compound.

The block copolymer mixture can be obtained by mixing two types of block copolymers (A) and block copolymers (B).
As such a mixing method, after completion of each polymerization reaction, the reaction solution is mixed and water, alcohol, acid or the like is added to deactivate the active species, or after completion of each polymerization reaction, the reaction solution is separated separately. And a method of separating the polymerization solvent by, for example, steam stripping and drying the resulting mixed solution.
The block copolymer (A) and the block copolymer (B) may be obtained by blending the block copolymer obtained by separating and drying the polymerization solvent separately from each reaction solution with a roll or the like. .

The block copolymer mixture can also be obtained by the following method.
After the block copolymer (A) is polymerized, a copolymer product obtained by adding a predetermined amount of a suitable coupling agent to the organolithium compound in the polymerization system is converted into the block copolymer (B). And the obtained block copolymer (B) can be obtained by mixing with the block copolymer (A).
In the block copolymer mixture obtained by such a method, the molecular weight and molecular weight distribution of the polymer block portion mainly composed of vinyl aromatic hydrocarbon are the same in the block copolymer (A) and the block copolymer (B). Therefore, it can be set as the lamination sheet and film which are excellent in the peeling strength of a surface layer and an intermediate | middle layer.

  The block copolymer (A) and the block copolymer (B) can be produced by a conventionally known method in the same manner as the block copolymer (C) described later, and the type of vinyl aromatic hydrocarbon, the type of conjugated diene, As for the kind of the hydrocarbon solvent, the kind of the organic lithium compound, the kind of the polar compound and the randomizing agent, the same one as the block copolymer (C) can be used.

When the block copolymer (B) is obtained by coupling reaction of the block copolymer (A), examples of the coupling agent include difunctional diglycidyl ether and di (glycidyloxy) (methyl). Epoxy compounds such as phenylsilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethoxymethylsilane, triethoxysilane, tetramethoxysilane, alkoxysilicon compounds such as tetraethoxysilane, methyl benzoate, ethyl benzoate, etc. Ester compounds, vinyl allenes such as divinylbenzene, silicon halide compounds such as dichlorodimethylsilane and phenylmethyldichlorosilane, tin compounds such as dichlorodimethyltin and tetrachlorotin, and ketones such as tetrachlorosilane Containing compounds, and the like.
Among these, bifunctional coupling agents are preferably used, and non-halogen coupling agents are preferably used from the viewpoint of heat discoloration during processing.
A coupling agent may use only 1 type and may mix and use 2 or more types.

The block copolymer (C) is a polymer having a vinyl aromatic hydrocarbon content of 60 to 95% by mass and a conjugated diene content of 5 to 40% by mass.
Preferably, the vinyl aromatic hydrocarbon content is 63 to 95% by mass, the conjugated diene content is 5 to 37% by mass, and the vinyl aromatic hydrocarbon content and the conjugated diene content are within such ranges. Moreover, it can be set as the laminated sheet and film which are excellent in physical property balance, such as impact resistance, and are excellent in transparency.

The peak molecular weight by GPC measurement of the block copolymer (C) is 30,000 to 500,000, preferably 50,000 to 400,000, and the peak molecular weight of the vinyl aromatic hydrocarbon polymer block is 10,000 to 100,000, Preferably, it has at least one in the range of 13,000 to 80,000.
When the peak molecular weight of the block copolymer (C) is within such a range, a constituent material having excellent mechanical strength can be obtained, and the peak molecular weight of the vinyl aromatic hydrocarbon polymer block is within such a range. Thereby, it can be set as the lamination sheet and film which are excellent in rigidity and impact resistance, and a moldability becomes favorable.

The block ratio of the vinyl aromatic hydrocarbon polymer block incorporated in the block copolymer (C) is preferably 10 to 98% by mass, more preferably 15 to 95% by mass, and further preferably 20 to 90% by mass. preferable.
When the block rate is 10 to 98% by mass, the balance between rigidity and impact resistance of the laminated sheet and film of this embodiment is excellent.

The block ratio of the vinyl aromatic hydrocarbon block is the mass ratio of the vinyl aromatic hydrocarbon and the conjugated diene in the step of copolymerizing at least a part of the vinyl aromatic hydrocarbon and the conjugated diene during the production of the block copolymer. It can be controlled by adjusting the polymerization reactivity ratio and the like.
As a specific method, (a) a mixture of a vinyl aromatic hydrocarbon and a conjugated diene is continuously supplied to a polymerization system for polymerization, and / or (b) a polar compound and / or a randomizing agent is added. And a method of copolymerizing a vinyl aromatic hydrocarbon and a conjugated diene.

  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; Examples thereof include sodium alkoxide.

The block ratio of the vinyl aromatic hydrocarbon polymer block of the block copolymer (C) is determined by a method in which the block copolymer is oxidatively decomposed with di-tertiary butyl hydroperoxide using osmium tetroxide as a catalyst [I. M.M. KOLTHOFF, et al. , J .; Polym. Sci. 1,429 (1946)], and the vinyl aromatic hydrocarbon polymer block component (excluding vinyl aromatic hydrocarbon polymer components having an average degree of polymerization of about 30 or less) was determined. Can be calculated by the following equation.

Vinyl aromatics in block copolymers.
Mass of hydrocarbon polymer block Block ratio (%) = ――――――――――――――――――――― × 100
Total vinyl in block copolymer
Aromatic hydrocarbon mass

  The block copolymer (C) comprises a vinyl aromatic hydrocarbon content of 60 to 95 mass% and a conjugated diene of 5 to 40 mass%, has a peak molecular weight of 30,000 to 500,000 by GPC measurement, and is a vinyl aromatic carbonization. It has at least one peak molecular weight of the hydrogen polymer block in the range of 10,000 to 100,000 and is not particularly limited as long as it is a block copolymer, but may be a block copolymer as follows. preferable.

The block copolymer (C) includes a block copolymer comprising at least one polymer block A mainly composed of vinyl aromatic hydrocarbons and at least one polymer block B of conjugated diene. May be.
As the polymer block A mainly composed of vinyl aromatic hydrocarbons, “mainly composed” means containing more than 90% by mass of vinyl aromatic hydrocarbons. An aromatic hydrocarbon homopolymer block or a copolymer block of a vinyl aromatic hydrocarbon and a conjugated diene containing more than 90% by mass of a vinyl aromatic hydrocarbon can be mentioned.
Examples of the conjugated diene polymer block B include a copolymer block of a vinyl aromatic hydrocarbon and a conjugated diene, or a conjugated diene homopolymer block containing 5 to 90% by mass of a vinyl aromatic hydrocarbon.

When a random copolymer portion of vinyl aromatic hydrocarbon and conjugated diene is present in polymer block A mainly composed of vinyl aromatic hydrocarbon and polymer block B of conjugated diene, the copolymerized vinyl The aromatic hydrocarbon may be distributed uniformly in the polymer block A or the polymer block B, or may be distributed in a taper (gradual decrease).
In the random copolymer portion of the vinyl aromatic hydrocarbon and the conjugated diene, a plurality of portions where the vinyl aromatic hydrocarbon is uniformly distributed and / or portions where the vinyl aromatic hydrocarbon is distributed in a tapered shape may coexist.

  When the block copolymer (C) is composed of a plurality of one or both of the polymer block A and the polymer block B, the plurality of polymer blocks are different in molecular weight, composition, type and the like. There may be.

  The block copolymer (C) can be synthesized by a conventionally known method. For example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-17879, Japanese Patent Publication No. 48-2423, Japanese Patent Publication No. 49. No. 36957, JP-B-57-49567, JP-B-58-11446, etc., and vinyl aromatic hydrocarbons using anionic polymerization initiators such as organolithium compounds in hydrocarbon solvents It can be synthesized by a method of block copolymerizing a conjugated diene.

Examples of the polymer structure of the block copolymer (C) include linear block copolymers such as the following (i) to (iii).
A- (BA) _n (i)
A- (BA) _n -B (ii)
B− (A−B) _{n + 1} (iii)
Here, A is a polymer block A mainly composed of vinyl aromatic hydrocarbons, and B is a polymer block B of conjugated diene.
The boundary between the polymer block A and the polymer block B does not necessarily need to be clearly distinguished.
n is an integer greater than or equal to 1, and is generally 1-5.
The polymer structure of the block copolymer (C) includes the following structures (iv) to (vii) in addition to the linear block copolymer.
[(A−B) _k ] _m −X (iv)
[(A−B) _k −A] _m −X (v)
[(BA) _k ] _m -X (vi)
[(B−A) _k −B] _m −X (vii)
Here, A and B are the same as in formulas (i) to (iii), and k and m are integers of 1 or more, and are generally 1 to 5.
X represents, for example, a residue of a coupling agent such as silicon tetrachloride or tin tetrachloride, or a residue of an anionic polymerization initiator such as a polyfunctional organolithium compound. As the block copolymer, a radial block copolymer is used. Mixtures or mixtures of any polymer structures of these block copolymers can be used.

Examples of the vinyl aromatic hydrocarbon include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, 1,1. -Diphenylethylene etc. are mentioned, Styrene is preferable.
Only 1 type may be used for a vinyl aromatic hydrocarbon, and 2 or more types may be mixed and used for it.

The conjugated diene is a diolefin having a pair of conjugated double bonds. For example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3- Examples thereof include butadiene, 1,3-pentadiene, 1,3-hexadiene, and 1,3-butadiene and isoprene are preferable.
Only 1 type may be used for a conjugated diene, and 2 or more types may be mixed and used for it.

When 1,3-butadiene and isoprene are used in combination as the conjugated diene, the isoprene content is preferably 10% by mass or more and 25% by mass or more based on the total mass of 1,3-butadiene and isoprene. Is more preferable, and it is further more preferable that it is 40 mass% or more.
When the isoprene content is 10% by mass or more, thermal decomposition does not occur during molding at high temperature and the molecular weight does not decrease, so that a block copolymer having a good balance between appearance characteristics and mechanical strength can be obtained.

  When producing a block copolymer (C), it is preferable to make it react in a hydrocarbon solvent using an anionic polymerization initiator.

As the anionic polymerization initiator, an organic lithium compound can be used, and examples thereof include an organic monolithium compound, an organic dilithium compound, an organic polylithium compound, and the like. Specifically, ethyllithium, n-propyllithium, isopropyl Examples include lithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexamethylenedilithium, butadienyldilithium, and isoprenyldilithium.
Only 1 type may be used for an anionic polymerization initiator, and 2 or more types may be mixed and used for it.

Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, and octane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane; benzene, Aromatic hydrocarbons such as toluene, ethylbenzene, xylene and the like can be mentioned.
As a hydrocarbon solvent, only 1 type may be used and 2 or more types may be mixed and used.

  When the block copolymer (C) is produced, the polymerization rate is adjusted, the microstructure (cis, trans, vinyl ratio) of the polymerized conjugated diene is changed, and the reaction between the vinyl aromatic hydrocarbon and the conjugated diene. For the purpose of adjusting the ratio, a polar compound and / or a randomizing agent can be used.

The polymerization temperature of the block copolymer (C) 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 in general, it can be carried out within 48 hours, and the polymerization can be carried out in 1 to 10 hours by selecting particularly favorable conditions.
Moreover, it is preferable that the atmosphere of the system at the time of polymerization is in a state where it is substituted with an inert gas such as nitrogen gas.
The pressure at which the polymerization is performed is particularly limited as long as the pressure is sufficient to maintain the vinyl aromatic hydrocarbon and conjugated diene as monomers and the hydrocarbon solvent as a reaction solvent in the liquid layer at the polymerization temperature. It is not something.
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 (C) is obtained as a solution in the polymerization step, but is separated from the solution by removing the catalyst residue as necessary.
As a method for separating the solvent, for example, a polar solvent which is a poor solvent for the block copolymer, such as acetone or alcohol, is added to the solution after polymerization or after hydrogenation by a conventionally known method. , A method of precipitating and recovering the block copolymer, a method of charging the block copolymer solution into hot water with stirring, removing the solvent by steam stripping, and further heating the solution directly. And a method of distilling off the solvent.
You may add stabilizers, such as various phenol type stabilizers, phosphorus type stabilizers, a sulfur type stabilizer, an amine type stabilizer, to a block copolymer (C) as needed.

The intermediate layer constituting the laminated sheet and film of this embodiment may further contain a vinyl aromatic hydrocarbon polymer in addition to the block copolymer mixture and the block copolymer (C).
By further combining the vinyl aromatic hydrocarbon polymer, a laminated sheet and a film having excellent rigidity can be obtained.
The content of the vinyl aromatic hydrocarbon polymer is preferably 0.1 to 80% by mass, more preferably 0.3 to 75% by mass as the resin component constituting the intermediate layer. More preferably, it is -70 mass%.

As the vinyl aromatic hydrocarbon polymer, it is preferable to use at least one selected from the group consisting of the following (a) to (c).
(A) Styrenic polymer (b) At least one aliphatic unsaturated hydrocarbon selected from a vinyl aromatic hydrocarbon, an aliphatic unsaturated carboxylic acid, an aliphatic unsaturated carboxylic acid anhydride, and an aliphatic unsaturated carboxylic acid ester Copolymer with saturated carboxylic acid or derivative thereof (c) Rubber-modified styrene polymer

  (A) A styrenic polymer is a polymer obtained by polymerizing a copolymerizable monomer and styrene (excluding (b)), and as a monomer copolymerizable with styrene, α- Examples include methylstyrene and acrylonitrile.

Examples of the styrenic polymer include polystyrene, styrene-α-methylstyrene copolymer, acrylonitrile-styrene copolymer, and polystyrene is preferable.
(A) As a manufacturing method of a styrene-type polymer, the well-known method of manufacturing a styrene-type resin, for example, a block polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method etc. can be used.

The weight average molecular weight of the styrene polymer is generally 50,000 to 500,000.
Only one kind of styrenic polymer may be used, or two or more kinds of styrenic polymers may be mixed and used as a rigidity improving agent.

(B) a vinyl aromatic hydrocarbon and at least one aliphatic unsaturated carboxylic acid selected from an aliphatic unsaturated carboxylic acid, an aliphatic unsaturated carboxylic acid anhydride, and an aliphatic unsaturated carboxylic acid ester, or a derivative thereof In the copolymer, the aliphatic unsaturated carboxylic acid derivative includes an aliphatic unsaturated carboxylic acid anhydride and an aliphatic unsaturated carboxylic acid ester.
Examples of the aliphatic unsaturated carboxylic acid include acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic acid and the like.
Examples of the aliphatic unsaturated carboxylic acid anhydride include fumaric anhydride, itaconic anhydride, maleic anhydride and the like.
Examples of the aliphatic unsaturated carboxylic acid ester include mono- or diesters of an aliphatic unsaturated carboxylic acid and an alcohol having C1 to C12, preferably C2 to C12.
Examples of the aliphatic unsaturated carboxylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (meth) Examples include acrylic acid esters such as hexyl acrylate, methacrylic acid esters, fumaric acid, itaconic acid, maleic acid, and the like, and α, β unsaturated dicarboxylic acid monoesters or diesters of C1-C12 alcohols.

  The content of the aliphatic unsaturated carboxylic acid and / or the aliphatic unsaturated carboxylic acid derivative is generally 5 to 50% by mass, preferably 8 to 30% by mass, and more preferably 10 to 25% by mass.

  (B) As a manufacturing method of a copolymer, the well-known method of manufacturing a styrene resin, for example, a block polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method etc. can be used.

(B) The weight average molecular weight of the copolymer is generally 50,000 to 500,000.
(B) A copolymer may use only 1 type and may mix and use 2 or more types.

  As the copolymer (b), among the copolymers of vinyl aromatic hydrocarbon and aliphatic unsaturated carboxylic acid ester, styrene-aliphatic unsaturated carboxylic acid ester copolymer is preferable because it can maintain transparency. .

Among the aliphatic unsaturated carboxylic acid ester-styrene copolymers, particularly preferred are copolymers mainly composed of styrene and n-butyl acrylate, and the total amount of styrene and n-butyl acrylate. Is preferably 50% by mass or more, and more preferably a styrene-aliphatic unsaturated carboxylic acid ester copolymer in which the total amount of styrene and n-butyl acrylate is 60% by mass or more.
Laminated sheets and films further comprising an aromatic hydrocarbon-aliphatic unsaturated carboxylic acid ester copolymer mainly composed of styrene and n-butyl acrylate as an intermediate layer have good transparency and impact resistance. .

Examples of the (c) rubber-modified styrenic polymer include those obtained 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.
Examples of the copolymerizable elastomer include natural rubber, synthetic isoprene rubber, butadiene rubber, styrene-butadiene rubber, and high styrene rubber.
The elastomer is generally 3 to 50 parts by mass with respect to 100 parts by mass of the vinyl aromatic hydrocarbon and copolymerizable monomer, and is dissolved in this monomer or becomes a latex to form emulsion polymerization, bulk polymerization, bulk- Used for suspension polymerization and the like.

Preferred examples of the rubber-modified styrene polymer (c) include an impact-resistant rubber-modified styrene polymer (HIPS).
(C) The rubber-modified styrenic polymer can be used as an agent for improving rigidity and impact resistance.

(C) The weight average molecular weight of the rubber-modified styrenic polymer is generally 50,000 to 500,000.
(C) One type of rubber-modified styrenic polymer may be used, or two or more types may be mixed and used.

  The content of the rubber-modified styrenic polymer is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the block copolymer in consideration of maintaining transparency.

The vinyl aromatic hydrocarbon polymer preferably has a melt flow rate (MFR, temperature 200 ° C. under G condition, load 5 kg) of 0.1 to 100 g / 10 min, more preferably from the viewpoint of molding. It is 0.5-50 g / 10min, More preferably, it is 1-30 g / 10min.
In the case of an intermediate layer containing a block copolymer and a vinyl aromatic hydrocarbon polymer, an additive may be blended as necessary.

  Preferred additives in this embodiment include organic polysiloxanes, softeners and plasticizers such as mineral oil, hindered phenol antioxidants, antioxidants such as phosphorus heat stabilizers, hindered amine light stabilizers, benzoates. Triazole-based UV absorbers, flame retardants, antistatic agents, organic fibers, glass fibers, carbon fibers, metal whiskers and other reinforcing agents, colorants, etc. are also used, such as "rubber / plastic compounding chemicals" (edited by Rubber Digest) For example, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium sulfate, barium sulfate, silica, clay, talc, mica, wollastonite, montmorillonite, zeolite, alumina, titanium oxide, magnesium oxide, Inorganic fillers such as zinc oxide, slug wool, glass fiber; Pigments such as bon black, iron oxide; lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bisstearamide; mold release agents; paraffinic process oil, naphthenic process oil, aroma Family process oil, paraffin and the like.

The method for producing the composition constituting the intermediate layer is not particularly limited, and a known method can be used.
For example, a melt kneading method using a general mixer such as an open roll, a Banbury mixer, a single screw extruder, a twin screw extruder, a kneader, a multi-screw extruder, etc., after dissolving or dispersing and mixing each component, A method of removing the solvent by heating can be applied.
In particular, a melt kneading method using an extruder is preferable from the viewpoints of productivity and good kneading properties.
The melt kneading temperature is the softening temperature, melt viscosity, block copolymer (A), block copolymer (B) and block copolymer (C) of the vinyl aromatic hydrocarbon polymer used as necessary. In consideration of thermal deterioration and the like, 100 to 350 ° C is preferable, 150 to 350 ° C is more preferable, and 180 to 330 ° C is more preferable.
The melt kneading time (or the average residence time of the melt kneading step) is the degree of kneading (dispersibility) and productivity, the block copolymer (A), the block copolymer (B) and the block copolymer (C), In consideration of deterioration of the vinyl aromatic hydrocarbon polymer and the like, 0.2 to 60 minutes are preferable, 0.5 to 30 minutes are more preferable, and 1 to 20 minutes are more preferable.

(Configuration of laminated sheet and film)
The laminated sheet and film of this embodiment are not particularly limited as long as they have at least two layers having a surface layer and an intermediate layer.
The laminated configuration in the present embodiment is a two-type configuration consisting of a surface layer / intermediate layer. The thickness ratio between the surface layer and the intermediate layer constituting the laminated sheet and film is preferably 2/1 to 30/1 as the intermediate layer / surface layer in terms of adhesion effect and transparency. More preferably, it is ˜20 / 1.
The thickness ratio when the layer structure is 2 layers / 3 layers of surface layer / intermediate layer / surface layer is preferably 1/2/1 to 1/30/1 as surface layer / intermediate layer / surface layer. (In the present embodiment, the thickness ratio between the intermediate layer and the surface layer is 2/1 to 30/1.), 1/4/1 to 1/20/1. More preferred.

[Laminated sheet and film manufacturing method]
The laminated sheet and film of this embodiment can be manufactured by co-extruding the material which comprises an intermediate | middle layer and a surface layer using the extruder provided with T-die. In extruding, an existing method such as a T-die method or a tubular method may be employed.
Further, the laminated sheet and film of this embodiment can be produced even if the material constituting the intermediate layer and the material constituting the surface layer are separately formed into sheets and then laminated using a press method, a roll nip method, or the like. it can.

  The laminated sheet and film of the present embodiment are preferably not substantially stretched in order to reduce the dimensional change during the molding process, and 10 in 70 ° C. warm water in the extrusion direction (MD) and the orthogonal direction of extrusion (TD). The heat shrinkage rate per second is preferably 3% or less. In the present embodiment, “not substantially stretched” means that the film may be slightly stretched by a winding stress at the time of molding, and means that the film is not stretched in a heat shrink film or the like.

  Hereinafter, the present embodiment will be described in more detail with reference to examples and comparative examples. The present embodiment is not limited by the examples described later. In addition, the measuring method and evaluation method used in a present Example are as follows.

(1) Styrene content It calculated from the absorption intensity of 262 nm using the ultraviolet spectrophotometer (Hitachi UV200).

(2) Peak molecular weight by GPC measurement of block copolymer 10 mg of block copolymer was dissolved in 10 mL of tetrahydrofuran (THF), and the resulting solution was prepared for monodisperse polystyrene by gel permeation chromatography (GPC) measurement. The peak molecular weight was determined from the line. The measurement conditions for GPC are shown below.
Monodisperse polystyrene: TSK standard polystyrene (manufactured by Tosoh Corporation)
Column: TSK gel super multipore HZ-M (manufactured by Tosoh Corporation)
Column temperature: 42 ° C
Solvent: THF
Flow rate: 2mL / min
Measuring device: HLC-8220 (manufactured by Tosoh Corporation)
Detector: RI

(3) Block ratio A method of oxidatively decomposing a block copolymer with di-tertiary butyl hydroperoxide using osmium tetroxide as a catalyst [I. M.M. KOLTHOFF, et al. , J .; Polym. Sci. 1,429 (1946)] was quantified and determined from the following formula.

Mass of styrene block Block ratio (%) = ――――――――――――――――――― × 100
Total styrene mass

(4) Peak molecular weight of styrene block The styrene block component obtained by the same method as in (3) above was measured and determined by the same method as in (2) above.

(5) Melt flow rate Based on ASTM D1238, it was measured under the conditions of 200 ° C. and a load of 5 kg.

(6) Tensile modulus (Rigidity standard)
As a test piece, what was cut out in the shape of a strip from a stretched film to a length of 10 mm in the MD and TD directions and 100 mm between the marked lines was used.
The measurement temperature was 23 ° C., the tensile speed was 10 mm / min, and the measurement was performed according to JIS K-6732. The average value in the MD and TD directions was taken as the tensile modulus (MPa).

(7) Dirt impact strength (impact resistance standard)
Measured according to ASTM D1709, except that the weight shape was a 1/2 inch radius (unit: kg · cm)

(8) Haze value (a measure of transparency)
Liquid paraffin was applied to the surface of the laminated sheet and measured according to ASTM D1003.

(9) Peel strength Measures the strength of peeling at a peeling rate of 150 mm / min in the MD direction with a width of 1 cm and a 180 ° direction with the layer containing the surface layer of the laminated sheet as the peeling layer and the layer containing the intermediate layer as the peeled layer. did. The larger the value, the stronger and more desirable the peel strength.

<Manufacture of block copolymer>
(Block copolymer A-1)
Using an autoclave equipped with a stirrer, in a nitrogen gas atmosphere, in a cyclohexane solution containing 37 parts by mass of styrene, 0.145 parts by mass of n-butyllithium and 0.3 times that of tetramethylethylenediamine with respect to n-butyllithium Mole was added and polymerization was carried out by continuously feeding at 65 ° C. for 45 minutes.
Next, polymerization was carried out by continuously supplying a cyclohexane solution containing 63 parts by mass of 1,3-butadiene at 65 ° C. for 75 minutes.
After completion of the reaction, methanol was added to the polymerizer in an equimolar amount with respect to n-butyllithium, and then 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4 as a stabilizer. , 6-di-t-pentylphenyl acrylate was added to 0.5 parts by mass with respect to 100 parts by mass of the block copolymer to obtain block copolymer A-1.

(Block copolymer A-2)
Using an autoclave equipped with a stirrer, in a nitrogen gas atmosphere, in a cyclohexane solution containing 45 parts by mass of styrene, 0.125 parts by mass of n-butyllithium and 0.3 times that of tetramethylethylenediamine with respect to n-butyllithium Mole was added and polymerization was carried out by continuously feeding at 65 ° C. for 50 minutes.
Next, polymerization was carried out by continuously supplying a cyclohexane solution containing 55 parts by mass of 1,3-butadiene at 65 ° C. for 65 minutes.
After completion of the reaction, methanol was added to the polymerizer in an equimolar amount with respect to n-butyllithium, and then 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4 as a stabilizer. , 6-di-t-pentylphenyl acrylate was added to 0.5 parts by mass with respect to 100 parts by mass of the block copolymer to obtain block copolymer A-2.

(Block copolymer A-3)
Using an autoclave equipped with a stirrer, in a nitrogen gas atmosphere, in a cyclohexane solution containing 20 parts by mass of styrene, 0.107 parts by mass of n-butyllithium and 0.3 times that of tetramethylethylenediamine with respect to n-butyllithium Mole was added and polymerization was carried out by continuously feeding at 65 ° C. for 25 minutes.
Next, polymerization was performed by continuously supplying a cyclohexane solution containing 80 parts by mass of 1,3-butadiene at 65 ° C. for 95 minutes.
After completion of the reaction, methanol was added to the polymerizer in an equimolar amount with respect to n-butyllithium, and then 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4 as a stabilizer. , 6-di-t-pentylphenyl acrylate was added to 0.5 parts by mass with respect to 100 parts by mass of the block copolymer to obtain block copolymer A-3.

(Block copolymer A-4)
Using an autoclave equipped with a stirrer, in a nitrogen gas atmosphere, in a cyclohexane solution containing 58 parts by mass of styrene, 0.155 parts by mass of n-butyllithium and 0.3 times that of tetramethylethylenediamine with respect to n-butyllithium Mole was added and polymerization was carried out by continuously feeding at 65 ° C. for 65 minutes.
Next, a cyclohexane solution containing 42 parts by mass of 1,3-butadiene was continuously supplied at 65 ° C. for 55 minutes for polymerization.
After completion of the reaction, methanol was added to the polymerizer in an equimolar amount with respect to n-butyllithium, and then 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4 as a stabilizer. , 6-di-t-pentylphenyl acrylate was added to 0.5 parts by mass with respect to 100 parts by mass of the block copolymer to obtain block copolymer A-4.

(Block copolymer A-5)
Using an autoclave equipped with a stirrer, in a nitrogen gas atmosphere, in a cyclohexane solution containing 38 parts by mass of styrene, 0.243 parts by mass of n-butyllithium and 0.3 times that of tetramethylethylenediamine with respect to n-butyllithium Mole was added and polymerization was carried out by continuously feeding at 65 ° C. for 45 minutes.
Next, polymerization was carried out by continuously supplying a cyclohexane solution containing 62 parts by mass of 1,3-butadiene at 65 ° C. for 75 minutes.
After completion of the reaction, methanol was added to the polymerizer in an equimolar amount with respect to n-butyllithium, and then 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4 as a stabilizer. , 6-di-t-pentylphenyl acrylate was added to 0.5 parts by mass with respect to 100 parts by mass of the block copolymer to obtain block copolymer A-5.

(Block copolymer A-6)
Using an autoclave equipped with a stirrer, in a nitrogen gas atmosphere, in a cyclohexane solution containing 48 parts by mass of styrene, 0.099 parts by mass of n-butyllithium and 0.3 times that of tetramethylethylenediamine with respect to n-butyllithium Mole was added and polymerization was carried out by continuously feeding at 65 ° C. for 55 minutes.
Next, polymerization was carried out by continuously supplying a cyclohexane solution containing 52 parts by mass of 1,3-butadiene at 65 ° C. for 70 minutes.
After completion of the reaction, methanol was added to the polymerizer in an equimolar amount with respect to n-butyllithium, and then 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4 as a stabilizer. , 6-di-t-pentylphenyl acrylate was added to 0.5 part by mass with respect to 100 parts by mass of the block copolymer to obtain block copolymer A-6.

(Block copolymer A-7)
Using an autoclave equipped with a stirrer, in a nitrogen gas atmosphere, in a cyclohexane solution containing 31 parts by mass of styrene, 0.284 parts by mass of n-butyllithium and 0.3 times that of tetramethylethylenediamine with respect to n-butyllithium Mole was added and polymerization was carried out by continuously feeding at 65 ° C. for 40 minutes.
Next, polymerization was carried out by continuously supplying a cyclohexane solution containing 69 parts by mass of 1,3-butadiene at 65 ° C. for 80 minutes.
After completion of the reaction, methanol was added to the polymerizer in an equimolar amount with respect to n-butyllithium, and then 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4 as a stabilizer. , 6-di-t-pentylphenyl acrylate was added to 0.5 parts by mass with respect to 100 parts by mass of the block copolymer to obtain block copolymer A-7.

  Table 1 shows the styrene content (% by mass) of the block copolymers A-1 to A-7, the peak molecular weight (10,000) of the block copolymer, and the peak molecular weight (10,000) of the styrene block.

(Block copolymer B-1)
After completion of the polymerization reaction similar to A-1, after adding an equivalent amount of dimethoxysilane as a coupling agent to n-butyllithium in the polymerization vessel to cause a coupling reaction, 2- [1- (2- Hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate is added to 0.5 parts by mass with respect to 100 parts by mass of the block copolymer, Copolymer B-1 was obtained.

(Block copolymer B-2)
After completion of the polymerization reaction similar to A-2, an equivalent amount of dimethoxysilane as a coupling agent to n-butyllithium was added to the polymerization vessel to cause a coupling reaction, and then 2- [1- (2- Hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate is added to 0.5 parts by mass with respect to 100 parts by mass of the block copolymer, Copolymer B-2 was obtained.

(Block copolymer B-3)
After completion of the polymerization reaction similar to A-3, an equivalent amount of dimethoxysilane as a coupling agent to n-butyllithium was added to the polymerization vessel to cause a coupling reaction, and then 2- [1- (2- Hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate is added to 0.5 parts by mass with respect to 100 parts by mass of the block copolymer, Copolymer B-3 was obtained.

(Block copolymer B-4)
After completion of the same polymerization reaction as in A-4, an equivalent amount of dimethoxysilane as a coupling agent to n-butyllithium was added to the polymerization vessel to cause a coupling reaction, and then 2- [1- (2- Hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate is added to 0.5 parts by mass with respect to 100 parts by mass of the block copolymer, Copolymer B-4 was obtained.

(Block copolymer B-5)
Using an autoclave equipped with a stirrer, in a nitrogen gas atmosphere, in a cyclohexane solution containing 19 parts by mass of styrene, 0.049 parts by mass of n-butyllithium and 0.3 times that of tetramethylethylenediamine with respect to n-butyllithium Mole was added and polymerization was carried out by continuously feeding at 65 ° C. for 25 minutes.
Next, polymerization was carried out by continuously supplying a cyclohexane solution containing 62 parts by mass of 1,3-butadiene at 65 ° C. for 75 minutes.
Next, a cyclohexane solution containing 19 parts by mass of styrene was continuously supplied at 65 ° C. for 25 minutes for polymerization.
After completion of the reaction, methanol was added to the polymerizer in an equimolar amount with respect to n-butyllithium, and then 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4 as a stabilizer. , 6-di-t-pentylphenyl acrylate was added to 0.5 parts by mass with respect to 100 parts by mass of the block copolymer to obtain block copolymer B-5.

(Block copolymer B-6)
Using an autoclave equipped with a stirrer, in a nitrogen gas atmosphere, in a cyclohexane solution containing 48 parts by mass of styrene, 0.07 parts by mass of n-butyllithium and 0.3 times that of tetramethylethylenediamine with respect to n-butyllithium Mole was added and polymerization was carried out by continuously feeding at 65 ° C. for 60 minutes.
Next, polymerization was carried out by continuously supplying a cyclohexane solution containing 52 parts by mass of 1,3-butadiene at 65 ° C. for 65 minutes.
After completion of the reaction, methanol was added to the polymerizer in an equimolar amount with respect to n-butyllithium, and then 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4 as a stabilizer. , 6-di-t-pentylphenyl acrylate was added to 0.5 parts by mass with respect to 100 parts by mass of the block copolymer to obtain block copolymer B-6.

(Block copolymer B-7)
Using an autoclave equipped with a stirrer, in a nitrogen gas atmosphere, in a cyclohexane solution containing 11 parts by mass of styrene, 0.08 parts by mass of n-butyllithium and 0.3 times that of tetramethylethylenediamine with respect to n-butyllithium Mole was added and polymerization was carried out by continuously supplying at 65 ° C. for 15 minutes.
Next, polymerization was carried out by continuously supplying a cyclohexane solution containing 35 parts by mass of 1,3-butadiene at 65 ° C. for 45 minutes.
Next, polymerization was carried out by continuously supplying a cyclohexane solution containing 10 parts by mass of styrene at 65 ° C. for 15 minutes.
Next, polymerization was carried out by continuously supplying a cyclohexane solution containing 34 parts by mass of 1,3-butadiene at 65 ° C. for 45 minutes.
Next, polymerization was carried out by continuously supplying a cyclohexane solution containing 10 parts by mass of styrene at 65 ° C. for 15 minutes.
After completion of the reaction, methanol was added to the polymerizer in an equimolar amount with respect to n-butyllithium, and then 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4 as a stabilizer. , 6-di-t-pentylphenyl acrylate was added to 0.5 parts by mass with respect to 100 parts by mass of the block copolymer to obtain block copolymer B-7.

  Table 2 shows the styrene content (% by mass) of the block copolymers B-1 to B-7, the peak molecular weight (10,000) of the block copolymer, and the peak molecular weight (10,000) of the styrene block.

(Block copolymer C-1)
Using an autoclave equipped with a stirrer, in a nitrogen gas atmosphere, in a cyclohexane solution containing 31 parts by mass of styrene, 0.075 parts by mass of n-butyllithium and 0.3 times that of tetramethylethylenediamine with respect to n-butyllithium Mole was added and polymerization was carried out by continuously feeding at 65 ° C. for 35 minutes.
Next, polymerization was performed by continuously supplying a cyclohexane solution containing 36 parts by mass of 1,3-butadiene and 2 parts by mass of styrene at 65 ° C. for 45 minutes.
Next, polymerization was carried out by continuously supplying a cyclohexane solution containing 31 parts by mass of styrene at 65 ° C. for 35 minutes.
After completion of the reaction, methanol was added to the polymerizer in an equimolar amount with respect to n-butyllithium, and then 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4 as a stabilizer , 6-Di-t-pentylphenyl acrylate was added in an amount of 0.5 parts by mass with respect to 100 parts by mass of the block copolymer. Then, after solvent removal, it pelletized and the block copolymer C-1 was obtained.

(Block copolymer C-2)
Using an autoclave equipped with a stirrer, in a nitrogen gas atmosphere, in a cyclohexane solution containing 29 parts by mass of styrene, 0.058 parts by mass of n-butyllithium and 0.3 times that of tetramethylethylenediamine with respect to n-butyllithium Mole was added and polymerization was carried out by continuously feeding at 65 ° C. for 35 minutes.
Next, polymerization was performed by continuously supplying a cyclohexane solution containing 27 parts by mass of 1,3-butadiene and 16 parts by mass of styrene at 65 ° C. for 55 minutes.
Next, polymerization was carried out by continuously supplying a cyclohexane solution containing 28 parts by mass of styrene at 65 ° C. for 35 minutes.
After completion of the reaction, methanol was added to the polymerizer in an equimolar amount with respect to n-butyllithium, and then 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4 as a stabilizer , 6-Di-t-pentylphenyl acrylate was added in an amount of 0.5 parts by mass with respect to 100 parts by mass of the block copolymer. Then, after removing the solvent, it was pelletized to obtain a block copolymer C-2.

(Block copolymer C-3)
Using an autoclave equipped with a stirrer, in a nitrogen gas atmosphere, in a cyclohexane solution containing 30 parts by mass of styrene, 0.070 parts by mass of n-butyllithium and 0.3 times that of tetramethylethylenediamine with respect to n-butyllithium Mole was added and polymerization was carried out by continuously feeding at 65 ° C. for 30 minutes.
Next, polymerization was performed by continuously supplying a cyclohexane solution containing 17 parts by mass of 1,3-butadiene and 23 parts by mass of styrene at 65 ° C. for 40 minutes.
Next, polymerization was carried out by continuously supplying a cyclohexane solution containing 30 parts by mass of styrene at 65 ° C. for 30 minutes.
After completion of the reaction, methanol was added to the polymerizer in an equimolar amount with respect to n-butyllithium, and then 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4 as a stabilizer , 6-Di-t-pentylphenyl acrylate was added in an amount of 0.5 parts by mass with respect to 100 parts by mass of the block copolymer. Then, after removing the solvent, it was pelletized to obtain a block copolymer C-3.

  Table 3 shows the styrene content (% by mass) of the block copolymers C-1 to C-3, the peak molecular weight of the block copolymer, the peak molecular weight of the styrene block, and the block ratio.

<Production example of vinyl aromatic hydrocarbon copolymer>
Vinyl aromatic hydrocarbon copolymers D-1 and D-2 were prepared.
To a 10 L autoclave with a stirrer, 5 kg of styrene and n-butyl acrylate were added at the ratio shown in Table 4 below, and at the same time, 0.3 kg of ethylbenzene and 1,1 bis (t-butylperoxy) were used to adjust MFR. ) A predetermined amount of cyclohexane was charged, polymerized at 110 to 150 ° C. for 2 to 10 hours, and then unreacted styrene, n-butyl acrylate and ethylbenzene were collected and produced by a vent extruder.
The obtained MFR of D-1 was 3.0 g / 10 min. The MFR of D-2 was 2.6 g / 10 min.
Table 4 shows the styrene content (% by mass) of the vinyl aromatic hydrocarbon polymers D-1 and D-2.

<Thermoplastic resin>
Table 5 shows the thermoplastic resins used in the examples.

[Examples 1 to 10, Comparative Examples 1 to 9]
The block copolymers (A), (B), and (C) shown in Tables 6 and 7 are used as the intermediate layer, and the thermoplastic resins shown in Tables 7 and 8 are used as the surface layer. : Surface layer = 15: 1, melted in an extruder set in the range of resin temperature of the intermediate layer of 200 to 210 ° C. and resin temperature of the surface layer of 210 to 260 ° C. Extrusion was performed using seed 3 layers (lamination ratio (surface layer: intermediate layer: surface layer) = 0.5: 15: 0.5) and cooled with a cast roll to obtain a laminate sheet having a thickness of 0.4 mm.
The block copolymers (A) and (B) used for the intermediate layer were mixed in the form of a solution and then pelletized after solvent removal.
The physical property results of the obtained laminated sheet are shown in Table 8 and Table 9. As is clear from the results shown in Tables 8 and 9, the laminated sheets (Examples 1 to 10) of this embodiment are excellent in transparency, rigidity, impact resistance and peel strength, and are food cases and packaging materials. It was found to be suitable for blisters and the like. Moreover, the thermal shrinkage rate for 10 seconds in 70 degreeC warm water of the extrusion direction (MD) and extrusion orthogonal direction (TD) of the lamination sheet of Examples 1-10 and Comparative Examples 1-9 is 3% or less, and a dimension The change was small.

  Since the laminated sheet and film of the present invention can be used as food cases, packaging materials, blisters, etc., they have industrial applicability.

Claims (12)

A laminated sheet or film comprising a surface layer and an intermediate layer,
The surface layer includes at least one thermoplastic resin (provided that the surface layer does not include a polyester resin) ;
1 to 60% by mass of the intermediate layer, a block copolymer (A) composed of a vinyl aromatic hydrocarbon and a conjugated diene, a block copolymer (B) composed of a vinyl aromatic hydrocarbon and a conjugated diene, And a block copolymer mixture (C) comprising 40 to 99% by mass of a vinyl aromatic hydrocarbon and a conjugated diene,
The block copolymer mixture includes 50 to 80% by mass of the block copolymer (A) and 20 to 50% by mass of the block copolymer (B),
The block copolymer (A) has a vinyl aromatic hydrocarbon content of 30 to 50 mass% and a conjugated diene content of 50 to 70 mass%, has a peak molecular weight of 30,000 to 70,000 as measured by GPC, Having at least one peak molecular weight of the aromatic hydrocarbon polymer block in the range of 10,000 to 30,000,
The block copolymer (B) has a vinyl aromatic hydrocarbon content of 30 to 50% by mass and a conjugated diene content of 50 to 70% by mass, and has a peak molecular weight of more than 70,000 and not more than 130,000 by GPC measurement. , Having at least one peak molecular weight of the vinyl aromatic hydrocarbon polymer block in the range of 10,000 to 30,000,
The block copolymer mixture is more than 30,000 to 70,000 and more than 70,000 as peaks derived from the peak molecular weight of the block copolymer (A) measured by GPC and the peak molecular weight of the block copolymer (B) measured by GPC Having one peak at 130,000 or less,
The block copolymer (C) comprises a vinyl aromatic hydrocarbon content of 60 to 95% by mass and a conjugated diene of 5 to 40% by mass, and has a peak molecular weight of 30,000 to 500,000 as measured by GPC.
A laminated sheet or film having at least one peak molecular weight of the vinyl aromatic hydrocarbon polymer block in the range of 10,000 to 100,000.   The lamination according to claim 1, wherein the block copolymer mixture comprises 55 to 75% by mass of the block copolymer (A) and 25 to 45% by mass of the block copolymer (B). Sheet or film.   The laminated sheet or film according to claim 1 or 2, wherein the block copolymer (B) is a block copolymer obtained from the block copolymer (A) using a non-halogen coupling agent.   The thermoplastic resin is polyolefin resin, AS resin, ABS resin, PMMA resin, styrene-butadiene-methyl methacrylate terpolymer resin (MBS resin), polyester resin, polyamide resin, polycarbonate resin, polyurethane resin. And a laminated sheet or film according to any one of claims 1 to 3, which is at least one selected from polyphenylene ether-based resins. When the intermediate layer has a total mass of the intermediate layer of 100% by mass, 1 to 55% by mass of the block copolymer mixture and 40 to 97% by mass of the block copolymer (C), Including
5. The composition according to claim 1, further comprising 0.1 to 20 % by mass of at least one vinyl aromatic hydrocarbon polymer selected from the group consisting of the following (a) to (c). The laminated sheet or film described.
(A) Styrenic polymer (b) At least one kind of aliphatic hydrocarbon selected from vinyl aromatic hydrocarbons and aliphatic unsaturated carboxylic acids, aliphatic unsaturated carboxylic acid anhydrides and aliphatic unsaturated carboxylic acid esters Copolymer with saturated carboxylic acid or derivative thereof (c) Rubber-modified styrene polymer   The laminated sheet or film according to any one of claims 1 to 5, wherein a thickness ratio between the intermediate layer and the surface layer is 2/1 to 30/1. A method for producing a laminated sheet or film comprising a surface layer and an intermediate layer,
The surface layer includes at least one thermoplastic resin (however, the surface layer does not include a polyester resin);
1 to 60% by mass of the intermediate layer, a block copolymer (A) composed of a vinyl aromatic hydrocarbon and a conjugated diene, a block copolymer (B) composed of a vinyl aromatic hydrocarbon and a conjugated diene, And a block copolymer mixture (C) comprising 40 to 99% by mass of a vinyl aromatic hydrocarbon and a conjugated diene,
The block copolymer mixture includes 50 to 80% by mass of the block copolymer (A) and 20 to 50% by mass of the block copolymer (B),
  The block copolymer (A) has a vinyl aromatic hydrocarbon content of 30 to 50 mass% and a conjugated diene content of 50 to 70 mass%, has a peak molecular weight of 30,000 to 70,000 as measured by GPC, Having at least one peak molecular weight of the aromatic hydrocarbon polymer block in the range of 10,000 to 30,000,
  The block copolymer (B) has a vinyl aromatic hydrocarbon content of 30 to 50% by mass and a conjugated diene content of 50 to 70% by mass, and has a peak molecular weight of more than 70,000 and not more than 130,000 by GPC measurement. , Having at least one peak molecular weight of the vinyl aromatic hydrocarbon polymer block in the range of 10,000 to 30,000,
The block copolymer (C) comprises a vinyl aromatic hydrocarbon content of 60 to 95% by mass and a conjugated diene of 5 to 40% by mass, and has a peak molecular weight of 30,000 to 500,000 as measured by GPC.
Having at least one peak molecular weight of the vinyl aromatic hydrocarbon polymer block in the range of 10,000 to 100,000;
The manufacturing method of a lamination sheet or a film including the process of obtaining a block copolymer mixture from a block copolymer (A) and a block copolymer (B). The lamination according to claim 7, wherein the block copolymer mixture comprises 55 to 75% by mass of the block copolymer (A) and 25 to 45% by mass of the block copolymer (B). A method for producing a sheet or film. The production of a laminated sheet or film according to claim 7 or 8, wherein the block copolymer (B) is a block copolymer obtained from the block copolymer (A) by using a non-halogen coupling agent. Method. The thermoplastic resin is polyolefin resin, AS resin, ABS resin, PMMA resin, styrene-butadiene-methyl methacrylate terpolymer resin (MBS resin), polyester resin, polyamide resin, polycarbonate resin, polyurethane resin. And a method for producing a laminated sheet or film according to any one of claims 7 to 9, which is at least one selected from polyphenylene ether-based resins. When the intermediate layer has a total mass of the intermediate layer of 100% by mass, 1 to 55% by mass of the block copolymer mixture and 40 to 97% by mass of the block copolymer (C), Including
11 to 20% by mass, further comprising at least one vinyl aromatic hydrocarbon polymer selected from the group consisting of the following (a) to (c): The manufacturing method of the lamination sheet or film of description.
(A) Styrene polymer
(B) a vinyl aromatic hydrocarbon and at least one aliphatic unsaturated carboxylic acid selected from aliphatic unsaturated carboxylic acid, aliphatic unsaturated carboxylic acid anhydride and aliphatic unsaturated carboxylic acid ester, or a derivative thereof; Copolymer
(C) Rubber-modified styrene polymer The method for producing a laminated sheet or film according to any one of claims 7 to 11, wherein a thickness ratio between the intermediate layer and the surface layer is 2/1 to 30/1.