JP2012131077A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate excellent in mechanical strength, easy moldability and solvent resistance, and to provide a decorative laminate to be laminated on a molded body, a decorative sheet, and a decorated molded article which use the same.SOLUTION: The laminate includes: a layer (A) made from a polycarbonate resin material with a resin component of a polycarbonate resin; and a layer (B) made from a thermoplastic resin material with a resin component of a thermoplastic resin having a ring structure, laminated on one surface of the layer (A). Here, a glass-transition temperature TgA (°C) of the polycarbonate resin material is 125°C or below.

Description

  The present invention relates to a laminate and a decorative laminate for bonding a molded body using the laminate, a decorative sheet, and a decorative molded product.

  Conventionally, methacrylic resin films are excellent in transparency, weather resistance, surface hardness, surface appearance, and surface glossiness, so they are bonded to the surface of molded products as decorative films on the surfaces of molded products such as automobile interiors and home appliances. Widely used in applications related to optics such as transparent materials and displays. However, a methacrylic resin film for use as a transparent material has insufficient mechanical strength and solvent resistance.

  Patent Document 1 discloses a transparent layer obtained by laminating a layer containing a thermoplastic resin having a lactone ring structure on a layer containing a methacrylic resin in order to improve the mechanical strength and solvent resistance of the methacrylic resin film. A thermoplastic resin laminate has been proposed. However, the laminate has insufficient mechanical strength, and further has low resistance to a solvent used as a fragrance in an automobile, and there is a problem that the surface of the laminate is whitened by the solvent.

  In addition, as a thermoplastic resin laminate having excellent mechanical strength and solvent resistance, Patent Document 2 discloses a layer containing a thermoplastic resin having a lactone ring structure on the surface of a layer mainly composed of a polycarbonate resin. A thermoplastic resin laminate obtained by laminating layers has been proposed. However, the laminate has a polycarbonate resin as a main component and is excellent in resistance to fragrance and mechanical strength, but it needs to be molded at a high temperature and has a problem in ease of molding.

JP 2002-120326 A JP 2002-254544 A

  An object of the present invention is to provide a laminate having excellent mechanical strength and ease of molding, and excellent solvent resistance, a laminate for decorating a molded product using the laminate, a sheet for decorating, and a decorative molding. The purpose is to provide goods.

  The present inventors have intensively studied to solve the above problems. As a result, a thermoplastic resin containing a thermoplastic resin having a ring structure on at least one surface of the layer (A) made of a polycarbonate resin material containing a polycarbonate resin having a glass transition point of 125 ° C. or lower as a resin component. By laminating the layer (B) made of the material, it was found that a laminate having excellent mechanical strength and ease of molding and excellent solvent resistance was obtained, and the present invention was completed.

That is, the present invention has the following configuration.
(1) A layer (B) made of a thermoplastic resin material containing a thermoplastic resin having a ring structure as a resin component is laminated on at least one surface of a layer (A) made of a polycarbonate resin material containing a polycarbonate resin as a resin component. A laminated body, wherein the polycarbonate resin material has a glass transition point TgA (° C.) of 125 ° C. or lower.
(2) The laminate according to (1), wherein the ring structure is a lactone ring structure.
(3) The laminate according to (1) or (2), wherein the thermoplastic resin is a methacrylic resin.
(4) The laminate according to any one of (1) to (3), wherein the polycarbonate resin material is a polycarbonate resin composition containing 70 to 99 parts by weight of a polycarbonate resin and 1 to 30 parts by weight of a plasticizer.
(5) The laminate according to (4), wherein the plasticizer is a phosphate ester compound.
(6) The said thermoplastic resin material contains 0.5-10 weight part of ultraviolet absorbers with respect to 100 weight part of thermoplastic resins which have a ring structure of said (1)-(5) characterized by the above-mentioned. The laminated body in any one.
(7) The total thickness is 20 to 200 μm, the thickness of the layer (A) is 10 to 80% of the total thickness, and the thickness of the layer (B) is 10 μm or more (1 The laminated body in any one of (6).
(8) The laminate according to any one of (1) to (7), wherein a polycarbonate resin material and a thermoplastic resin material are coextruded.
(9) The laminate according to any one of (1) to (8), wherein the layer (B) is laminated on one surface of the layer (A).
(10) The laminate according to any one of (1) to (8), wherein the layer (B) is laminated on both sides of the layer (A).
(11) A decorative laminate, wherein the surface of the laminate (A) side of the laminate according to (9) is decorated.
(12) A decorative laminate, wherein one surface of the laminate according to (10) is decorated.
(13) A decorative sheet, wherein a thermoplastic resin sheet is laminated on a surface on the decorative side of the decorative laminate according to (11) or (12).
(14) A decorative molded product, wherein a thermoplastic resin is injection-molded on a surface on the decorative side of the decorative laminate according to (11) or (12).
(15) A decorative molded product, wherein a thermoplastic resin is injection-molded on a surface of the decorative sheet according to (13) on the thermoplastic resin sheet side.

  It is possible to produce a laminate having excellent mechanical strength and ease of molding, and excellent solvent resistance, and a laminate for decorating, a sheet for decorating, and a decorative molded product using the laminate. it can.

The laminate of the present invention comprises a layer made of a thermoplastic resin material containing a thermoplastic resin having a ring structure on at least one surface of a layer made of a polycarbonate resin material containing a polycarbonate resin as a resin component (A) ( B) is laminated.
Here, the polycarbonate resin material contains a polycarbonate resin as an essential component and contains other components as necessary, that is, a polycarbonate resin or a polycarbonate resin composition.
The thermoplastic resin material is an essential component of a thermoplastic resin having a ring structure and contains other components as necessary. That is, a thermoplastic resin having a ring structure or a thermoplastic resin having a ring structure. Means a composition.

<Polycarbonate resin>
Examples of the polycarbonate resin that is an essential component of the polycarbonate resin material constituting the layer (A) include those obtained by reacting a dihydric phenol and a carbonylating agent by an interfacial polycondensation method or a melt transesterification method, Examples thereof include those obtained by polymerizing a carbonate prepolymer by a solid phase transesterification method, and those obtained by polymerizing a cyclic carbonate compound by a ring opening polymerization method.

  Examples of the dihydric phenol include hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-dimethyl) phenyl} methane, 1,1- Bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis { (4-hydroxy-3-methyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dibromo) ) Phenyl} propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl} propane, 2,2-bis {(4 Hydroxy-3-phenyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4 -Methylpentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3 5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy 3-methyl) phenyl} fluorene, α, α′-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfoxide, 4 , 4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ester, etc., and if necessary, use two or more of them You can also.

  Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3 -Methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) It is preferable to use one or more dihydric phenols selected from the group consisting of -3,3,5-trimethylcyclohexane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, Use of bisphenol A alone, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, bisphenol One or more selected from the group consisting of A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene Combination with dihydric phenol is preferred.

  Examples of the carbonylating agent include carbonyl halides such as phosgene, carbonate esters such as diphenyl carbonate, haloformates such as dihaloformates of dihydric phenols, etc., and these may be used alone. Two or more kinds can also be used.

The polycarbonate resin material constituting the layer (A) has a glass transition point TgA (° C.) of usually 125 ° C. or lower, preferably 120 ° C. or lower. If TgA (° C.) is higher than 125 ° C., the molding process becomes difficult.
In addition, the polycarbonate resin material constituting the layer (A) has a glass transition point TgA (° C.) in order to obtain a laminate that is easy to process and mold the laminate of the present invention and suitable for simultaneous injection molding. However, in relation to the glass transition point TgB (° C.) of the thermoplastic resin material constituting the layer (B), the formula: | TgB−TgA | <25 ° C. is satisfied. That is, the difference between TgA and TgB is made smaller than 25 ° C.

<Plasticizer>
As the polycarbonate resin material, a polycarbonate resin within the above glass transition point range may be used alone, or a polycarbonate resin composition in which the polycarbonate resin is mixed with other components within the above glass transition point range. May be used. As the polycarbonate resin composition, those containing a polycarbonate resin and a plasticizer are particularly preferably used.

  Examples of the plasticizer include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, and the like. Phosphate ester compounds, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis (2-ethylhexyl phthalate), diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalyl ethyl glycolate, phthalate ester compounds, Tris (2 -Ethylhexyl) trimellitic acid ester compounds such as trimellitate, dimethyl adipate, dibutyl acetate Pate, diisobutyl adipate, bis (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, diisodecyl adipate, bis (butyldiglycol) adipate, bis (2-ethylhexyl) azelate, dimethyl sebacate, dibutyl sebacate, bis (2- Ethylhexyl) aliphatic dibasic acid ester compounds such as sebacate and diethyl succinate, ricinoleic acid ester compounds such as methyl acetyl ricinoleate, acetic acid ester compounds such as triacetin and octyl acetate, and sulfones such as N-butylbenzenesulfonamide Examples include amide compounds. Among these, phosphate compounds, particularly cresyl diphenyl phosphate and tricresyl phosphate are preferred because of good compatibility with the polycarbonate resin and good transparency of the resin after compatibility.

  The mixing ratio of the polycarbonate resin and the plasticizer is 70 to 99 parts by weight for the polycarbonate resin and 1 to 30 parts by weight for the plasticizer, preferably 90 to 98 parts for the polycarbonate resin, with respect to 100 parts by weight in total. It is preferable that the weight part and the plasticizer are 2 to 10 parts by weight. When the blending ratio of the plasticizer is less than 1 part by weight with respect to 100 parts by weight of the total amount of the polycarbonate resin and the plasticizer, the plasticizing effect is insufficient and TgA is not sufficiently lowered, and TgA should be 125 ° C. or lower. It becomes difficult and it becomes difficult to process and form the obtained laminate. On the contrary, when the blending ratio of the plasticizer is more than 30 parts by weight, the fluidity of the polycarbonate resin composition is remarkably increased, and a multilayer film having a good appearance is obtained by the method of laminating with the thermoplastic resin material and co-extrusion molding. It becomes difficult.

<Thermoplastic resin having a ring structure>
The thermoplastic resin, which is an essential component of the thermoplastic resin material constituting the layer (B), may have any ring structure in the molecular chain. Examples of the ring structure include a lactone ring structure and glutaric anhydride. Examples include a structure, a glutarimide structure, a maleic anhydride structure, and a maleimide structure. Among these, a lactone ring structure is preferable. In addition, the resin component is not particularly limited, but an acrylic resin, particularly a methacrylic resin, is preferable in terms of the transparency and surface hardness of the resulting film.

  As a thermoplastic resin having a ring structure, for example, a methacrylic resin having a lactone ring structure in a molecular chain is obtained by subjecting a methacrylic resin having a hydroxyl group and an ester group in the molecular chain to a cyclocondensation reaction in the molecule. be able to. As a methacrylic resin having a hydroxyl group and an ester group in the molecular chain, for example, a monomer component containing monomers such as alkyl methacrylate, alkyl acrylate and 2- (hydroxyalkyl) alkyl acrylate is polymerized. What can be obtained can be mentioned.

  Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and the like, and the alkyl group usually has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Of these, methyl methacrylate is preferably used.

  Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like. The alkyl group usually has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms.

Preferred examples of the 2- (hydroxyalkyl) alkyl acrylate include 2- (hydroxymethyl) acrylic acid ester monomers.
Examples of 2- (hydroxymethyl) acrylic acid ester monomers include, for example, methyl 2- (hydroxymethyl) acrylate, 2- (hydroxymethyl) ethyl acrylate, 2- (hydroxymethyl) propyl acrylate, 2- (Hydroxymethyl) butyl acrylate and the like can be mentioned, and the alkyl group usually has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Of these, methyl 2- (hydroxymethyl) acrylate is preferably used.

It is also possible to use monomers other than alkyl methacrylate, alkyl acrylate, and 2- (hydroxyalkyl) alkyl acrylate, and monofunctional monomers, that is, polymerizable carbon-carbon doubles in the molecule. A compound having one bond is preferably used.
Examples of the compound having one polymerizable carbon-carbon double bond in the molecule include aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene, alkenyl cyanide compounds such as acrylonitrile, methacrylic acid and acrylic acid. Etc.

  In addition, the alkyl methacrylate, the alkyl acrylate, the alkyl 2- (hydroxymethyl) acrylate, and monomers other than these may each use 2 or more types as needed.

  The preferred composition of the monomer components is that the total of all monomers is 100% by weight, the alkyl methacrylate is 95 to 10% by weight, the alkyl acrylate is 0 to 50% by weight, and the alkyl 2- (hydroxymethyl) acrylate 5 to 50% by weight, and other monomers are preferably 0 to 30% by weight. If the ratio of 2- (hydroxymethyl) alkyl acrylate is less than the above range, the amount of the ring structure in the polymer obtained by polymerizing these monomer components decreases, so that the solvent resistance may be lowered. .

  The methacrylic resin having a hydroxyl group and an ester group in the molecular chain can be prepared by polymerizing the monomer component by a method such as solution polymerization or bulk polymerization. At that time, a chain transfer agent may be used at the time of polymerization in order to obtain a viscosity indicating ease of molding into a suitable laminate. The amount of the chain transfer agent may be appropriately determined according to the type of monomer and the ratio thereof.

  A methacrylic resin having a lactone ring structure in the molecular chain can be prepared by cyclizing and condensing the methacrylic resin having a hydroxyl group and an ester group in the molecular chain by a method such as using an organic phosphorus compound as a catalyst. it can. This cyclization condensation reaction is a reaction in which a hydroxyl group and an ester group, or further a carboxyl group present in the molecular chain of the methacrylic resin are cyclized and condensed to form a lactone ring structure.

  The thermoplastic resin material constituting the layer (B) may have a glass transition point TgB (° C.) within the range of the glass transition point satisfying the above relational expression: | TgB−TgA | <25 ° C. TgB is preferably 110 to 140 ° C. When TgB exceeds 140 ° C., it is not preferable from the viewpoint of moldability.

<Ultraviolet absorber>
The thermoplastic resin material preferably contains an ultraviolet absorber. By containing the ultraviolet absorber, the ultraviolet rays are absorbed, and when the layer (B) is laminated on at least one surface of the layer (A), decomposition degradation due to light energy in the layer (A) and the layer (B) When used in a place where light having ultraviolet rays such as sunlight hits, the stability of the laminate can be improved.

As the ultraviolet absorber, for example, a benzotriazole-based ultraviolet absorber or a benzophenone-based ultraviolet absorber can be used alone or in admixture of two or more.
Examples of the benzotriazole ultraviolet absorber include 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3 , 5-Di-tert-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di-tert-a Mil-2-hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole, 2- [2-hydroxy-3- (3,4,5,6) -Tetrahydrophthalimidomethyl) -5-methylphenyl] -2H-benzotriazole and the like.
Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-methoxy-4'-chlorobenzophenone. 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and the like.
Among them, from the viewpoint of reducing the volatile content from the film and preventing the deterioration of the printed pattern, a high molecular weight benzotriazole-based ultraviolet absorber such as 2,2′-methylenebis [6- (2H-benzotriazole 2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] and the like are preferable.

  The content of the ultraviolet absorber is 0.5 to 10 parts by weight, preferably 0.8 to 8 parts by weight, more preferably 1 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin having a ring structure. It should be 7 parts by weight. When the content of the ultraviolet absorber is less than 0.5 parts by weight, the ultraviolet energy is not sufficiently absorbed by the ultraviolet absorber, and when the layer (B) is laminated on at least one surface of the layer (A), The layer (A) and the layer (B), in particular the layer (A), is decomposed and deteriorated, and the laminate is not preferable. On the contrary, if the content of the ultraviolet absorber is more than 10 parts by weight, an effect corresponding to the cost cannot be obtained.

<Acrylic rubber particles>
The thermoplastic resin material preferably contains acrylic rubber particles. By containing the acrylic rubber particles, the resulting laminate can be made more difficult to break.

  The acrylic rubber particle is a particle containing an elastic polymer mainly composed of an acrylate ester as a rubber component, and may be a single-layered particle made of only this elastic polymer, or made of this elastic polymer. Although it may be a multi-layered particle having a layer, it is preferably a multi-layered particle from the viewpoint of the surface hardness of the layer (B) made of a thermoplastic resin material. The elastic polymer may be a homopolymer of an acrylate ester or a copolymer of 50% by weight or more of an acrylate ester and 50% by weight or less of other monomers. . Here, as the acrylic ester, an alkyl ester of acrylic acid is usually used.

  The preferred monomer composition of the elastic polymer mainly composed of acrylic acid ester is 50 to 99.9% by weight of alkyl acrylate and 0 to 49% of alkyl methacrylate based on the total of 100% by weight of all monomers. 0.9 wt%, monofunctional monomers other than these are 0 to 49.9 wt%, and polyfunctional monomers are 0.1 to 10 wt%.

  Examples of the alkyl acrylate in the elastic polymer are the same as those of the alkyl acrylate mentioned above as the monomer component of the methacrylic resin, and the alkyl group usually has 1 to 8 carbon atoms, preferably 1 to 1 carbon atoms. 4.

  Examples of the alkyl methacrylate in the elastic polymer are the same as those of the alkyl methacrylate previously mentioned as the monomer component of the methacrylic resin, and the alkyl group usually has 1 to 8 carbon atoms, preferably 1 to 1 carbon atoms. 4.

  Examples of monofunctional monomers other than alkyl acrylate and alkyl methacrylate include aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene, alkenyl cyanide compounds such as acrylonitrile and methacrylonitrile, acrylic acid and methacrylic acid. Examples include acids, maleic anhydride, and N-substituted maleimides. Of these, aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene are preferably used.

  Examples of polyfunctional monomers include polyunsaturated carboxylic acid esters of polyhydric alcohols such as ethylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate, allyl acrylate, allyl methacrylate, allyl cinnamate Alkenyl esters of unsaturated carboxylic acids such as polyallyl esters of polybasic acids such as diallyl phthalate, diallyl maleate, triallyl cyanurate and triallyl isocyanurate, and aromatic polyalkenyl compounds such as divinylbenzene. Of these, alkenyl esters of unsaturated carboxylic acids and polyalkenyl esters of polybasic acids are preferably used.

  In addition, as for said alkyl methacrylate, alkyl acrylate, monofunctional monomers other than these, and a polyfunctional monomer, you may use those 2 or more types as needed, respectively.

When the acrylic rubber particles having a multilayer structure are used, a preferable example thereof is a polymer mainly composed of methacrylic acid ester outside the layer composed of the above-mentioned elastic polymer mainly composed of acrylate ester. There can be mentioned those having at least a two-layer structure having a layer, that is, the above-mentioned elastic polymer mainly composed of an acrylate ester as an inner layer and a polymer mainly composed of a methacrylic ester as an outer layer. Here, as the methacrylic acid ester which is a monomer component of the polymer in the outer layer, alkyl methacrylate is usually used.
The outer layer polymer is usually formed at a ratio of 10 to 400 parts by weight, preferably 20 to 200 parts by weight with respect to 100 parts by weight of the inner layer elastic polymer. By setting the polymer of the outer layer to 10 parts by weight or more with respect to 100 parts by weight of the elastic polymer of the inner layer, the elastic polymer is hardly aggregated, and the transparency of the base material layer is improved.

  The preferred monomer composition of the polymer in the outer layer is 50 to 100% by weight of alkyl methacrylate, 0 to 50% by weight of alkyl acrylate, and 100% by weight of all other monomers. The functional monomer is 0 to 50% by weight, and the polyfunctional monomer is 0 to 10% by weight.

  Examples of the alkyl methacrylate in the polymer of the outer layer are the same as those of the alkyl methacrylate previously mentioned as the monomer component of the methacrylic resin, and the alkyl group usually has 1 to 8 carbon atoms, preferably 1-4. Of these, methyl methacrylate is preferably used.

  Examples of the alkyl acrylate in the polymer of the outer layer are the same as those of the alkyl acrylate mentioned above as the monomer component of the methacrylic resin, and the alkyl group usually has 1 to 8 carbon atoms, preferably 1-4.

Examples of monomers other than alkyl methacrylate and alkyl acrylate in the outer layer polymer include monofunctional monomers other than alkyl methacrylate and alkyl acrylate listed above as the monomer component of the elastic polymer. This is the same as the example.
Further, examples of the polyfunctional monomer in the polymer of the outer layer are the same as the examples of the polyfunctional monomer mentioned above as the monomer component of the elastic polymer.

  In addition, as for the alkyl methacrylate, the alkyl acrylate, the monomer other than these, and the polyfunctional monomer in the polymer of the outer layer, two or more kinds thereof may be used as necessary.

  Further, as a suitable example of the acrylic rubber particles having a multilayer structure, an inner layer of the above-mentioned two-layer structure made of the above-mentioned elastic polymer mainly composed of an acrylate ester, and a layer mainly composed of a methacrylic ester. A polymer having a layer composed of a polymer, that is, a polymer mainly composed of this methacrylic acid ester is used as an inner layer, and the above-mentioned elastic polymer mainly composed of an acrylate ester is used as an intermediate layer, and the above methacrylic acid ester is mainly used. Mention may also be made of at least a three-layer structure with the polymer as the outer layer. Here, as a methacrylic acid ester which is a monomer component of the polymer of the inner layer, alkyl methacrylate is usually used. The polymer of the inner layer is usually formed at a ratio of 10 to 400 parts by weight, preferably 20 to 200 parts by weight, with respect to 100 parts by weight of the elastic polymer of the intermediate layer.

  A preferable monomer composition of the polymer of the inner layer is 70 to 100% by weight of alkyl methacrylate, 0 to 30% by weight of alkyl acrylate based on 100% by weight of the total of all monomers, The functional monomer is 0 to 30% by weight, and the polyfunctional monomer is 0 to 10% by weight.

  Examples of the alkyl methacrylate in the polymer of the inner layer are the same as those of the alkyl methacrylate previously mentioned as the monomer component of the methacrylic resin, and the alkyl group usually has 1 to 8 carbon atoms, preferably 1-4. Of these, methyl methacrylate is preferably used.

  Examples of the alkyl acrylate in the polymer of the inner layer are the same as those of the alkyl acrylate mentioned above as the monomer component of the methacrylic resin, and the alkyl group usually has 1 to 8 carbon atoms, preferably 1-4.

  Examples of monomers other than alkyl methacrylate and alkyl acrylate in the inner layer polymer are monofunctional monomers other than alkyl methacrylate and alkyl acrylate mentioned above as the monomer component of the elastic polymer. The example of the polyfunctional monomer in the polymer of the inner layer is the same as the example of the polyfunctional monomer mentioned above as the monomer component of the elastic polymer.

  In addition, as for the alkyl methacrylate in the polymer of the said inner layer, and monomers other than these, respectively, you may use those 2 or more types as needed.

  Acrylic rubber particles can be prepared by polymerizing the monomer component of the above-mentioned elastic polymer mainly composed of an acrylate ester by at least one stage reaction by an emulsion polymerization method or the like. At that time, as described above, when a layer made of a polymer mainly composed of methacrylic acid ester is formed outside the layer made of the elastic polymer, the monomer component of the polymer in the outer layer is What is necessary is just to graft to the said elastic polymer by making it superpose | polymerize by reaction of at least 1 step | paragraph by emulsion polymerization method etc. in presence of the said elastic polymer. Further, as described above, when a layer made of a polymer mainly composed of methacrylic acid ester is formed inside the layer made of the above elastic polymer, first, the monomer component of the polymer of the inner layer Is polymerized by an emulsion polymerization method or the like in at least one stage reaction, and then the monomer component of the elastic polymer is reacted in the presence of the obtained polymer by at least one stage reaction by an emulsion polymerization method or the like. In the presence of the resulting elastic polymer, the monomer component of the outer layer polymer is reacted in at least one step by emulsion polymerization or the like in the presence of the resulting elastic polymer. May be grafted to the above elastic polymer by polymerization. When the polymerization of each layer is performed in two or more stages, it is sufficient that the monomer composition as a whole is within a predetermined range, not the monomer composition of each stage.

  Regarding the particle diameter of the acrylic rubber particles, the average particle diameter of the elastic polymer layer mainly composed of acrylic acid ester in the rubber particles is preferably 0.01 to 0.4 μm, and more preferably 0. It is 05-0.3 micrometer, More preferably, it is 0.07-0.25 micrometer. If the average particle size of the elastic polymer layer is larger than 0.4 μm, the transparency of the layer (B) made of the thermoplastic resin material is lowered and the transmittance is lowered, which is not preferable. On the other hand, if the average particle diameter of the elastic polymer layer is smaller than 0.01 μm, the surface hardness of the layer (B) is lowered, and it is not preferable because it is easily damaged.

  In addition, the average particle diameter is a portion obtained by mixing acrylic rubber particles with a methacrylic resin to form a film, dyeing the layer made of the elastic polymer with ruthenium oxide in the cross section, and observing with an electron microscope It can be calculated from the diameter. That is, when acrylic rubber particles are mixed with methacrylic resin and the cross section is dyed with ruthenium oxide, the methacrylic resin of the parent phase is not dyed, and the polymer mainly composed of methacrylic acid ester on the outer side of the elastic polymer layer. In the case where a layer made of is present, the outer polymer is not dyed, and only the layer made of the elastic polymer is dyed. Thus, the diameter of the portion dyed in this way and observed in a substantially circular shape with an electron microscope From this, the particle diameter can be determined. When a layer made of a polymer mainly composed of methacrylic acid ester exists inside the layer made of the elastic polymer, the polymer of the inner layer is not dyed, and the layer made of the elastic polymer outside is dyed. However, in this case, the outer diameter of the layer made of the above elastic polymer may be considered.

  The blending ratio of the thermoplastic resin material and the acrylic rubber particles is 85 to 100 parts by weight of the thermoplastic resin material and 0 to 15 parts by weight of the acrylic rubber particles based on the total of 100 parts by weight of both. When the blending ratio of the acrylic rubber particles is larger than 15 parts by weight, it becomes easy to whiten during bending or molding, and the surface hardness of the layer (B) is lowered and easily damaged, and the product after shape transfer. Appearance deteriorates. Therefore, even if the acrylic rubber particles are not blended, the acrylic rubber particles may not be blended if the required strength can be obtained as a film.

  The amount of the elastic polymer mainly composed of acrylic ester in the acrylic rubber particles is preferably 0 to 10 parts by weight based on 100 parts by weight of the total of the thermoplastic resin material and the acrylic rubber particles. More preferably, it is -8 weight part.

  The thermoplastic resin material constituting the layer (B) may contain other components, for example, organic dyes, inorganic dyes, pigments, antioxidants, antistatic agents and the like as necessary.

In order to develop a mat-like design, organic fine particles or inorganic fine particles are added to the polycarbonate resin material constituting the layer (A), the thermoplastic resin material constituting the layer (B), or both. It is effective that the layer (A) and / or the layer (B) is contained as a light diffusing mat layer.
As the organic fine particles, for example, cross-linked acrylic polymer particles or cross-linked styrene polymer particles are used, and as the inorganic fine particles, for example, silica or alumina is used.
The content of these fine particles is appropriately adjusted depending on the desired surface gloss and design, but if included in the polycarbonate resin material, it is usually 0.1 to 50% by weight with respect to 100% by weight of the polycarbonate resin material. If it is contained in the thermoplastic resin material, it is usually 0.1 to 50% by weight with respect to 100% by weight of the thermoplastic resin material.

<Laminated body>
The layer (B) is formed on at least one surface of the layer (A) using the polycarbonate resin material that is the constituent material of the layer (A) and the thermoplastic resin material that is the constituent material of the layer (B). Is laminated and integrated to obtain the laminate of the present invention.
As a method of laminating and integrating the layer (B) on at least one surface of the layer (A), for example, each constituent material is melted by an extruder and laminated using a feed block method or a multi-manifold method. Examples include coextrusion molding and filming of polycarbonate resin materials by extrusion molding, etc., and coating the surface of this film by dissolving the thermoplastic resin material in a solvent if necessary. Is preferably used.

In the co-extrusion molding method, each constituent material is melted, and a laminated resin obtained by integrating multiple layers is brought into close contact with a roll or a belt to form a film. The number, arrangement, and material of the rolls and belts at this time are not particularly limited, but the molten resin material is brought into contact with and passed between the two metal rolls or between the metal roll and the metal belt, and the surface of the roll or belt is laminated. The method of transferring to a resin is preferable for improving the surface accuracy of the film surface and improving the decorating property. Alternatively, the method in which both sides of the laminated resin are brought into contact with and passed through both roll surfaces with a metal roll and a metal roll having elasticity reduced distortion during molding and reduced anisotropy in strength and heat shrinkability. It is suitable for obtaining a film.
The metal elastic roll includes, for example, a shaft roll and a cylindrical metal thin film that is disposed so as to cover the outer peripheral surface of the shaft roll and is in contact with the laminated resin. Examples include a medium in which a temperature-controlled fluid such as water or oil is enclosed, or a rubber roll wound with a metal belt.

The thickness of the laminate thus obtained is usually 20 to 200 μm, preferably 30 to 150 μm, more preferably 50 to 100 μm. When the thickness of the laminate is greater than 200 μm, for example, when molding as an automobile interior material, it takes time for molding, and the effect of improving physical properties and design properties is small, and the cost is also high. On the other hand, if the thickness is less than 20 μm, the film formation by extrusion molding becomes difficult due to mechanical constraints, the breaking strength is reduced, and the probability of production failure is increased.
Here, the thickness of the multilayer film can be adjusted by adjusting the film forming speed, the thickness of the discharge port of the T-shaped die, the gap between the rolls, and the like.

  The thickness (A) of the polycarbonate resin material is preferably 10 to 80% of the thickness of the entire laminate. When the thickness of the layer (A) is less than 10% of the total thickness of the laminate, the laminate is brittle and easily cracked. The layer (B) of the thermoplastic resin material has a thickness of usually 10 μm or more, preferably 15 μm or more, more preferably 20 μm or more. When the thickness of the layer (B) is thinner than 10 μm, the surface hardness becomes insufficient. In addition, when arrange | positioning a layer (B) on both surfaces of a layer (A), the thickness of each layer (B) should just be normally 10 micrometers or more, Preferably it is 15 micrometers or more, More preferably, it is 20 micrometers or more.

<Decorating film>
The laminate of the present invention is preferably used as a decorative film. In the case of a laminate in which the layer (B) is laminated on one side of the layer (A), it is preferable that the surface on the layer (A) side is decorated, and both sides of the layer (A) In the case of a laminate in which the layer (B) is laminated, it is preferable that decoration is applied to one surface of the layer (B).
In consideration of decorating properties and surface hardness after commercialization, a laminate in which the layer (B) is formed on both sides of the layer (A) is preferably used.
As decoration means, for example, a method of directly printing wood grain or various designs on the surface by continuous gravure printing or silk printing, a method of applying metal plating to the surface by vapor deposition or sputtering, printing, Examples include a method of laminating other resin films that have been decorated such as vapor deposition.

<Decoration sheet>
Moreover, this decorative film can also be made into a decorative sheet by laminating a thermoplastic resin sheet as a backing material on the above-described decorative surface.
Here, examples of the resin constituting the thermoplastic resin sheet include ABS resin, methacrylic resin, polyvinyl chloride resin, polyurethane resin, polyester resin, and polyolefin resin. Further, the thickness of the thermoplastic resin sheet includes the thickness of a so-called film region, and is usually 0.1 to 2 mm.

<Decorated molded products>
And by laminating the decorative film or decorative sheet thus obtained on the thermoplastic resin molded product so that the resin layer side on which the decorative layer is not provided is arranged on the front side, that is, with the decorative film If there is, by laminating the thermoplastic resin molded product on the surface of the decorative side, and if it is a decorative sheet, by laminating the thermoplastic resin molded product on the surface of the thermoplastic resin sheet side, A decorative molded product can be obtained.
Here, examples of the resin constituting the thermoplastic resin molded article include ABS resin, methacrylic resin, polyvinyl chloride resin, polyurethane resin, polyester resin, and polyolefin resin.

As a method for obtaining a decorative molded product, an injection molding simultaneous bonding method is advantageously employed.
The injection molding simultaneous bonding method is a molten resin in which a decorative film or decorative sheet is inserted into an injection mold without preforming a decorative film or decorative sheet, and a thermoplastic resin molded product is formed there. To form an injection-molded product, and at the same time, a method of adhering a decorative film or a decorative sheet to the molded product (sometimes referred to as a simultaneous injection molding method in a narrow sense), a decorative film or After pre-molding the decorative sheet by vacuum molding or pressure molding, etc., it is inserted into an injection mold, and the molten resin constituting the thermoplastic resin molded product is injected there to form an injection molded product. A method of bonding a decorative film or decorative sheet to the molded product (sometimes called an insert molding method), or a decorative film or decorative sheet by vacuum molding or pressure molding in an injection mold. A method of injecting a molten resin constituting a thermoplastic resin molded product to form an injection molded product and then bonding a decorative film or a decorative sheet to the molded product (in-mold molding) (Sometimes called the law). More detailed explanation of the simultaneous injection molding method is described in, for example, Japanese Patent Publication No. 63-6339, Japanese Patent Publication No. 4-9647, Japanese Patent Application Laid-Open No. 7-9484, and the like.

  The laminated body thus obtained and the decorative laminate for bonding a molded body using the laminate, the decorative sheet, and the decorative molded product are used for automobile interior materials, home appliance skin materials, building material skin materials, and the like. used.

  Examples of the present invention will be described below, but the present invention is not limited thereto. In the examples,% and parts representing the content are based on weight unless otherwise specified. The glass transition point is an extrapolated glass transition start temperature obtained at a heating rate of 10 ° C./min by differential scanning calorimetry according to JIS K7121: 1987.

  “Caliber 303-10” (glass transition point 145 ° C.) manufactured by Sumitomo Dow Co., Ltd. was used as the polycarbonate resin.

  Cresyl diphenyl phosphate (“CDP” manufactured by Daihachi Chemical Industry Co., Ltd.) was used as a plasticizer.

  As the methacrylic resin 1 (methacrylic resin not having a ring structure), “SUMIPEX (MHF grade)” (glass transition point 104 ° C.) manufactured by Sumitomo Chemical Co., Ltd. was used.

[Production of methacrylic resin 2]
In a 1 m ³ reaction kettle equipped with a stirrer, temperature sensor, cooling pipe, and nitrogen introduction pipe, 136 kg of methyl methacrylate (MMA), 34 kg of methyl 2- (hydroxymethyl) acrylate (MHMA), and 166 kg of toluene were added. Charged and heated to 105 ° C while passing nitrogen, and when refluxed, 187 g of tertiary amyl peroxyisononanoate (manufactured by Arkema Yoshitomi Co., Ltd., trade name: “Lupasol 570”) was added as an initiator. At the same time, solution polymerization was carried out under reflux (about 105 to 110 ° C.) while dropping a solution consisting of 374 g of initiator and 3.6 kg of toluene over 2 hours, followed by further aging for 4 hours.
To the obtained polymer solution, 170 g of stearyl phosphate / distearyl phosphate mixture (manufactured by Sakai Chemical Industry Co., Ltd., trade name: “Phoslex A-18”) was added under reflux (about 90 to 110 ° C.). The cyclization condensation reaction was carried out for 5 hours. Subsequently, the polymer solution obtained by the above cyclization condensation reaction was vented with a barrel temperature of 250 ° C., a rotation speed of 150 rpm, a degree of vacuum of 13.3 to 400 hPa (10 to 300 mHg), a rear vent number of 1 and a forebelt number of 4 It is introduced into a type screw twin screw extruder (φ = 42 mm, L / D = 42) at a processing rate of 13 kg / h in terms of the amount of resin, subjected to cyclization condensation reaction and devolatilization in the extruder, and then extruded. Thus, a transparent pellet was obtained.
Subsequently, using a single screw extruder with a vent having a 50 mmφ, L / D = 36 with a polymer filter (filtration accuracy 5 μ) in a clean room of class 10,000, the pellets obtained above were 440 ppm. Melt kneading and devolatilization treatment with zinc acetate and 500 ppm stearyl alcohol at a treatment rate of 85 kg / h and simultaneously filtration treatment, and then extruding and pelletizing as a strand to methacrylic resin 2 (acrylic system having a lactone ring structure) Resin) pellets were prepared.
The resulting methacrylic resin 2 had a melt flow rate of 16.3 g / 10 min, a weight average molecular weight of 114,000, and a glass transition point of 127 ° C.
The melt flow rate of methacrylic resin 2 was measured at a test temperature of 240 ° C. and a load of 10 kg based on JIS-K7210.
Moreover, the weight average molecular weight of the methacryl resin 2 was calculated | required by polystyrene conversion of the gel permeation chromatography (Tosoh Co., Ltd. product GPC system) which used chloroform for the developing liquid.

As the acrylic rubber particles, the innermost layer is a hard polymer obtained by polymerization of a monomer consisting of 93.8% methyl methacrylate, 6% methyl acrylate, and 0.2% allyl methacrylate, and the intermediate layer is An elastic polymer obtained by polymerization of a monomer composed of 81% butyl acrylate, 17% styrene, and 2% allyl methacrylate. The outermost layer is composed of 94% methyl methacrylate and 6% methyl acrylate. It is a hard polymer obtained by polymerization of monomers, the polymerization ratio of innermost layer / intermediate layer / outermost layer is 35/45/20, and the average particle size of the elastic polymer layer of the intermediate layer is 0.00. Particles having a spherical three-layer structure by an emulsion polymerization method having a size of 22 μm were used.
The average particle diameter of the elastic polymer layer of the intermediate layer in the acrylic rubber particles was measured by the following method.

(Measurement of average particle diameter of elastic polymer layer)
Acrylic rubber particles are mixed with a methacrylic resin to form a film, the resulting film is cut into a suitable size, and the slice is immersed in an aqueous 0.5% ruthenium tetroxide solution at room temperature for 15 hours. The coalesced layer was stained. Further, the sample was cut to a thickness of about 80 nm using a microtome, and then photographed with a transmission electron microscope. From this photograph, 100 dyed elastic polymer layers were randomly selected, their diameters were calculated, and the number average value was determined.

<Examples 1-2 and Comparative Examples 1-2>
Polycarbonate resin is melted with a 75 mmφ twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), a liquid plasticizer is fed from the middle of the barrel with a pump, and the polycarbonate resin and the plasticizer are mixed at a ratio shown in Table 1, and polycarbonate is mixed. The resin composition was obtained as pellets (Example 1, Example 2). Table 1 shows the glass transition point of the polycarbonate resin composition.

  Further, methacrylic resin 1 and acrylic rubber particles were mixed at a ratio shown in Table 1 with a super mixer and melt kneaded with a twin screw extruder to obtain a methacrylic resin composition as pellets (Comparative Example 2). .

  Next, the above polycarbonate resin composition (Example 1, Example 2), polycarbonate resin (Comparative Example 1), or methacrylic resin composition (Comparative Example 2) as a material for forming the layer (A) is a 65 mmφ single screw extruder [ The methacrylic resin 2 used as the material for forming the layer (B) is melted with a 45 mmφ single-screw extruder (manufactured by Toshiba Machine Co., Ltd.), and melt laminated and integrated by a multi-manifold method. And extruding it through a T-shaped die at a set temperature of 255 ° C. (Example 1, Example 2, Comparative Example 2) or 265 ° C. (Comparative Example 1), and the resulting film-like product is a metal having a pair of smooth surfaces Molded by sandwiching between rolls made of metal. Thus, a laminate having a three-layer structure of layer (B) / layer (A) / layer (B) was produced, the following evaluation was performed, and the results are shown in Table 2.

<Pencil hardness test>
It measured according to JIS K 5600-5-4.

<Haze (H) test>
A 50 mm square test piece was prepared from the laminate, and measured according to JIS K7361 using “HR-100” manufactured by Murakami Color Research Laboratory.

<Strength (tensile fracture strain) test>
First, a strip-shaped test piece of 10 mm × 150 mm was cut out from the obtained laminate with a cutter. At this time, five test pieces (test pieces in the MD direction) cut out so that the long side of the test piece is parallel to the forming direction of the laminate, and the long side of the test piece is relative to the forming direction of the laminate. Five test pieces (test pieces in the TD direction) cut out so as to be vertical were prepared.
Next, each test piece was applied to JIS-K7127 using an Instron universal testing machine (“INSTRON5500R” manufactured by Instron Japan Co., Ltd.) under conditions of 50 mm between chucks, 25 ° C. temperature and 50 mm / min. Similarly, the test piece was stretched until it was broken, and the tensile fracture strain (%) or the preliminary strain (%) during tensile fracture was measured. And the average value of five test pieces was calculated | required for each direction, and this was made into the tensile fracture strain (%) of each direction. It can be said that the larger the tensile fracture strain (%) in each direction, the better the elongation and the stronger the strong laminate.

<Impact resistance (absorbed energy in Charpy impact test) test>
First, a 10 mm × 120 mm strip-shaped test piece was cut out from the obtained laminate with a cutter. At this time, 10 test pieces (test pieces in the MD direction) cut out so that the long sides of the test pieces are parallel to the forming direction of the laminate, and the long sides of the test pieces are relative to the forming direction of the laminate. Ten test pieces in the direction of (TD) cut out so as to be vertical were prepared.
Next, double-sided pressure-sensitive adhesive tape (“Bond” manufactured by Konishi Co., Ltd.) is applied to each test piece so that impact is applied from the direction perpendicular to the plane of the test piece (the film surface before cutting). For fixing the double-sided tape "), Charpy impact test was conducted according to JIS-K7111, and the absorbed energy (J) required for breaking the test piece was measured. And the average value of 10 test pieces was calculated | required for every direction, and this was made into the absorbed energy (J) of each direction. It can be said that the greater the absorbed energy (J) in each direction, the stronger and more durable the laminate.

<Ease of forming (maximum stress) test>
A 10 × 150 mm strip-shaped test piece was cut out from the obtained laminate with a cutter so that the long side was parallel to the molding direction of the laminate, and the obtained test piece was used as an Instron universal testing machine. (Instron Japan Co., Ltd. “INSTRON5500R”) is stretched until the test piece breaks under conditions of 50 mm between chucks, 140 ° C. temperature, 50 mm / min, and maximum stress during stretching (kgf) Was measured. In the ordinary simultaneous injection molding method, the temperature of the laminate surface at the time of preforming such as vacuum forming or pressure forming is about 140 to 160 ° C. Therefore, the smaller the maximum stress during stretching at 140 ° C., the lower the molding. It can be said that it is easy.

<Fragrance resistance test>
A 50 mm square test piece was prepared from the laminate, and a Teflon (registered trademark) cylinder having an inner diameter of 37 mm and a height of 20 mm was placed on the surface of the obtained test piece, and the opening was firmly attached to the test piece with a crimping device. 5 ml of an air freshener for automobile (“Grace Mate Poppy Citrus” manufactured by Dia Chemical Co., Ltd.) was injected into the flask. The opening was covered with a glass plate and sealed, and then placed in an oven maintained at 55 ° C. and left for 4 hours. Thereafter, the crimper was removed, the test piece was washed with water, dried, the surface state of the test part was observed, and the fragrance resistance of the test piece was evaluated according to the following criteria.
○: No change is observed.
X: Whitening or foaming is recognized.

Claims (15)

A layer (B) made of a thermoplastic resin material containing a thermoplastic resin having a ring structure as a resin component is laminated on at least one surface of a layer (A) made of a polycarbonate resin material containing a polycarbonate resin as a resin component. A laminate,
A laminate having a glass transition point TgA (° C.) of the polycarbonate resin material of 125 ° C. or lower.   The laminate according to claim 1, wherein the ring structure is a lactone ring structure.   The laminate according to claim 1 or 2, wherein the thermoplastic resin is a methacrylic resin.   The laminate according to any one of claims 1 to 3, wherein the polycarbonate resin material is a polycarbonate resin composition containing 70 to 99 parts by weight of a polycarbonate resin and 1 to 30 parts by weight of a plasticizer.   The laminate according to claim 4, wherein the plasticizer is a phosphate ester compound.   The laminate according to any one of claims 1 to 5, wherein the thermoplastic resin material contains 0.5 to 10 parts by weight of an ultraviolet absorber with respect to 100 parts by weight of a thermoplastic resin having a ring structure. body.   The total thickness is 20 to 200 µm, the thickness of the layer (A) is 10 to 80% of the total thickness, and the thickness of the layer (B) is 10 µm or more. The laminated body in any one.   The laminate according to any one of claims 1 to 7, wherein the polycarbonate resin material and the thermoplastic resin material are coextruded.   The layered product according to any one of claims 1 to 8, wherein the layer (B) is laminated on one surface of the layer (A).   The layered product according to any one of claims 1 to 8, wherein the layer (B) is laminated on both sides of the layer (A).   The laminated body for decoration characterized by decorating the surface by the side of the layer (A) of the laminated body of Claim 9.   A decorative laminate, wherein one surface of the laminate according to claim 10 is decorated.   A sheet for decorating, wherein a thermoplastic resin sheet is laminated on the surface on the decorating side of the laminate for decorating according to claim 11 or 12.   A decorative molded product, wherein a thermoplastic resin is injection-molded on the surface of the decorative laminate of the decorative laminate according to claim 11 or 12.   A decorative molded product, wherein a thermoplastic resin is injection-molded on the surface of the decorative sheet according to claim 13 on the thermoplastic resin sheet side.