TW201429715A - Laminate sheet - Google Patents

Abstract

The present invention is related to providing a laminate sheet which is not easy to be subjected to the warpage under the highly humid environment and has the excellent impact tolerance and surface hardness. The laminate sheet (1) of the present invention comprises the lamination structure of: the sequential lamination of the Methacrylic acid resin layer (C) containing the rubber-like polymer and the Methacrylic acid resin layer (B) on one of the surface (I) of the polycarbonate resin layer (A), and the sequential lamination of the Methacrylic acid resin layer (D) and the Methacrylic acid resin layer (E) containing the rubber-like polymer on the other surface (II) of the polycarbonate layer (A). The laminate sheet (1) of the present invention can be manufactured by means of, for example, the method mentioned below, which comprises the lamination carried out by means of the co-extrusion molding of the polycarbonate resin layer (A), the Methacrylic acid resin layers (B) and (D), and the Methacrylic acid resin layers (C) and (E) containing the rubber- like polymer.

Description

Laminate

The present invention relates to a laminate comprising a polycarbonate resin layer used in the fields of exterior use, kanban use, and the like.

Polycarbonate resin sheets are excellent in transparency, impact resistance, etc., and are used in various fields such as lighting applications and display front panel applications, mainly in the fields of appearance applications and kanban applications.

However, polycarbonate resin sheets generally have problems of durability and poor surface hardness.

In order to solve this problem, there is proposed a laminate in which an acrylic resin layer is laminated on one surface of a polycarbonate resin layer (for example, Patent Document 1). Further, the acrylic resin layer is inferior in impact resistance and may be cracked. Therefore, there is proposed a laminate which is not the above-mentioned acrylic resin layer but has a methyl group laminated on both sides of the polycarbonate resin layer. In the laminate of the acrylic resin layer, the methacrylic resin layer contains a crosslinked acrylate-based elastomer in an amount of 25 parts by weight based on 100 parts by weight of the methacrylic resin.

Such laminates, usually, are formed by extrusion molding To. In particular, a technique in which a methacrylic resin layer containing a rubber-like polymer such as a crosslinked acrylate-based elastomer and a polycarbonate resin layer are extrusion-molded and laminated and integrated is very useful, and the range of use is wide. .

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 08-025589

[Patent Document 2] Japanese Patent Laid-Open No. Hei 11-58627

However, the laminate in which one layer of the polycarbonate resin layer described in Patent Document 1 is laminated with an acrylic resin layer has a problem that warpage is increased in a high-humidity environment. In addition, a laminate of a methacrylic resin layer containing a crosslinked acrylate-based elastomer on both surfaces of the polycarbonate resin layer described in Patent Document 2 has a problem that the surface hardness is lowered.

Therefore, in the present invention, in view of the above problems, in order to solve the problem, it is an object of the present invention to provide a laminate which is less likely to warp in a high-humidity environment and which has excellent impact resistance and surface hardness.

As a result of intensive studies to solve the above problems, the inventors of the present invention found that the means for solving the following structures are completed. Cost invention. However, the present invention is not limited to the following invention.

[1] A laminate comprising: one side (I) of a polycarbonate resin layer (A), from which a rubber-like polymer-containing methacrylic resin layer is sequentially laminated; (C) and the methacrylic resin layer (B), and the other surface (II) of the polycarbonate resin layer (A), the methacrylic resin layer (D) is sequentially laminated from the surface (II) and The structure of the methacrylic resin layer (E) containing a rubbery polymer.

[2] The laminate according to the above [1], wherein the thickness of the methacrylic resin layer (B) and the thickness of the methacrylic resin layer (D) are each 20 to 100 μm.

[3] The laminate according to the above [1] or [2], wherein the thickness of the rubber-containing polymer-containing methacrylic resin layer (C) and the rubber-containing polymer-containing methacrylic resin layer ( The thickness of E) is 20 to 100 μm each.

[4] The laminate according to any one of the above [1], wherein the thickness of the methacrylic resin layer (B) and the rubber-containing polymer-containing methacrylic resin layer (C) The total thickness is 50 to 200 μm.

[5] The laminate according to any one of the above [1], wherein the thickness of the methacrylic resin layer (D) and the rubber-containing polymer-containing methacrylic resin layer (E) The total thickness is 50 to 200 μm.

[6] The laminate according to any one of the above [1], wherein the thickness of the methacrylic resin layer (B) and the rubber-containing polymer-containing methacrylic resin layer (C) The total thickness, the thickness of the methacrylic resin layer (D), and the methyl group of the rubber-containing polymer described above The difference in the total thickness of the acrylic resin layer (E) is -50 to 50 μm.

[7] A method of producing a laminate according to any one of the above [1] to [6], wherein the method comprises the step of forming the polycarbonate resin layer by co-extrusion molding. (A), the methacrylic resin layers (B) and (D), and the rubber-containing polymer-containing methacrylic resin layers (C) and (E) are laminated.

According to the present invention, a laminate which is less likely to warp in a high-humidity environment and which has excellent impact resistance and surface hardness can be obtained.

1‧‧‧Laminated boards

2, 3‧‧‧ rubbery polymer

11,12,13‧‧‧Extrusion machine

14‧‧‧Feed module

15‧‧‧die

16‧‧‧1st chill roll

17‧‧‧2nd cooling roller

18‧‧‧3rd cooling roller

A‧‧‧ polycarbonate resin layer

B‧‧‧methacrylic resin layer

C‧‧‧methacrylic resin layer containing rubbery polymer

D‧‧‧methacrylic resin layer

E‧‧‧methacrylic resin layer containing rubbery polymer

One side of the I‧‧‧ polycarbonate resin layer

II‧‧‧The other side of the polycarbonate resin layer

Fig. 1 is a cross-sectional view showing a laminate according to an embodiment of the present invention.

[Fig. 2] is a schematic explanatory view showing a method of manufacturing a laminate according to an embodiment of the present invention.

The laminate of the present invention will be described based on Fig. 1 . Fig. 1 is a cross section showing a laminate 1 according to an embodiment of the present invention. The laminate 1 of the present invention has a side (I) of a polycarbonate resin layer (A), and a methacrylic resin layer (C) containing a rubber-like polymer is sequentially laminated from the surface (I). With methacrylic resin layer (B), and in polycarbon The other surface (II) of the acid ester resin layer (A) is formed by sequentially laminating a layer of the methacrylic resin layer (D) and the rubber-like polymer-containing methacrylic resin layer (E) from the surface (II). Structure. That is, the laminate 1 of the present invention has five layers laminated in the order of B, C, A, D, and E as shown in Fig. 1 (i.e., the laminate 1 of the present invention has ( B) / (C) / (A) / (D) / (E) laminated structure).

The polycarbonate resin which can form the polycarbonate resin layer (A) is not particularly limited, and examples thereof include a reaction between a dihydric phenol and a carbonylating agent by an interfacial polycondensation method, a melt transesterification method, or the like. A method obtained by polymerizing a carbonate prepolymer by a solid phase transesterification method or the like, or a method of polymerizing a cyclic carbonate compound by a ring-opening polymerization method.

Examples of the dihydric phenol system include hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)methane, and bis{(4-hydroxy-3,5- Dimethyl)phenyl}methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-dual ( 4-hydroxyphenyl)propane (commonly known as 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)benzene Propane, 2,2-bis{(4-hydroxy-3-phenyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxybenzene) 3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,4-bis(4-hydroxyphenyl)-2-methyl Butane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl) Cyclohexane, 1,1-bis(4-hydroxyl Phenyl)-4-isopropylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 9,9-bis(4-hydroxybenzene ,茀,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-hydroxyl) Phenyl)-5,7-dimethyl adamantane, 4,4'-dihydroxydiphenylanthracene, 4,4'-dihydroxydiphenylarylene, 4,4'-dihydroxydiphenyl sulfide , 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ester, and the like. These may be used alone or in combination of two or more.

Among these dihydric phenols, preferred are 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-dual (4 -hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and α,α'-bis(4-hydroxyl Phenyl)-m-diisopropylbenzene. In particular, it is preferred to use bisphenol A alone, or bisphenol A, and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-double At least one selected from the group consisting of {(4-hydroxy-3-methyl)phenyl}propane and α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene is used in combination.

As the carbonylating agent, for example, a carbonyl halide (for example, carbonyl dichloride or the like), a carbonate (for example, diphenyl carbonate or the like), a haloformate (for example, a dihalogen of a dihydric phenol) can be used. Formate, etc.). These may be used alone or in combination of two or more.

Further, it is not particularly limited to the above solid phase transesterification method The carbonate prepolymer to be used, or the cyclic carbonate compound used in the ring-opening polymerization method, can be used as known in the art.

Further, in the present invention, commercially available polycarbonate can also be used.

The molecular weight of the polycarbonate resin contained in the polycarbonate resin layer (A) is not particularly limited, and is, for example, 10,000 to 30,000, preferably 15,000 to 25,000. In addition, these values are all weight average molecular weights.

The methacrylic resin which forms the methacrylic resin layers (B) and (D) is a polymer obtained by polymerizing a monomer mainly containing a methacrylate, and examples thereof include a homopolymer of methacrylate. a copolymer of 50% by weight or more of methacrylate and 50% by weight or less of a monomer other than methacrylate. In the case of a copolymer, it is preferably 70% by weight or more based on the total weight of the monomers, 30% by weight or less of the other monomers, more preferably 90% by weight or more of the methacrylate, and the like. The monomer is 10% by weight or less.

Further, the methacrylic resin layers (B) and (D) may be formed of the same methacrylic resin or may be formed of different methacrylate resins. The methacrylic resin layers (B) and (D) are preferably formed of the same methacrylic resin from the viewpoint of controlling warpage.

The methacrylate is not particularly limited, and examples thereof include a methacrylate having a substituent and a linear or branched alkyl group having 1 to 20 carbon atoms in the ester moiety. The substituent of the alkyl group of the ester moiety is not particularly The limitation is, for example, an alkoxy group having 1 to 12 carbon atoms. Further, the number of substituents and the position at which the alkyl group is substituted are not particularly limited. More specific examples of the methacrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and methyl group. Isobutyl acrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-decyl methacrylate, isodecyl methacrylate, Ethyl methacrylate, eleven methacrylate, n-amyl methacrylate, isoamyl methacrylate, lauryl methacrylate, methoxyethyl methacrylate, ethoxy ethoxy acrylate Ester and the like. The methacrylate type may be used alone or in combination of two or more. Among these, a methacrylate having an alkyl group having 1 to 8 carbon atoms is preferred, and methyl methacrylate is more preferred.

The methacrylic resin containing methyl methacrylate, specifically, a polymer containing 50% by weight or more, preferably 70% by weight or more of methyl methacrylate, may be methyl methacrylate. The polymer (i.e., polymethyl methacrylate) may also be a copolymer of methyl methacrylate with other monomers (i.e., other monomers capable of copolymerizing with methyl methacrylate).

The monomer other than the methacrylate is not particularly limited, and examples thereof include an acrylate, an aromatic vinyl compound, a maleimide, an unsaturated nitrile, a hydroxyalkyl ether of an ethylenically unsaturated carboxylic acid, and no ethylene. Saturated carboxylic acid decylamine, ethylenically unsaturated acid, ethylenically unsaturated sulfonate, ethylenically unsaturated alcohol and ester thereof, ethylenically unsaturated ether, ethylenically unsaturated amine, ethylenically unsaturated decane compound, fat Group conjugated diene and the like. Such Among them, an acrylate is preferred. The monomers other than the methacrylate may be used singly or in combination of two or more.

The acrylate is not particularly limited, and examples thereof include an acrylate having a substituent having an alkyl group having a linear or branched carbon number of 1 to 20 in the ester portion. The substituent of the alkyl group of the ester moiety is not particularly limited, and examples thereof include an alkoxy group having 1 to 12 carbon atoms. Further, the number of substituents and the position at which the alkyl group is substituted are not particularly limited. Specific examples of the acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, heptyl acrylate, and acrylic acid 2- Ethylhexyl ester, n-octyl acrylate, n-decyl acrylate, isodecyl acrylate, decyl acrylate, decyl acrylate, n-amyl acrylate, isoamyl acrylate, lauryl acrylate, methoxy acrylate Ethyl ester, ethoxyethyl acrylate, and the like. Among these, an acrylate having an alkyl group having 1 to 8 carbon atoms is preferred, and methyl acrylate is more preferred.

The aromatic vinyl compound is not particularly limited, and examples thereof include styrene, halogenated styrene (for example, chlorostyrene, bromostyrene, etc.), and alkylstyrene (for example, vinyl toluene, α-methylstyrene). Such as styrene or the like having a linear or branched alkyl group having 1 to 12 carbon atoms).

The maleidinide is not particularly limited, and examples thereof include saturated or unsaturated alicyclic horses such as aromatic maleidinide such as phenylmaleimide and cyclohexylmaleimide.醯imine and so on.

The unsaturated nitrile is not particularly limited, and examples thereof include acrylonitrile, α-chloroacrylonitrile, α-methoxy acrylonitrile, methacrylonitrile, and dicyandiamide. Ethylene and the like.

The hydroxyalkyl ether of the ethylenically unsaturated carboxylic acid is not particularly limited, and examples thereof include a (meth) acrylate having at least one hydroxyl group and an alkyl group having a linear or branched carbon number of 1 to 20 in the ester portion. More specifically, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, etc. are mentioned.

The ethylenically unsaturated carboxylic acid amide is not particularly limited, and examples thereof include (meth) acrylamide which may have a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent. The substituent which the alkyl group may have is not particularly limited, and examples thereof include an alkoxy group having 1 to 12 carbon atoms. Further, the number of substituents and the position at which the alkyl group is substituted are not particularly limited. Further, the number of alkyl groups and the position at which the decylamine is substituted are not particularly limited. Specific examples of the ethylenically unsaturated carboxylic acid decylamine include acrylamide, methacrylamide, N-butoxymethyl acrylamide, N-butoxymethyl methacrylamide, and N. - Butoxyethyl acrylamide, N-butoxyethyl methacrylamide, N-methoxymethyl propylene amide, N-methoxymethyl methacrylamide, Nn-propyl Oxymethyl methacrylamide, Nn-propoxymethyl methacrylamide, N-methyl acrylamide, N-methyl methacrylamide, N, N-dimethyl decylamine, N,N-dimethylmethacrylamide, N,N-diethylacrylamide, N,N-diethylmethacrylamide, and the like.

The ethylenically unsaturated acid is not particularly limited, and examples thereof include ethylene having 2 to 20 carbon atoms such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, fumaric anhydride, maleic acid, and maleic anhydride. Saturated carboxylic acid or An anhydride thereof; an ethylenically unsaturated sulfonic acid having 2 to 20 carbon atoms such as vinylsulfonic acid or isoprenesulfonic acid. The ethylenically unsaturated acid can also be neutralized with an alkali metal such as sodium or potassium, ammonia or the like.

The ethylenically unsaturated sulfonate is not particularly limited, and examples thereof include an ethylenically unsaturated sulfonate having 2 to 20 carbon atoms having a linear or branched alkyl group having 1 to 20 carbon atoms in the ester portion, and the like. Specific examples thereof include alkyl vinyl sulfonate and alkyl isoprene sulfonate.

The ethylenically unsaturated alcohol and the ester thereof are not particularly limited, and examples thereof include an ethylenically unsaturated alcohol having 2 to 20 carbon atoms (for example, vinyl alcohol, allyl alcohol, methyl allyl alcohol, etc.), and carbon. An ester of 2 to 20 ethylenically unsaturated alcohols with a carboxylic acid or sulfonic acid having 1 to 20 carbon atoms (for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, benzene) Vinyl carrate, allyl acetate, methyl allyl hexanoate, allyl laurate, allyl benzoate, vinyl sulfonate, allyl sulfonate, vinyl aryl sulfonate and many more.

The ethylenically unsaturated ether is not particularly limited, and examples thereof include an ether having an alkyl group having 1 to 20 carbon atoms and an ethylenically unsaturated group having 2 to 20 carbon atoms (for example, methyl vinyl ether or ethyl vinyl group). Ether, n-propyl vinyl ether, isopropyl vinyl ether, methyl allyl ether, ethyl allyl ether, etc.).

The ethylenically unsaturated amine is not particularly limited, and examples thereof include an alkyl group having at least one carbon number of 2 to 20 and a linear or branched alkyl group having a carbon number of 1 to 20 as required and/or Grade 1 to 3rd amine of an aromatic group having 6 to 20 carbon atoms (for example, vinyl dimethyl group) Amine, vinyl diethylamine, vinyl diphenylamine, allyldimethylamine, methallyldiethylamine, etc.).

The ethylenically unsaturated decane compound is not particularly limited, and examples thereof include an alkyl group having at least one carbon number of 2 to 20 and a linear or branched alkyl group having a carbon number of 1 to 20 as required. Examples of the decane compound of a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) include vinyltriethyl decane, methylvinyl dichlorodecane, and dimethylallyl chlorodecane. Vinyl trichloromethane and the like.

The aliphatic conjugated diene is not particularly limited, and examples thereof include 1,3-butadiene, 2-methyl-1,3-butadiene, and 2,3-dimethyl-1,3-butane. Alkene, 2-neopentyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,2-dichloro-1,3-butadiene, 2,3-dichloro- 1,3-butadiene, 2-bromo-1,3-butadiene, 2-cyano-1,3-butadiene, substituted linear conjugated pentadienes, linear and side chain conjugates An aliphatic conjugated diene having 4 to 20 carbon atoms such as hexadiene.

The molecular weight of the methacrylic resin contained in the methacrylic resin layers (B) and (D) is not particularly limited, and is, for example, 80,000 to 250,000, preferably 100,000 to 200,000. In addition, these values are all weight average molecular weights.

The methacrylic resin layers (B) and (D) may further contain a rubbery polymer to be described later, as needed, within a range that does not adversely affect the surface hardness. In other words, the methacrylic resin layers (B) and (D) may each contain a methacrylic resin as a resin component, and further comprise a methacrylate resin composition containing a rubbery polymer. Methyl propylene in this methacrylic resin composition Examples of the acid resin include the above methacrylic resins. The rubbery polymer is exemplified as a rubbery polymer exemplified as a description of a methacrylic resin composition (C) and (E) methacrylic resin composition constituting a rubber-like polymer to be described later.

a rubber polymer contained in the methacrylic resin composition constituting the methacrylic resin layers (B) and (D), and a methyl group constituting the rubber-containing polymer-containing methacrylic resin layers (C) and (E) The rubbery polymer contained in the acrylic resin composition may be the same or different.

In the methacrylic resin layers (B) and (D), the content of the rubbery polymer is 2% by weight or less, preferably 1%, based on 100% by weight of the total of the methacrylic resin and the rubbery polymer. The weight% or less is more preferably 0.5% by weight or less. When the content of the rubbery polymer is too large, the surface hardness of the laminate 1 and especially the surface hardness of the methacrylic resin layer (B) may become low.

The methacrylic resin layers (C) and (E) containing a rubbery polymer are each formed of a methacrylic resin composition. The methacrylic resin composition contains at least a methacrylic resin and a rubbery polymer.

Examples of the methacrylic resin include methacrylic resins contained in the methacrylic resin layers (B) and (D).

The methacrylic resin contained in the methacrylic resin composition of the methacrylic resin layer (C) containing the rubbery polymer is formed, and the methacrylic resin layer (E) which forms the rubbery polymer is formed. The methacrylic resin contained in the methacrylic resin composition may be the same or different.

Further, a methacrylic resin which forms the methacrylic resin layers (B) and (D), and a methacrylic resin composition which forms the methacrylic resin layers (C) and (E) containing the rubbery polymer The methacrylic resin contained may be all the same, may be partially the same, or may be completely different. From the viewpoint of narrowing the difference in refractive index, it is preferred that all of them are the same methacrylic resin.

The rubbery polymer (2, 3) contained in the methacrylic resin layer (C) containing the rubber-like polymer and the methacrylic resin composition of (E) is a polybutadiene rubber, for example. a diene rubber such as an acrylonitrile/butadiene copolymer rubber or a styrene/butadiene copolymer rubber; a homopolymer of an alkyl acrylate (for example, polybutyl acrylate, polypropyl acrylate, poly- Acrylic rubber such as 2-ethylhexyl acrylate or the like, a copolymer of an alkyl acrylate and another monomer; and an ethylene/propylene/non-conjugated diene rubber. A graft copolymer obtained by graft-polymerizing these rubber polymers with a monomer such as an alkyl methacrylate, an alkyl acrylate, a styrene, a substituted styrene, an acrylonitrile or a methacrylonitrile described later, or Suitable for use as a rubbery polymer. When the rubbery polymer is a graft copolymer, it is usually used in an amount of 5 to 80 parts by weight based on the rubber component and 20 to 95 parts by weight of the monomer for grafting. For the above-mentioned graft copolymers, for example, those described in JP-A-55-147514, JP-A-47-9740, and the like can be used.

Preferred examples of the graft copolymer are exemplified by The above rubber component is used as an inner layer, and a graft polymerized chain is used as a multilayer polymer of an outer layer. In this case, as the rubber component of the inner layer, the above-mentioned acrylic rubber can be preferably used. The acrylic rubber may be a homopolymer of an alkyl acrylate, or may be a copolymer of 50% by weight or more of an alkyl acrylate and 50% by weight or less of a monomer other than an alkyl acrylate.

The alkyl acrylate type may, for example, be an alkyl acrylate having a linear or branched alkyl group having 1 to 20 carbon atoms in the ester portion, and specifically, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate or the like. .

Examples of the single system other than the alkyl acrylate include an alkyl methacrylate having a linear or branched alkyl group having 1 to 20 carbon atoms in the ester portion, and an alkoxy group having 1 to 12 carbon atoms. The ester portion has an alkoxyalkyl acrylate having a linear or branched alkyl group having 1 to 20 carbon atoms, and an cyano cyanoalkyl group having a cyano group having an alkyl group having a linear or branched carbon number of 1 to 20 in the ester portion. An ester (for example, cyanoethyl acrylate or the like), a hydroxyalkyl acrylate having a acrylamide, a hydroxyl group, an alkyl group having a linear or branched carbon number of 1 to 20 in the ester portion, and a carbon having a hydroxyl group in the ester portion. a linear or branched alkyl group of 1 to 20 hydroxyalkyl methacrylate, acrylic acid, methacrylic acid, styrene, substituted styrene (for example, vinyl toluene, α-methyl styrene, etc.) A linear or branched alkyl group of 1 to 12, such as styrene, acrylonitrile or methacrylonitrile.

Further, a monomer other than the alkyl acrylate may be used in a (meth) acrylate (for example, allyl methacrylate) having an ethylenically unsaturated group having 2 to 20 carbon atoms in the ester portion. Crosslinkable monomer.

The glass transition point (Tg) of the acrylic rubber is preferably less than 25 °C.

The graft polymerized chain of the outer layer may, for example, be a homopolymer of an alkyl methacrylate having an alkyl group having a carbon number of 1 to 4, and an alkyl methacrylate having an alkyl group having a carbon number of 1 to 4 and 50% by weight. The above copolymer with 50% by weight or less of another monomer (a monomer other than an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms). Here, the above alkyl methacrylate is preferably methyl methacrylate.

The single system other than the alkyl methacrylate may, for example, be an alkyl group having 5 or more carbon atoms, preferably an alkyl methacrylate having a carbon number of 5 to 20, and having a carbon number of 1 to 20 in the ester portion. a straight or branched alkyl alkyl acrylate, styrene, substituted styrene (for example, vinyl acrylonitrile, α-methyl styrene, etc., a straight or branched alkyl group having a carbon number of 1 to 12; Ethylene, etc.), acrylonitrile, methacrylonitrile, and the like.

Further, the monomer other than the alkyl acrylate may be used in a (meth) acrylate (for example, allyl methacrylate) having an ethylenically unsaturated group having 2 to 20 carbon atoms in the ester portion. A unitary monomer.

The Tg of the additional layer polymer is preferably at least 25 °C.

Further, the same polymer as the outer layer polymer may be present at the inner side of the inner layer of the acrylic rubber.

The polymer having a multilayer structure as described above contains an acrylic rubber layer in an amount of preferably 20 to 60% by weight based on the total weight of the polymer.

For the polymer of the above-mentioned multilayer structure, for example, those described in Japanese Patent Publication No. Sho 55-27576, JP-A-H06-80739, and JP-A-49-23292.

In the rubber-containing methacrylic resin layers (C) and (E), the content of the rubbery polymer in the methacrylic resin composition is 100% by weight based on the total of the methacrylic resin and the rubbery polymer. It is usually 3 to 50% by weight, preferably 4 to 30% by weight, more preferably 5 to 20% by weight. If the proportion of the rubbery polymer is within the above range, the resin sheet 1 becomes less likely to be broken (that is, the impact resistance is further improved).

The rubbery polymer 3 contained in the methacrylic resin composition forming the methacrylic resin layer (E) containing the rubbery polymer, and the methacrylic resin layer (C) forming the rubbery polymer The rubbery polymer 2 contained in the acrylic resin composition may be the same or different. From the viewpoint of controlling warpage, it is preferred that any methacrylic resin composition has the same composition (that is, the same methacrylic resin and the same rubbery polymer are used).

In the polycarbonate resin layer (A), the methacrylic resin layers (B) and (D), and the methacrylic resin layers (C) and (E) containing the rubbery polymer, respectively, depending on the need Adding, for example, an antistatic agent (for example, sodium alkylsulfonate, sodium alkyl sulfate, stearic acid monoglyceride, polyether ester decylamine, etc.), an antioxidant (for example, hindered phenol, etc.), a flame retardant (for example) , phosphate esters, etc.), lubricants (eg, palmitic acid, stearyl alcohol, etc.), light stabilizers (eg, hindered amines, etc.), UV absorbers (for example, a benzotriazole-based ultraviolet absorber, a diphenylketone-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, a malonate-based ultraviolet absorber, an oxalic anilide-based ultraviolet absorber, An acetate-based ultraviolet absorber, etc.), a light diffusing agent, a dye, a pigment, a fluorescent whitening agent, and the like. These additives may be used in combination of two or more kinds as needed.

The method of blending the additive is, for example, a method in which a resin and an additive are mechanically mixed by a Henschel mixer, a tumbler, or the like, followed by melt-kneading. The melt kneading system can be carried out using a uniaxial or biaxial extruder, various kneaders, or the like.

The laminate 1 of the present invention can be laminated by co-extrusion molding by means of a laminate structure having the above (B) / (C) / (A) / (D) / (E) And properly manufactured. The co-extrusion molding, for example, when the methacrylic resin layers (B) and (D) have the same composition, and the methacrylic resin layers (C) and (E) containing the rubbery polymer have the same composition, It is carried out using a 3-base single or twin screw extruder. That is, each of the polycarbonate resin layer (A), the methacryl resin layers (B) and (D), and the rubber-like polymer-containing methacrylic resin layers (C) and (E) After the material is melt-kneaded, it is laminated by a feed block die, a multimanifold die, or the like, and the laminate 1 can be manufactured. The melted resin which is laminated and integrated may be cooled and solidified by using a cooling unit such as a roll unit. The laminate produced by the co-extrusion molding is preferable from the viewpoint of easy secondary formation as compared with the use of the adhesive or the adhesive to bond the produced laminate.

The laminate 1 is based on whether the methacrylic resin layers (B) and (D) are the same or not, and the methacrylic resin layers (C) and (E) containing the rubbery polymer are the same or not, and have a 3~ 5-layer structure of 5 types of layers.

Further, in the laminate 1 of the present invention, although the thickness of each layer is not particularly limited, the thickness of the layer B is, for example, 1 to 40%, preferably 2 to 35%, and the thickness of the layer C with respect to the thickness of the layer A. For example, 1 to 40%, preferably 2 to 35%, the thickness of the layer D is, for example, 1 to 40%, preferably 2 to 35%, and the thickness of the layer E is, for example, 1 to 40%, preferably 2 to 2. 35%.

Further, the total thickness of the B layer and the C layer is, for example, 2 to 80%, preferably 4 to 70%, with respect to the thickness of the A layer, and the total thickness of the D layer and the E layer is relative to the thickness of the A layer. For example, 2 to 80%, preferably 4 to 70%.

Further, the total of the thicknesses of the B layer and the C layer, and the ratio of the total thickness of the D layer to the E layer (B+C: D+E) is, for example, 1:0.5 to 1:2.

Hereinafter, an embodiment of the method for producing the laminated board 1 of the present invention will be described in detail with reference to Fig. 2, taking as an example a case where the production is performed by co-extrusion molding. In addition, this example is a manufacturing method of the laminated board 1 which has the 5-layer structure which consists of the methacryl-resin layer (B) and (D) same, and the rubber-like polymer methacrylic resin Layers (C) and (E) are the same three types of layers.

As shown in Fig. 2, the polycarbonate resin layer (A), the methacrylic resin layers (B) and (D), and the rubber-containing polymer are used. Each of the methacrylic resin layers (C) and (E) is heated and melted by individual extruders 11, 12, and 13 and supplied to the feed module 14 to melt the respective materials. After laminating and laminating, it is extruded from the die 15.

Further, in the case where the methacrylic resin layers (B) and (D) are different or the rubber-containing polymer-containing methacrylic resin layers (C) and (E) are different, they are provided separately. In the corresponding extruder, the material is supplied to the feed module 14 by each extruder, and the molten resin is extruded from the die 15 to produce the laminate 1 having a 5-layer structure.

Then, the sheet-like or film-like molten resin extruded from the die 15 is interposed between the first cooling roll 16 and the second cooling roll 17 which are disposed to face each other in the horizontal direction. The first cooling roller 16 and the second cooling roller 17 are configured such that at least one of them is connected to a rotation driving means such as a motor, and the two rollers rotate at a specific peripheral speed. Among the two rolls, the second cooling roll 17 is a winding roll (or a transfer roll), and the sheet-like or film-like laminate 1 which is held between the rolls is wound up (that is, in the layer) The splicing plate 1 is directly conveyed in contact with at least a part of the outer circumferential surface of the second cooling roll 17).

The first cooling roll 16 and the second cooling roll 17 may be formed by a metal roll or a metal elastic roll, or may be formed by combining a metal roll and a metal elastic roll.

In the case of obtaining the laminate 1 having a low hysteresis value, it is preferable to form the first cooling roller 16 by a combination of a metal roller and a metal elastic roller. And the second cooling roller 17 . That is, when the molten resin is held between the metal roll and the metal elastic roll, the metal elastic roll is elastically deformed along the outer peripheral surface of the metal roll by the molten resin, and the metal elastic roll and the metal roll pass through the molten resin. And can be contacted with a specific contact length. In this way, the metal roll and the metal elastic roll are pressed together in a surface contact with the molten resin, and the molten resin is held between the rolls, and the film can be formed by uniformly pressing into a planar shape. As a result, the laminate 1 having a low deformation at the time of film formation and having a low hysteresis value can be obtained.

In the case of combining the metal roll and the metal elastic roll, it is preferable to use the first cooling roll 16 as a metal elastic roll and the second metal roll 17 as a metal roll. Thereby, the hysteresis value of the obtained laminate 1 can be further reduced.

The molten resin sandwiched between the first cooling roll 16 and the second cooling roll 17 is wound in the order of the second cooling roll 17 and the third cooling roll 18. Specifically, the molten resin wound around the second cooling roll 17 is wound around the third cooling roll 18 between the second cooling roll 17 and the third cooling roll 18 . In other words, the molten resin is directly conveyed in contact with at least a part of the outer peripheral surface of the second cooling roll 17, and then held between the second cooling roll 17 and the third cooling roll 18, and then in contact with the first 3 At least a part of the outer peripheral surface of the cooling roll 18 is directly conveyed. Thereby, since the molten resin can be gradually cooled, the hysteresis value of the obtained laminate 1 can be reduced. In addition, the second cooling roll 17 and the third cooling roll 18 may be opened at a specific interval, and the molten resin may be sandwiched between the rolls without a specific interval.

The third cooling roll 18 is not particularly limited, and a normal metal roll used in conventional extrusion molding can be used. Specific examples include a drilled roll, a spiral roll, and the like. It is preferable that the surface state of the third cooling roll 18 is a mirror surface. In addition, after the third cooling roll 18, a plurality of cooling rolls may be provided one by one according to the fourth cooling roll and the fifth cooling roll, and the sheet may be wound (or conveyed) in the form of a sheet or a film of the third cooling roll 18. The laminate 1 is sequentially wound (or carried) to the next cooling roll.

The layered sheet 1 of the present invention is obtained by winding (or transporting) the third cooling roll 18 and pulling the slowly cooled laminate by a pulling roll (not shown). The thickness of the laminate 1 as a whole is preferably 0.2 to 3 mm, more preferably 0.3 to 2 mm, still more preferably 0.4 to 1.5 mm. If the laminate 1 has a thickness in the above range, it is easier to form and the productivity is further improved. The thickness of the entire laminate 1 can be arbitrarily adjusted by adjusting the thickness of the entire laminate in a molten state, the interval of the rolls or belts provided in the cooling unit, the peripheral speed, and the like.

In the laminate 1 of the present invention, the thickness of the polycarbonate resin layer (A) is preferably from 20 to 2,900 μm. The thickness of the methacrylic resin layers (B) and (D) is 20 to 100 μm, preferably 30 to 90 μm, and more preferably 40 to 90 μm. The thickness of the methacrylic resin layers (C) and (E) containing the rubbery polymer is 20 to 100 μm, preferably 30 to 80 μm, more preferably 30 to 70 μm. In particular, the thicker the thickness of the methacrylic resin layer (B), the higher the surface hardness, and the thicker the thickness of the methacrylic resin layer (E) containing the rubbery polymer, the higher the impact resistance.

In the laminate 1 of the present invention, the total thickness of the methacryl resin layer (B) and the thickness of the methacrylic resin layer (C) containing the rubbery polymer, and the thickness of the methacrylic resin layer (D) The total thickness of the methacrylic resin layer (E) containing the rubbery polymer is 50 to 200 μm, preferably 60 to 150 μm, more preferably 70 to 120 μm.

Further, the total thickness of the methacrylic resin layer (B) and the thickness of the methacrylic resin layer (C) containing the rubbery polymer, the thickness of the methacrylic resin layer (D), and the rubbery polymer-containing polymer The difference in the total thickness of the methacrylic resin layer (E) is -50 to 50 μm, preferably -40 to 40 μm, more preferably -30 to 30 μm. In addition, the difference in thickness can be obtained by [the total thickness of the methacrylic resin layer (B) and the thickness of the methacrylic resin layer (C) containing the rubbery polymer] - [methacrylic resin layer ( Calculated by the total thickness of D) and the thickness of the methacrylic resin layer (E) containing the rubbery polymer. Alternatively, it may be a combination of [the thickness of the methacrylic resin layer (D) and the thickness of the methacrylic resin layer (E) containing the rubbery polymer] - [the thickness of the methacrylic resin layer (B) And the total thickness of the methacrylic resin layer (C) containing the rubbery polymer] is calculated.

The thickness of the polycarbonate resin layer (A), the methacrylic resin layers (B) and (D), and the methacrylic resin layers (C) and (E) containing the rubbery polymer can be adjusted by respectively The amount of supply from each extruder is arbitrarily adjusted.

Methacrylic resin layer (B) and rubbery polymer The methacrylic resin layer (C) is preferably a layer having a certain thickness in order to impart a surface hardness to the laminate 1. The methacrylic resin layer (D) and the rubber-like polymer-containing methacrylic resin layer (E) are provided so as to impart an effect of suppressing warpage while imparting impact resistance to the laminate 1 to be close to methacrylic acid. The thickness of the resin layer (B) and the methacrylic resin layer (C) containing the rubbery polymer is preferred. That is, as for the thickness, it is preferable to make the thickness of the methacrylic resin layer (B) and the thickness of the methacrylic resin layer (C) containing the rubbery polymer as large as possible, and the methacrylic resin layer (D). The thickness of the methacrylic resin layer (E) containing the rubber-like polymer is close to the total, and the larger the difference between the two, the higher the warpage tends to be.

The laminate 1 of the present invention can be suitably used for appearance applications, kanban applications, lighting applications, front panel applications, and the like, and is particularly suitable for use as a front panel of a display. When the laminate 1 of the present invention is used as the front panel of the display, the methacrylic resin layer (B) is on the side of the viewer, and the methacrylic resin layer (E) containing the rubbery polymer is used as the display side. It is preferable from the viewpoint of the surface hardness and impact resistance of the laminate 1. Further, the laminate 1 of the present invention is not limited to the applications exemplified, and can be suitably used in an area where the appearance is emphasized. Further, in this case, it is preferable that the methacryl resin layer (B) is on the side of the viewer.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples and comparative examples. The invention is not limited to the embodiments described herein.

The extrusion apparatus used in the examples and the comparative examples is the apparatus shown in Fig. 2, and the configuration is as follows.

Extruder 11: an extruder having a screw diameter of 65 mm, a single shaft, and a vent hole (manufactured by Toshiba Machine Co., Ltd.).

Extruder 12: an extruder having a screw diameter of 45 mm, a single shaft, and a vent hole (manufactured by Hitachi Shipbuilding Co., Ltd.).

Extruder 13: an extruder having a screw diameter of 45 mm, a single shaft, and a vent hole (manufactured by Hitachi Shipbuilding Co., Ltd.).

Feed module 14: Three types of 5-layer distribution type feed modules (Hitachi Shipbuilding Co., Ltd.).

Die 15: T die having a lip width of 1400 mm and a lip gap of 1 mm (manufactured by Hitachi Shipbuilding Co., Ltd.).

Cooling rolls 16, 17, 18: Horizontal rolls, 1400 mm long, 300 mm diameter cooling rolls.

When the cooling roll is more specifically described, a metal elastic roller is used as the first cooling roll 16. In the metal elastic roller, a metal film is disposed so as to cover the outer peripheral surface of the shaft roller, and the fluid is sealed between the shaft roller and the metal film.

The shaft roller of the metal elastic roller of the first cooling roll 16 is made of stainless steel. A metal film is a mirror metal sleeve made of stainless steel having a thickness of 2 mm. Further, by using oil as the fluid and controlling the temperature of the oil, temperature control of the metal elastic roller can be performed. More specifically, it is controlled by the ON-OFF of the temperature regulator. The oil is heated and cooled to control the temperature and circulate between the shaft roll and the metal film.

The second cooling roll 17 and the third cooling roll 18 are made of a highly rigid metal roll. The surface condition of this metal roll is a mirror-shaped stainless steel spiral roll.

The resins used in the examples and comparative examples were the following three types.

Resin 1: A polycarbonate resin "CALIBRE 301-10" manufactured by Sumitomo Dow Co., Ltd. having a heat distortion temperature (Th) of 140 ° C was used.

Resin 2: 0.5 parts by weight of benzotriene mixed with 100 parts by weight of polymethyl methacrylate (PMMA) resin "SUMIPEX MH" manufactured by Sumitomo Chemical Co., Ltd. at a heat distortion temperature (Th) of 100 °C. A composition of an azole-based ultraviolet absorber (LA-31 manufactured by ADEKA Co., Ltd.).

Resin 3: A mixture of 86% by weight of a copolymer of methyl methacrylate/methyl acrylate = 98/2 (weight ratio) and 14% by weight of a rubbery polymer obtained in Synthesis Example 1 below.

(Synthesis Example 1) (Manufacture of rubbery polymer)

Into a glass reaction vessel having an internal volume of 5 L, 1,700 g of ion-exchanged water, 0.7 g of sodium carbonate, and 0.3 g of sodium persulfate were charged, and the mixture was stirred under a nitrogen stream. 4.44 g of "Pelex OT-P" manufactured by Kao Corporation, 150 g of ion-exchanged water, and 150 g of methyl methacrylate were placed therein. And 0.3 g of allyl methacrylate, and the temperature was raised to 75 ° C, and the mixture was stirred for 150 minutes.

Next, a mixture of 689 g of butyl acrylate, 162 g of styrene, and 17 g of allyl methacrylate, and 0.85 g of sodium persulfate, 7.4 g of a dispersant (Pelex OT-P), and 50 g of ion-exchanged water were added for 90 minutes. Further polymerize it for 90 minutes.

Then, a mixture of 326 g of methyl methacrylate and 14 g of ethyl acrylate and 30 g of ion-exchanged water in which 0.34 g of sodium persulfate was dissolved was further added for 30 minutes. After the end of the addition, the polymerization was completed by further maintaining for 60 minutes.

The obtained latex was placed in a 0.5% by weight aqueous solution of aluminum chloride to coagulate the rubbery polymer. This was washed 5 times with warm water and dried to obtain a rubbery polymer.

(Examples 1 to 4 and Comparative Examples 1 to 5) (production of laminates)

First, as shown in Fig. 2, the extruders 11, 12, 13, the feed module 14, the die 15, and the cooling rolls 16, 17, 18 are disposed. Then, the resin shown in Table 1 was melt-kneaded by the extruder 11 as a resin for forming a polycarbonate resin layer (A) (hereinafter referred to as a resin layer A), and the resin shown in Table 1 was melt-kneaded by the extruder 12 as a resin. A resin in which a methacrylic resin layer (B) (hereinafter referred to as a resin layer B) and a methacryl resin layer (D) (hereinafter referred to as a resin layer D) are formed, and the resin shown in Table 1 is melt-kneaded by an extruder 13 As a methacrylic resin layer forming a rubber-like polymer (C) (hereinafter referred to as resin layer C) and a resin containing a rubber-like polymer methacrylic resin layer (E) (hereinafter referred to as resin layer E) are supplied to the feed module 14 respectively.

Next, it is extruded from the die 15 to laminate a resin layer C formed from the extruder 13 via the feed module 14 on one side of the resin layer A formed from the extruder 11 via the feed module 14. On the surface of the resin layer C, a resin layer B formed from the extruder 12 via the feed module 14 is laminated, and then, on the other side of the resin layer A, a film is fed from the extruder 12 via the feed die. The resin layer D formed in the group 14 is laminated on the surface of the resin layer D with a film-like molten resin of the resin layer E formed from the extruder 13 via the feed module 14.

Then, the film-like molten resin extruded from the die 15 is sandwiched between the first cooling roll 16 and the second cooling roll 17 disposed opposite to each other, and is wound (or conveyed) to the third cooling roll 18. After molding, the resin layer C and the resin layer B are sequentially laminated on one surface of the resin layer A, and the resin layer D and the resin layer E are sequentially laminated on the other surface of the resin layer A to obtain A laminate 1 of a 5-layer structure having a thickness shown in Table 1 below.

Further, the surface temperature of the first cooling roll 16 was 120 ° C, the surface temperature of the second cooling roll 17 was 125 ° C, and the surface temperature of the third cooling roll 18 was 130 ° C. These temperatures are values obtained by actually measuring the surface temperatures of the respective chill rolls.

With respect to each of the obtained laminates (laminates of Examples 1 to 4 and Comparative Examples 1 to 5), the surface hardness was evaluated by the following method. Degree (pencil hardness), "warpage" and "impact resistance" (falling strength). The results are shown in Table 2 below.

Further, in the laminate of Comparative Example 5, the polycarbonate resin 1 was supplied from the extruder 11 to the feed module 14, and a polycarbonate resin layer A was formed in the same manner as described above, from the extruder 12 The methacrylic resin 2 is supplied to the feed module 14, a methacrylic resin layer C is formed on one side of the resin layer A, and a methacrylic resin layer D is formed on the other side of the resin layer A, and then, from the extruder 13 The methacrylate resin 3 containing the rubbery polymer is supplied to the feed module 14, and a methacrylic resin layer B containing a rubbery polymer is formed on the surface of the methacrylic resin layer C, and the methacrylic resin is used. The surface of the layer D forms a methacrylic resin layer E containing a rubbery polymer.

"surface hardness" (pencil hardness)

The pencil hardness was measured in accordance with JIS K 5400.

Warp

The obtained laminate was cut into a size of 100 mm (pressing flow direction) × 55 mm (extrusion width direction) to obtain a test piece. The amount (mm) (initial) of the four corners of the obtained test piece was measured. The test piece was exposed to an environment of 85% humidity at a temperature of 85 ° C for 72 hours, and then allowed to stand at a temperature of 25 ° C in an environment of 55% humidity for 4 hours. Thereafter, the surface of the resin layer (B) was used as the upper surface, and the amount (mm) of the four-angle floating (after exposure) was measured. + indicates that the surface of the resin layer (B) is concave, - system It indicates that the surface of the resin layer (B) is convex.

Impact resistance (falling strength)

The obtained laminate was cut into a size of 60 × 60 mm to obtain a test piece. The surface of the resin layer (B) of the test piece was set to the upper side (ball drop side), and the metal ball (63.8 g, diameter: 20 mm) was dropped to the test piece while the height of the surface of the resin layer (B) was increased by 5 cm. The height at which the test piece was cracked was evaluated as the falling ball strength. It is shown that the higher the height at which the test piece is cracked, the more excellent the impact resistance.

As shown in Table 2, the laminates obtained in Examples 1 to 4 were less likely to warp in a high-humidity environment, and did not cause cracks even when falling from a height of 80 cm or more, and the impact resistance was excellent, and the laminates were excellent. The surface also has an excellent surface hardness of 4H pencil hardness.

On the other hand, in Comparative Examples 1 to 5, the pencil hardness was 3H or less, and the surface hardness was low. Further, in Comparative Example 3, the warpage of the laminate was severe, and in Comparative Example 4, the impact resistance was high. Significantly reduced sex. Therefore, it is understood that the laminates obtained in Comparative Examples 1 to 5 are at least one of poor in surface hardness, warpage in high-humidity environment, and impact resistance, and cannot be obtained to satisfy surface hardness and warpage. Impact resistance Laminates.

[Industrial availability]

The laminate of the present invention can be suitably used in the fields of appearance use, kanban use, lighting use, display front panel use, and the like. In particular, the laminate of the present invention has excellent surface hardness, prevention of warpage in a high-humidity environment, and excellent impact resistance as described above, and therefore can be suitably used as a smart phone or a tablet. The front panel of a display such as a television or monitor.

In addition, the present application claims priority on the basis of Japanese Patent Application No. 2012-279655, filed on Dec.

1‧‧‧Laminated boards

2, 3‧‧‧ rubbery polymer

A‧‧‧ polycarbonate resin layer

B‧‧‧methacrylic resin layer

C‧‧‧methacrylic resin layer containing rubbery polymer

D‧‧‧methacrylic resin layer

E‧‧‧methacrylic resin layer containing rubbery polymer

One side of the I‧‧‧ polycarbonate resin layer

II‧‧‧The other side of the polycarbonate resin layer

Claims (7)

A laminate characterized by having one side (I) of a polycarbonate resin layer (A) from which a methacrylic resin layer (C) containing a rubbery polymer is sequentially laminated. And the methacrylic resin layer (B), and the other surface (II) of the polycarbonate resin layer (A), the methacryl resin layer (D) and the rubber-containing layer are sequentially laminated from the surface (II) The structure of the polymer methacrylic resin layer (E). The laminate according to claim 1, wherein the thickness of the methacrylic resin layer (B) and the thickness of the methacrylic resin layer (D) are each 20 to 100 μm. The laminate according to claim 1 or 2, wherein the thickness of the rubber-like polymer-containing methacrylic resin layer (C) and the thickness of the rubber-containing polymer-containing methacrylic resin layer (E) are Each is 20 to 100 μm. The laminate according to any one of claims 1 to 3, wherein a total thickness of the methacrylic resin layer (B) and a thickness of the rubber-containing polymer-containing methacrylic resin layer (C) is 50. ~200μm. The laminate according to any one of claims 1 to 4, wherein the thickness of the methacrylic resin layer (D) and the thickness of the rubber-containing polymer-containing methacrylic resin layer (E) are 50 in total. ~200μm. The laminate according to any one of claims 1 to 5, wherein a total thickness of the methacrylic resin layer (B) and a thickness of the rubber-containing polymer-containing methacrylic resin layer (C) are The thickness of the aforementioned methacrylic resin layer (D) and the aforementioned methyl propylene containing rubbery polymer The difference in the total thickness of the olefin resin layer (E) is -50 to 50 μm. A method for producing a laminate according to any one of claims 1 to 6, which comprises the step of forming the polycarbonate resin layer (A) by a co-extrusion molding. The acryl-based resin layers (B) and (D) and the rubber-like polymer-containing methacrylic resin layers (C) and (E) are laminated.