WO2016009831A1 - Laminate - Google Patents

Abstract

　Provided is a laminate having, on at least one surface of a polycarbonate resin layer (B), an acrylic resin layer (A) containing an acrylic resin (A1) and a copolymer (A2) having aromatic vinyl monomer units, (meth)acrylic acid ester monomer units, and unsaturated dicarboxylic acid anhydride monomer units, the mixture ratio of mass thereof being (A1)/(A2) = 80-20/20-80, wherein the laminate is intended for use as a substrate material or protective material, and has excellent transparency, impact resistance, surface hardness, and shape stability in high temperature or high humidity environments.

Description

Laminated body

The present invention relates to a laminate, and more specifically, is used as a substrate material or a protective material, and can be suitably used as a cover material for a surface protective panel of an image display device, a mobile phone, a smartphone, a tablet device, or the like. It relates to a laminate.

Conventionally, glass has been mainly used as a cover material for image display devices. However, since glass is easily broken by impact and is heavy, substitution with a resin material has been studied. Here, the resin material is mainly required to have impact resistance, surface hardness, and shape stability in a high temperature and high humidity environment.

Polycarbonate resin plates are transparent and have excellent impact resistance and heat resistance, so they are used for soundproofing partitions, carports, signboards, glazing materials, lighting equipment, etc. There is a drawback that it is easy to stick, and its use is limited.

For example, Patent Document 1 discloses a resin laminate in which a hard coat treatment is applied to a laminate obtained by coextruding a polycarbonate resin and an acrylic resin in order to improve this defect.

Patent Document 2 discloses a resin laminate in which a methyl methacrylate-styrene copolymer resin (MS resin) is laminated on a polycarbonate resin as a method for suppressing warpage.

As a method for suppressing warpage, Patent Document 3 discloses a resin laminate in which a glass transition temperature difference and a water absorption difference are defined for each layer in which a polycarbonate resin is laminated.

JP 2006-103169 A JP 2010-167659 A International Publication No. 2014/061817

In Patent Document 1, although the surface hardness is improved to some extent by adopting a two-layer structure, in applications where environmental changes such as high temperature and high humidity occur, heat resistance represented by mainly glass transition temperatures of polycarbonate resin and acrylic resin There is a problem that a dimensional change difference occurs due to a difference in water absorption characteristics and the like, and as a result, a large warp tends to occur.
In Patent Document 2, the MS resin has a lower water absorption than the acrylic resin, so that the effect of improving the warp is seen. However, as described in the evaluation in the examples, the temperature of the environmental test is 40 ° C. and the humidity is 90%. RH is still insufficient as a condition for high temperature and high humidity. Further, the MS resin having a reduced water absorption rate by increasing the styrene content of the copolymer component (40% by mass or more) is likely to have a low heat resistance and a low compatibility with the acrylic resin.
In Patent Document 3, the effect of improving the warp is seen, but as described in the disclosure and examples of the present invention, the means for achieving it is substantially fine stretching by the speed ratio of the roll when cooling the laminate. Is an essential manufacturing method. When the laminate is stretched slightly during the cooling process, there is a problem that heat shrinkability is imparted. In addition, the modified polycarbonate resin specifically used is a special raw material and has a problem in economy.

Therefore, the object of the present invention is to use a general-purpose material as a main raw material, which is excellent in economic efficiency, used for substrate materials and protective materials, transparency, impact resistance, surface hardness, and shape stability in high temperature and high humidity environments. It is providing the laminated body which is excellent in property.

As a result of intensive studies, the present inventors have made a laminate having a specific acrylic resin layer on at least one side of a polycarbonate resin layer, so that the impact resistance, surface hardness, high temperature and high humidity can be obtained. It has been found that the shape stability is excellent, and the present invention has been completed.
That is, according to the present invention, the following (1) to (20) are provided.
(1) A laminate having an acrylic resin layer (A) on at least one surface of a polycarbonate resin layer (B), wherein the acrylic resin layer (A) comprises an acrylic resin (A1) and an aromatic vinyl Copolymer (A2) having a monomer unit, a (meth) acrylic acid ester monomer unit and an unsaturated dicarboxylic anhydride monomer unit, and the mixing mass ratio thereof is (A1) / (A2 ) = 80-20 / 20-80.
(2) The acrylic resin (A1) has a methyl methacrylate monomer unit as a main component, and has a rr structure out of mm, mr and rr of triad fractions determined by nuclear magnetic resonance measurement ( ¹ H-NMR). The laminate according to (1) above, which has the highest molar ratio.
(3) The constituent unit of the copolymer (A2) is 45 to 85% by mass of an aromatic vinyl monomer unit, 4 to 45% by mass of a (meth) acrylic acid ester monomer unit, and an unsaturated dicarboxylic acid anhydride unit amount The laminate according to (1) or (2) above, wherein the body unit is 8 to 20% by mass.
(4) The mixing mass ratio of the acrylic resin (A1) and the copolymer (A2) is (A1) / (A2) = 80 to 55/20 to 45, The laminate according to any one of 3).
(5) A mixing mass ratio of the acrylic resin (A1) and the copolymer (A2) is (A1) / (A2) = 50 to 20/50 to 80, The laminate according to any one of 3).
(6) The glass transition temperature of the acrylic resin layer (A) measured at a heating rate of 10 ° C./min using a differential scanning calorimeter is 100 to 140 ° C., and the polycarbonate resin layer (B) 6. The laminate according to any one of (1) to (5) above, wherein the absolute value of the difference from the glass transition temperature is 20 ° C. or less.
(7) Acrylic resin layer (A) measured at a heating rate of 10 ° C./min using a differential scanning calorimeter, glass transition temperature of 115 to 140 ° C., and glass of polycarbonate resin layer (B) 6. The laminate according to any one of (1) to (5) above, wherein the absolute value of the difference from the transition temperature is 10 ° C. or less.
(8) The above-mentioned (1) to (7), wherein the polycarbonate-based resin layer (B) contains a polycarbonate-based resin (B1) and at least one modifier (B2) selected from the following: The laminated body of any one of Claims.
Modifier (B2)
(B2-1): As the carboxylic acid monomer (A) unit, 80 mol% or more of aromatic dicarboxylic acid and as the glycol monomer (B) unit, 40 mol% or more of 1,4-cyclohexanedimethanol are contained. Polyester resin comprising structural units (B2-2): acrylic copolymer (9) comprising 5 to 80% by mass of aromatic (meth) acrylate monomer units and 95 to 20% by mass of methyl methacrylate monomer units 9. The laminate according to any one of (1) to (8) above, wherein a phosphite antioxidant is mixed in the acrylic resin layer (A).
(10) The laminate as described in any one of (1) to (9) above, wherein a carbodiimide compound is mixed in the polycarbonate resin layer (B).
(11) The laminate as described in any one of (1) to (10) above, wherein the acrylic resin layer (A) has a thickness of 0.01 to 0.25 mm.
(12) When the total thickness of the acrylic resin layer (A) and the polycarbonate resin layer (B) is (T), the thickness ratio of the acrylic resin layer (A) 1 layer ((A) / (T)) The laminate according to any one of the above (1) to (11), wherein is from 0.01 to 0.35.
(13) The laminate as described in any one of (1) to (12) above, which is coextruded.
(14) The laminate as described in any one of (1) to (13) above, wherein the hard coat layer (C) is laminated on at least one surface of the laminate.
(15) The laminate according to (14), wherein the surface of the hard coat layer (C) has a pencil hardness of 4H or more.
(16) The laminate as described in (14) or (15) above, wherein the hard coat layer (C) comprises an organic / inorganic hybrid curable resin composition.
(17) The above (1) to (16), wherein at least one of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment is performed on one side or both sides The laminated body of any one of (1).
(18) A substrate material using the laminate according to any one of (1) to (17) above.
(19) A protective material using the laminate according to any one of (1) to (17) above.
(20) An image display device comprising the laminate according to any one of (1) to (17).

According to the present invention, it is possible to provide a laminate which is excellent in economy by using a general-purpose material as a main raw material, and excellent in transparency, impact resistance, surface hardness, and shape stability in a high temperature and high humidity environment. The laminate can be used as various substrate materials and protective materials. Specifically, portable display devices (mobile phone terminals, smartphones, portable electronic playground equipment, personal digital assistants, tablet devices, mobile PCs, etc.) and stationary display devices (LCD TVs, LCD monitors, desktop PCs, car navigation systems, It can be suitably used for automobile instruments and the like.

The present invention will be described in detail below.
The present invention is a laminate having an acrylic resin layer (A) on at least one side of a polycarbonate resin layer (B).

<Acrylic resin layer (A)>
The acrylic resin layer (A) includes an acrylic resin (A1), an aromatic vinyl monomer unit, a (meth) acrylic acid ester monomer unit, and an unsaturated dicarboxylic anhydride monomer unit. And a polymer (A2).
The acrylic resin layer (A) shares a function of expressing the surface hardness, heat resistance, etc., among the functions of the laminate. Therefore, the acrylic resin layer (A) may be laminated on both surfaces of the polycarbonate resin layer (B) described later, but it is necessary that the acrylic resin layer (A) be laminated on at least one surface. In the case of a display panel or the like, the acrylic resin layer (A) is preferably laminated on the outer surface side.

<Acrylic resin (A1)>
The acrylic resin (A1) is a resin containing a (co) polymer obtained by polymerizing a (meth) acrylic acid ester monomer unit as a main component and a derivative thereof as a main component. In the present specification, the (meth) acrylic acid ester monomer unit means an acrylic acid ester monomer unit or a methacrylic acid ester monomer unit. The monomer unit comprised here is methyl methacrylate, methacrylic acid, acrylic acid, benzyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate. 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2 -Ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate , Dicyclopentenyloxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, acrylic (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, maleic acid 2 -(Meth) acryloyloxyethyl, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate Examples thereof include dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate. These can be used alone or in combination of two or more. Examples of other monomer units that can be polymerized with these acrylic monomer units include olefin monomer units and vinyl monomer units.

Here, in the present invention, because of the compatibility with the copolymer (A2) and industrial availability, the homopolymer of methyl methacrylate or the copolymer of methyl methacrylate and methyl acrylate or ethyl acrylate. Coalescence can be suitably used. The stereoregularity is not particularly limited, but the three-dimensional structure of the (meth) acrylic acid ester monomer unit is preferably a syndiotactic structure because the glass transition temperature becomes higher and the heat resistance is improved. Specifically, among the triad fractions of mm, mr, and rr, those having the highest molar ratio of the rr structure can be suitably used. The triad fraction can be measured by a known method using a nuclear magnetic resonance measuring apparatus ( ¹ H-NMR).

Commercially available products may be used as the acrylic resin (A1) used in the present invention. Specific examples include trade names “Acrypet” manufactured by Mitsubishi Rayon Co., Ltd., and products manufactured by Sumitomo Chemical Co., Ltd. Examples include the name “SUMIPEX” and the product name “PARAPET” manufactured by Kuraray Co., Ltd.

<Copolymer (A2)>
The copolymer (A2) is a copolymer having an aromatic vinyl monomer unit, a (meth) acrylic acid ester monomer unit, and an unsaturated dicarboxylic anhydride monomer unit.

Here, as the aromatic vinyl monomer unit, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, α-methyl Examples include units derived from styrene monomers such as styrene and α-methyl-p-methylstyrene. These aromatic vinyl monomer units can be used alone or in combination of two or more. In the present invention, styrene units and α-methylstyrene units are preferred. Styrene units are preferred because they are easily available industrially and are economical, and α-methylstyrene units are preferred because they can improve the glass transition temperature.

(Meth) acrylic acid ester monomer units include methyl methacrylate monomers such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, dicyclopentanyl methacrylate, and isobornyl methacrylate. And units derived from an acrylate monomer such as methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, and decyl acrylate. These (meth) acrylic acid ester monomer units can be used alone or in combination of two or more. Here, in this invention, a methyl methacrylate monomer unit can be used suitably from compatibility with an acrylic resin (A1), an external appearance, etc.

Examples of the unsaturated dicarboxylic acid anhydride monomer unit include units derived from respective anhydride monomers such as maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, and aconitic acid anhydride. These unsaturated dicarboxylic acid anhydride monomer units can be used alone or in combination of two or more. Here, in the present invention, a maleic anhydride monomer unit can be preferably used in view of compatibility with the acrylic resin (A1) and transparency.

The constituent unit of the copolymer (A2) used in the present invention is preferably 45 to 85% by mass of an aromatic vinyl monomer unit, 4 to 45% by mass of a (meth) acrylic acid ester monomer unit, and an unsaturated dicarboxylic acid. Anhydride monomer unit is 8 to 20% by weight, more preferably aromatic vinyl monomer unit 55 to 85% by weight, (meth) acrylic acid ester monomer unit 5 to 30% by weight, unsaturated dicarboxylic acid The range of anhydride is 10 to 18% by mass.
Here, the structural unit of the copolymer (A2) can be qualitatively and quantitatively analyzed by a known method, for example, a nuclear magnetic resonance (NMR) measuring device or other instrumental analyzer.

Here, if the aromatic vinyl monomer unit is preferably 45% by mass or more, more preferably 55% by mass or more, the thermal stability is improved, and a good appearance is obtained when mixed with the acrylic resin (A1). Is preferable, and water absorption can be reduced. The (meth) acrylic acid ester monomer unit is preferably 4% by mass or more, and more preferably 5% by mass or more, since the compatibility with the acrylic resin (A1) is improved and the transparency is improved. If the unsaturated dicarboxylic acid anhydride monomer unit is preferably 8% by mass or more, more preferably 10% by mass or more, compatibility with the acrylic resin (A1) is improved, and transparency and heat resistance are improved. Therefore, it is preferable.

On the other hand, if the aromatic vinyl monomer unit is preferably 85% by mass or less, it is preferable because heat resistance can be improved and water absorption can be reduced while maintaining mixing with the acrylic resin (A1). If the (meth) acrylic acid ester monomer unit is preferably 45% by mass or less, more preferably 30% by mass or less, water absorption can be suppressed while ensuring compatibility with the acrylic resin (A1). preferable. Further, if the unsaturated dicarboxylic acid anhydride monomer unit is preferably 20% by mass or less, more preferably 18% by mass or less, the thermal stability of the acrylic resin (A1) is ensured while ensuring compatibility with the acrylic resin (A1). It is preferable because improvement and water absorption can be suppressed.

The copolymer (A2) used in the present invention is a copolymerizable monomer other than an aromatic vinyl monomer unit, a (meth) acrylic acid ester monomer unit, and an unsaturated dicarboxylic anhydride monomer unit. The copolymer unit may be contained in the copolymer within a range not inhibiting the effect of the present invention, and the content of the copolymerizable monomer unit is preferably 100% by mass of the copolymer (A2). 5% by mass or less. The copolymerizable units include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, N-methylmaleimide, N-ethylmaleimide, and N-butylmaleimide. Units derived from monomers such as N-alkylmaleimide monomers such as N-cyclohexylmaleimide, N-arylmaleimide monomers such as N-phenylmaleimide, N-methylphenylmaleimide and N-chlorophenylmaleimide Is mentioned. These copolymerizable monomer units can be used alone or in combination of two or more.

The copolymer (A2) used in the present invention preferably has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 100,000 to 200,000. Here, it is preferable that the weight average molecular weight (Mw) is in this range because the acrylic resin layer (A) obtained by mixing with the acrylic resin (A1) is excellent in moldability and appearance. From this viewpoint, a more preferable range of weight average molecular weight (Mw) is 110,000 to 180,000.

The method for producing the copolymer (A2) used in the present invention is not particularly limited and can be produced by a known polymerization method. For example, solution polymerization, bulk polymerization, and the like can be applied, and batch, semi-batch, and continuous methods can be appropriately employed as the polymerization process. In the present invention, a batch polymerization process can be suitably used in solution polymerization because there are few by-products and molecular weight adjustment and transparency can be easily controlled.

The copolymer (A2) used in the present invention may be a commercially available product. Specific examples include trade names “Regisphi® R-100”, “Regisphi® R-200” and “Regisphi® R-200” manufactured by Denki Kagaku Kogyo Co., Ltd. “Regisfi® R-300” can be exemplified.

Next, the acrylic resin layer (A) of the present invention comprises an acrylic resin (A1), an aromatic vinyl monomer unit, a (meth) acrylic acid ester monomer unit, and an unsaturated dicarboxylic anhydride monomer. And a copolymer (A2) having units, and the mixing mass ratio thereof is (A1) / (A2) = 80 to 20/20 to 80. Here, when the mixing ratio of the acrylic resin (A1) and the copolymer (A2) is within the above range, the surface is excellent in interlayer adhesion with the polycarbonate resin layer (B) and is a characteristic of the acrylic resin. It is preferable because heat resistance is improved and water absorption is suppressed while maintaining hardness and transparency. Further, when importance is attached to the surface hardness, it is preferable that (A1) / (A2) = 80 to 55/20 to 45. When importance is attached to improvement of heat resistance and suppression of water absorption, (A1) ) / (A2) = 50-20 / 50-80.

In the acrylic resin layer (A) of the present invention, various additives and other resins can be appropriately blended as long as the effects of the present invention are not impaired. Examples of the additive include an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant, a flame retardant, and a colorant. Examples of the other resin include methyl methacrylate-maleic anhydride copolymer.

(Antioxidant)
As the antioxidant, various commercially available products can be applied, and various types such as monophenol type, bisphenol type, polymer type phenol type, sulfur type and phosphite type can be exemplified.
Examples of monophenols include 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-4-ethylphenol, and the like. Examples of bisphenols include 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4 '-Thiobis- (3-methyl-6-tert-butylphenol), 4,4'-butylidene-bis- (3-methyl-6-tert-butylphenol), 3,9-bis [{1,1-dimethyl- Examples include 2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl} 2,4,9,10-tetraoxaspiro] 5,5-undecane.

Examples of the high molecular phenolic compound include 1,1,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris ( 3,5-di-tert-butyl-4-bidoxybenzyl) benzene, tetrakis- {methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate} methane, bis {(3,3'-bis-4'-hydroxy-3'-tert-butylphenyl) butyric acid} glycol ester, 1,3,5-tris (3 ', 5'-di-tert-butyl- Examples thereof include 4'-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) trione, tocopherol (vitamin E) and the like.

Examples of sulfur-based compounds include dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiopropionate.

Examples of phosphites include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, Crick neopentanetetrayl bis (octadecyl phosphite), tris (mono and / or di) phenyl phosphite, diisodecyl pentaerythritol diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10 -Dihydro-9-oxa-10-fo Phaphenanthrene, cyclic neopentanetetraylbis (2,4-di-tert-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6-di-tert-methylphenyl) phosphite, 2 , 2-methylenebis (4,6-tert-butylphenyl) octyl phosphite.
The said antioxidant can be used individually by 1 type or in combination of 2 or more types.

In the present invention, phenolic and phosphite-based antioxidants such as high-molecular-weight phenols are preferred in view of the effect of antioxidants, thermal stability, economy, etc. Among them, phosphite-based ones having excellent thermal decomposition resistance are preferred. Antioxidants are more preferred.
The amount of the antioxidant added is in the range of 0.001 to 0.5 parts by mass with respect to 100 parts by mass of the resin composition constituting the acrylic resin layer (A), and 0.05 to 0.3 It is preferable to add part by mass.

(UV absorber)
As the ultraviolet absorber, various commercially available products can be applied, and various types such as benzophenone, benzotriazole, triazine, and salicylic acid ester can be exemplified.
Examples of benzophenone ultraviolet absorbers include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-n-dodecyl. Oxybenzophenone, 2-hydroxy-4-n-octadecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-5-chlorobenzophenone, 2,4 Examples include -dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone.

Benzotriazole-based UV absorbers include hydroxyphenyl-substituted benzotriazole compounds including 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole 2- (2-hydroxy-3,5-dimethylphenyl) benzotriazole, 2- (2-methyl-4-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-3-methyl-5-tert-butylphenyl) And benzotriazole, 2- (2-hydroxy-3,5-di-t-amylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, and the like.
Examples of triazine ultraviolet absorbers include 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2- (4 , 6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyloxy) phenol and the like.
Examples of salicylic acid esters include phenyl salicylate and p-octylphenyl salicylate.
The said ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types.
The addition amount of the ultraviolet absorber is in the range of 0.3 to 5.0 parts by mass with respect to 100 parts by mass of the resin composition constituting the acrylic resin layer (A). It is preferable to add part by mass.

(Light stabilizer)
In addition to the above UV absorbers, hindered amine light stabilizers can be suitably used as light stabilizers that impart weather resistance. The hindered amine light stabilizer does not absorb ultraviolet rays like the ultraviolet absorber, but exhibits a remarkable synergistic effect when used together with the ultraviolet absorber.

(Hindered amine light stabilizer)
Examples of hindered amine light stabilizers include dimethyl-1- (2-hydroxyethyl) succinate-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1,1 , 3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {{2, 2,6,6-tetramethyl-4-piperidyl} imino}], N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2, 6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3 , 5-Di-tert-4- Mud alkoxybenzylacetic) -2-n-butyl malonic acid bis (1,2,2,6,6-pentamethyl-4-piperidyl), and others.
The amount of the hindered amine light stabilizer added is in the range of 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the resin composition constituting the acrylic resin layer (A), and 0.05 to 0 It is preferable to add 3 parts by mass.

<Polycarbonate resin layer (B)>
The polycarbonate resin layer (B) shares a function of expressing the impact resistance, heat resistance, etc., among the functions of the laminate. For this reason, although the polycarbonate-type resin layer (B) may use the polycarbonate-type resin (B1) alone, it can be used by mixing with various modifiers (B2).

(Polycarbonate resin (B1))
As the polycarbonate resin (B1), an aromatic polycarbonate resin can be preferably used, but an aliphatic polycarbonate resin may be used. Moreover, either a homopolymer or a copolymer with another copolymerizable monomer may be used. Furthermore, the structure may be a branched structure, a linear structure, or a mixture of a branched structure and a linear structure.
As a method for producing the polycarbonate resin (B1) used in the present invention, any known method such as a phosgene method, a transesterification method, or a pyridine method may be used.

The weight-average molecular weight of the polycarbonate resin (B1) used in the present invention is usually in the range of 10,000 to 100,000, preferably 20,000 to 40,000, particularly preferably 22,000 to 28,000. Can be used. The polycarbonate resin (B1) can be used alone or in combination of two or more. Here, if the weight average molecular weight is in the above range, impact resistance is ensured and extrusion moldability is also good, which is preferable.

A commercially available product can be used as the polycarbonate resin (B1) used in the present invention. Specific examples of the aromatic polycarbonate resin include trade names “CALIBER”, manufactured by Sumika Stylon Polycarbonate Co., Ltd., “ “SD POLYCA”, trade name “Iupilon” manufactured by Mitsubishi Engineering Plastics, “NOVAREX”, trade name “Panlite” manufactured by Teijin Limited, etc. Can be illustrated. Moreover, as a specific example of the aliphatic polycarbonate resin, a trade name “DURABIO” manufactured by Mitsubishi Chemical Corporation can be exemplified.

(Modifier (B2))
In the present invention, the modifier (B2) used by mixing with the polycarbonate resin (B1) is used for the purpose of adjusting the glass transition temperature and the melt viscosity and improving the hardness. Examples thereof include a resin (B2-1) and a specific acrylic resin (B2-2).

(Specific polyester resin (B2-1))
The specific polyester resin (B2-1) is composed of 80 mol% or more of aromatic dicarboxylic acid as a carboxylic acid monomer (A) unit and 1,4-cyclohexanedimethanol as a glycol monomer (B) unit. Is a polyester resin composed of structural units containing 40 mol% or more.

Here, the carboxylic acid monomer (A) unit of the polyester resin (B2-1) contains 80 mol% or more of aromatic dicarboxylic acid. Here, it is preferable that the aromatic dicarboxylic acid is 80 mol% or more in the carboxylic acid monomer (A) unit because the resulting polyester resin (B2-1) has sufficient heat resistance and mechanical strength. From such a viewpoint, the aromatic dicarboxylic acid is more preferably contained in the carboxylic acid monomer (a) unit with a lower limit of 85 mol% or more, and an upper limit of 100 mol% or less. preferable.
The aromatic dicarboxylic acid is not particularly limited, and includes terephthalic acid, isophthalic acid, naphthalene-1,4 or 2,6-dicarboxylic acid, anthracene dicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4′- Examples thereof include diphenyl ether dicarboxylic acid, 5-sulfoisophthalic acid, sodium 3-sulfoisophthalate and the like. The aromatic dicarboxylic acid may be subjected to polymerization as its ester. There is no restriction | limiting in particular as aromatic dicarboxylic acid ester, The ester of said aromatic dicarboxylic acid is preferable, and lower alkyl ester, aryl ester, carbonate ester, acid halide, etc. are mentioned. The carboxylic acid monomer (a) unit may contain a small amount of an aliphatic dicarboxylic acid (usually in a range of less than 20 mol%). The aliphatic dicarboxylic acid is not particularly limited, and oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, azelaic acid, dodecanedioic acid, dimer acid, 1,3 or 1,4-cyclohexanedicarboxylic acid And acid, cyclopentane dicarboxylic acid, 4,4′-dicyclohexyl dicarboxylic acid and the like. These carboxylic acid monomers (I) can be used alone or in combination of two or more.

Next, the glycol monomer (B) unit of the polyester resin (B2-1) contains 40 mol% or more of 1,4-cyclohexanedimethanol. There are no particular limitations on the glycol used in the glycol monomer (b) other than the above-mentioned components. Ethylene glycol, diethylene glycol (including by-product components), 1,2-propylene glycol, 1,3- Propanediol, 2,2-dimethyl-1,3-propanediol, trans- or -2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1 , 5-pentanediol, 1,6-hexanediol, 1,3-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2- Hydroxyethyl ether) and the like. These glycol monomers (b) can be used alone or in combination of two or more, and appropriately impart color tone, transparency, heat resistance, impact resistance, etc. to the polyester resin. However, ethylene glycol can be preferably used because it can provide thermal stability during molding of the resulting polyester-based resin and is inexpensive and easily available industrially.

1,4-cyclohexanedimethanol used for the glycol monomer (b) mainly imparts impact resistance to the resulting polyester resin (B2-1) and has a phase with the polycarbonate resin (B1). It improves solubility. In addition, 1,4-cyclohexanedimethanol has two types of isomers, cis-type and trans-type, and any of them may be used. Here, if the content in the glycol monomer (b) unit is 40 mol% or more, the effect of imparting impact resistance to the resulting polyester resin (B2-1) is sufficient, and the polycarbonate resin This is preferable because the compatibility with the resin (B1) is improved and the transparency is hardly lowered. From this point of view, 1,4-cyclohexanedimethanol preferably has a lower limit of 50 mol% or more in the glycol monomer (b) unit, and an upper limit of 100 mol% or less. Is more preferable, and 80 mol% or less is more preferable.

The polyester-based resin (B2-1) may be a commercially available product. Specific examples include a product name “SKYGREEN J2003” manufactured by SK Chemical Co., Ltd., and Eastman Chemical Co., Ltd. The product name “Easter (PCG Copolyester 24635)” can be exemplified.

The mixing mass ratio between the polycarbonate resin (B1) and the polyester resin (B2-1) is not particularly limited, but (B1) / (B2-1) = 99 to 1/1 to 99. It is preferably 95 to 5/5 to 95, more preferably 90 to 10/10 to 90. Since the mixed composition of the two is compatible, it can be arbitrarily adjusted between the glass transition temperature of the polycarbonate resin (B1) and the glass transition temperature of the polyester resin (B2-1), and thus is preferable.
The glass transition temperature of the acrylic resin layer (A) used in the present invention is preferably 100 to 140 ° C., more preferably 110 to 140 ° C., further preferably 115 to 140 ° C., 120 A temperature of ˜140 ° C. is particularly preferred. Here, the glass transition temperature of the polycarbonate resin layer (B) is preferably 100 to 160 ° C., but the mixing ratio is (B1) / (B2-1) = 80 to 20/20 to 80. Thus, the temperature can be adjusted to about 100 to 140 ° C. The absolute value of the difference between the glass transition temperature of the acrylic resin layer (A) and the glass transition temperature of the polycarbonate resin layer (B) is 30 ° C. or less, for example, at a temperature of 85 ° C. and a humidity of 85% RH. Even when exposed to such a high temperature and high humidity environment, warpage of the laminate can be suppressed, which is preferable. From this viewpoint, the absolute value of the difference is more preferably 20 ° C. or less, further preferably 10 ° C. or less, and particularly preferably 5 ° C. or less. This is because, under a high temperature and high humidity environment, the acrylic resin layer (A) is susceptible to various strain relaxation phenomena due to a decrease in softening temperature due to water absorption, but the absolute value of the difference is within the above range. It is considered that the dimensional change behavior of both layers becomes close in a high temperature and high humidity environment, and as a result, warpage is suppressed.
In the present invention, the glass transition temperature is measured using a differential scanning calorimeter at a heating rate of 10 ° C./min according to JIS K7121, but other known instrumental analyzers such as dynamic viscosity are used. It can also be measured with an elastic device.

(Specific acrylic resin (B2-2))
Next, the specific acrylic resin (B2-2) is an acrylic copolymer composed of 5 to 80% by mass of aromatic (meth) acrylate monomer units and 95 to 20% by mass of methyl methacrylate monomer units. .
Here, examples of the aromatic (meth) acrylate monomer unit include phenyl (meth) acrylate and benzyl (meth) acrylate. These can be used alone or in combination of two or more. Here, in the present invention, phenyl methacrylate and benzyl methacrylate are preferable from the viewpoint of compatibility with the polycarbonate resin (B1), and phenyl methacrylate is more preferable.
The acrylic resin (B2-2) can contain other copolymerizable monomer units other than the aromatic (meth) acrylate monomer unit and the methyl methacrylate monomer unit, if necessary. . When other monomer units are contained, the content is preferably 0.1 to 10% by mass in the acrylic resin (B2-2).

It is preferable that the aromatic (meth) acrylate monomer unit and the methyl methacrylate monomer unit are in the above ranges since compatibility with the polycarbonate resin (B1) and an effect of improving the surface hardness can be expressed. From this viewpoint, the aromatic (meth) acrylate monomer unit is preferably 10 to 70% by mass and the methyl methacrylate monomer unit 90 to 30% by mass, and the aromatic (meth) acrylate monomer unit 25 to More preferably, it is 60% by mass and 75 to 40% by mass of methyl methacrylate monomer units.

The acrylic resin (B2-2) preferably has a polystyrene-reduced weight average molecular weight (Mw) of 5,000 to 30,000 as measured by gel permeation chromatography (GPC). Here, when the weight average molecular weight (Mw) is within this range, the compatibility with the polycarbonate resin (B1) is good, and the resulting polycarbonate resin layer (B) has a moldability, surface hardness improvement effect and appearance. It is preferable because it is excellent. From such a viewpoint, the range of the weight average molecular weight (Mw) is more preferably 10,000 to 28,000.

As the acrylic resin (B2-2), a commercially available product can be used. As a specific example, a trade name “MATEBLEN H-880” manufactured by Mitsubishi Rayon Co., Ltd. can be exemplified.

The mixing ratio of the polycarbonate resin (B1) and the acrylic resin (B2-2) is not particularly limited, but (B1) / (B2-2) = 99 to 65/1 to 35% by mass. Preferably there is. Here, if the mixing ratio is within this range, the polycarbonate-based resin layer (B) obtained is preferable because it is excellent in moldability, surface hardness improvement effect, appearance, and the like. From this viewpoint, it is more preferable that (B1) / (B2-2) = 95 to 70/5 to 30% by mass.

In the resin composition constituting the polycarbonate-based resin layer (B) of the present invention, the above-described various additives and other resins can be appropriately blended within a range that does not impair the effects of the present invention. Examples of the additive include an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant, a flame retardant, a colorant, and a hydrolysis inhibitor.

(Hydrolysis inhibitor)
Examples of hydrolysis inhibitors include phenolic compounds, carbodiimide compound monomers or polymers, and oxazoline compound monomers or polymers. In the present invention, a monomer or polymer of a carbodiimide compound can be preferably used.

Examples of the carbodiimide compound include those having a basic structure represented by the following general formula (1).

In the general formula (1), n is an integer of 1 or more, and R represents an organic bond unit. For example, R can be either aliphatic, alicyclic, or aromatic. Also, n is usually selected from an appropriate integer between 1 and 50. When n is an integer of 2 or more, R of 2 or more may be the same or different.
Specific examples include bis (propylphenyl) carbodiimide, bis (dipropylphenyl) carbodiimide, poly (4,4′-diphenylmethanecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (tolyl). Carbodiimide), poly (diisopropylphenylene carbodiimide), poly (methyl-diisopropylphenylene carbodiimide), poly (triisopropylphenylene carbodiimide), aromatic polycarbodiimide, and the like, and carbodiimide compounds. The said carbodiimide compound can be used individually by 1 type or in combination of 2 or more types. The polymer of the carbodiimide compound preferably has a molecular weight of 2,000 to 50,000.

The carbodiimide compound may be a commercially available product. Specific examples thereof include trade names “Stabaxol P”, “Stabaxol P100” manufactured by Rhein 清 Chemie GmbH, and products manufactured by Nisshinbo Chemical Co., Ltd. Examples include the names “CARBODILITE HMV-8CA” and “CARBODILITE LA-1”.

The addition amount of the hydrolysis inhibitor is in the range of 0.001 to 1.0 part by mass with respect to 100 parts by mass of the resin composition constituting the polycarbonate resin layer (B), and 0.05 to 0.00. It is preferable to add 5 parts by mass.

<Laminated body>
The laminate of the present invention has an acrylic resin layer (A) on at least one side of a polycarbonate resin layer (B). In the present invention, a hard coat layer (C) described later can be further laminated on each layer. Specific examples of the layer structure include (A) / (B), (A) / (B) / (A), and a structure having a hard coat layer (C), (C) / (A) / (B) , (C) / (A) / (B) / (A), (C) / (A) / (B) / (C) and (C) / (A) / (B) / (A) / ( C) can be exemplified. Here, when two or more identical classification layers are included in the layer structure, the layers may have the same composition or different compositions. In the present invention, (A) / (B), (C) / (A) / (B) and (C) / (A) / (B) / (C) configurations are preferred. In the case of a display panel or the like, (outer side) (C) / (A) / (B) / (C) (inner side) or (outer side) (C) / (A) / (B) ( It is more preferable to arrange so that the inner surface side).

(Thickness of laminate)
The total thickness of the acrylic resin layer (A) and the polycarbonate resin layer (B) of the laminate of the present invention is not particularly limited, but is usually 0.1 to 3.0 mm. The total thickness is preferably 0.1 to 1.5 mm, and more preferably 0.15 to 1.2 mm.
Further, the total thickness has a preferable range depending on the application of the laminate of the present invention. For example, when applied to the front cover material of various image display devices, the thickness is preferably 0.5 to 1.5 mm, more preferably 0.6 to 1.2 mm, and 0.7 to 1. More preferably, it is 1 mm. If it is in this range, it is preferable because it is excellent in lightness, rigidity, and shape stability in a high temperature and high humidity environment. In addition, when an adhesive layer or the like is laminated on the laminate of the present invention to protect it from dirt or scratches on the surface of glass or the like, or to prevent scattering of broken pieces or the like, 0. It is preferably 1 to 0.6 mm, and more preferably 0.15 to 0.5 mm.

Next, the thickness of the acrylic resin layer (A) of the laminate of the present invention is not particularly limited, but the surface hardness and impact resistance of the laminate and shape stability in high temperature and high humidity environments. Etc. From this viewpoint, the thickness of the acrylic resin layer (A) is preferably 0.01 to 0.25 mm, more preferably 0.04 to 0.20 mm, and 0.06 to 0.10 mm. More preferably it is. Further, when the total thickness of the acrylic resin layer (A) and the polycarbonate resin layer (B) is (T), the thickness ratio of the acrylic resin layer (A) 1 layer ((A) / (T) ) Is preferably from 0.01 to 0.35, more preferably from 0.05 to 0.30, and even more preferably from 0.07 to 0.20. If it is in the range of the said thickness and thickness ratio, since it is excellent in the surface hardness of this laminated body, impact resistance, and the shape stability in high temperature and a high humidity environment, it is preferable.

(Total light transmittance)
When the total light transmittance is used as an index of transparency of the laminate of the present invention, it is preferably 85% or more, and more preferably 89% or more. The total light transmittance in the present invention is measured according to JIS K7361-1.

(Warp evaluation)
The warpage evaluation of the laminate of the present invention is performed as follows. That is, a 100 mm square test piece (n = 3) was cut out from the obtained laminate, and first left for 24 hours in a temperature 23 ° C., humidity 50% RH environment. Next, each test piece was allowed to stand for 120 hours in a temperature of 85 ° C. and a humidity of 85% RH, and then left for 24 hours in a temperature of 23 ° C. and a humidity of 50% RH. Then, the test piece was allowed to stand on a surface plate. The height from the platen at the four corners was measured as the amount of warpage, and the average value of the absolute values was evaluated. By making the environmental conditions the same before and after leaving in a high temperature and high humidity environment, only the influence under the high temperature and high humidity environment can be measured.
In the present invention, the amount of warpage is preferably 1.5 mm or less, more preferably 1.0 mm or less, further preferably 0.5 mm or less, and most preferably 0 mm. If it is in the said range, since a laminated body can be used in a wider use and environment, it is preferable.

The warpage evaluation was performed in the present invention under the conditions of a temperature of 85 ° C. and a humidity of 85% RH. However, as a high temperature and high humidity environment, conditions such as a temperature of 60 ° C., a humidity of 90% RH, a temperature of 70 ° C., a humidity of 90% RH, etc. May be used.
Further, as a method for reducing warpage, there is a method in which a film is formed so as not to give a strain that adversely affects the production of a laminate, or a strain is relaxed by annealing for several hours to several days in the vicinity of Tg. Specifically, it may be adjusted so as to reduce the thermal contraction rate under the environmental conditions to be evaluated. Furthermore, it can also adjust with the application | coating thickness and kind to the front and back of the hard-coat layer (C) mentioned later.

(Laminate manufacturing method)
Next, although the manufacturing method of the laminated body of this invention is demonstrated, it does not specifically limit. As a film forming method, a known method, for example, a single-screw extruder, a multi-screw extruder, a Banbury mixer, a kneader or the like has melt mixing equipment, and an extrusion casting method using a T die is a surface such as handleability and productivity. Can be suitably used. As a method for forming the laminate, a method in which a melt-kneaded resin is co-extruded with a T-die having a feed block or a multi-manifold can be suitably used. Moreover, in order to make the external appearance of a laminated body favorable, it is preferable to use the shaping | molding roll (metal elastic roll, polishing roll, etc.) by which the surface was mirror-finished.
The molding temperature in the extrusion casting method using a T-die is appropriately adjusted depending on the flow characteristics and film forming properties of the resin composition to be used, but is generally 300 ° C. or less, preferably 230 to 270 ° C. The forming roll is generally 90 to 130 ° C, preferably 95 to 115 ° C.

In the present invention, a single screw extruder or a multi-screw extruder can be preferably used, but each layer of the extruder preferably has a vent function and a filter function. The vent function is preferable because it can be used for drying the resin composition used for each layer, removing a small amount of volatile components, and the like, and a laminate having few defects such as bubbles can be obtained. Further, there are various types of filter functions, and specific examples include a leaf disc filter, a back disc filter, a cone type filter, a candle filter, and a cylindrical filter. Among them, a leaf disk filter that can easily secure an effective filtration area is preferable. The filter function can remove foreign matters, minute gels, and the like, and a laminated body with few appearance defects can be obtained.

The resin composition used in the present invention may be used by mixing each component in advance using a mixer such as a tumbler, V-type blender, Banbury mixer, or extruder, and each component measured at the supply port of the extruder may be used. The components may be directly supplied, or the components weighed separately may be supplied to each supply port of an extruder having two or more supply ports. Furthermore, the mixing method of various additives can use a well-known method. For example, (a) a master batch in which various additives are mixed in a suitable base resin at a high concentration (typically about 3 to 60% by mass) is prepared separately, and the concentration is added to the resin used. And (b) a method of directly mixing various additives into the resin to be used.

<Hard coat layer (C)>
The hard coat layer (C) is a layer that imparts excellent surface hardness and scratch resistance to the laminate of the present invention.
Here, regarding the surface hardness, the pencil hardness can be evaluated as one index. In the present invention, the pencil hardness was measured with respect to the surface to be measured with a load of 750 gf according to JIS K5600-5-4.
Regarding the surface of the acrylic resin layer (A) of the laminate of the present invention, the pencil hardness is preferably H or higher, more preferably 2H or higher, and particularly preferably 3H or higher. Moreover, about the surface of the hard-coat layer (C) applied to an outer surface side, it is preferable that pencil hardness is 4H or more, It is more preferable that it is 5H or more, It is especially preferable that it is 7H or more. When the pencil hardness is 4H or more, a laminate having excellent surface hardness can be provided. As for the surface of the hard coat layer (C) applied to the inner surface side, the pencil hardness is preferably F or more, and more preferably H or more. If the pencil hardness is F or more, it can function as a scratch-preventing layer for preventing the layered product from being scratched during transportation and processing within the process.

Next, regarding the scratch resistance of the surface of the hard coat layer (C) applied to the outer surface side, the steel wool test can be evaluated as one index. Here, it is preferable that the number of reciprocations until scratching is 20 times or more when rubbing with a load of 1000 gf using # 0000 steel wool. If the number of reciprocations until the surface is scratched when rubbed with the steel wool is 20 times or more, it is possible to provide a scratch-resistant laminate having excellent scratch resistance. From this point of view, the number of reciprocations until the surface is scratched is preferably 20 times or more, more preferably 300 times or more, and particularly preferably 500 times or more.

(Hard coat agent)
The hard coating agent is not particularly limited in the present invention, but a hard coating agent that cures by irradiating energy beams such as an electron beam, radiation, or ultraviolet rays, or that cures by heating can be applied. In the present invention, it is preferably made of an ultraviolet curable resin from the viewpoint of molding time and productivity.
Here, specific examples of the curable resin include acrylate compounds, urethane acrylate compounds, epoxy acrylate compounds, carboxyl group-modified epoxy acrylate compounds, polyester acrylate compounds, copolymer acrylates, alicyclic epoxy resins, glycidyl ether epoxy resins, Examples include vinyl ether compounds and oxetane compounds. These curable resins can be used alone or in combination of two or more. Examples of curable resins that impart superior surface hardness include radical polymerization curable compounds such as polyfunctional acrylate compounds, polyfunctional urethane acrylate compounds, and polyfunctional epoxy acrylate compounds, and heat such as alkoxysilanes and alkylalkoxysilanes. Polymerizable curable compounds can be mentioned, and an organic / inorganic composite curable resin composition obtained by adding an inorganic component to the curable resin can also be used.

An organic / inorganic hybrid curable resin composition can be exemplified as a curable resin composition that imparts particularly excellent surface hardness. Examples of the organic / inorganic hybrid curable resin composition include those composed of a curable resin composition containing an inorganic component having a reactive functional group in the curable resin.
Utilizing such an inorganic component having a reactive functional group, for example, an organic / inorganic composite in which this inorganic component is copolymerized and crosslinked with a radical polymerizable monomer, so that the organic binder simply contains the inorganic component. Compared to the system curable resin composition, it is preferable because curing shrinkage hardly occurs and high surface hardness can be expressed. Furthermore, from the viewpoint of reducing curing shrinkage, an organic / inorganic hybrid curable resin composition containing ultraviolet-reactive colloidal silica as an inorganic component having a reactive functional group can be mentioned as a more preferable example.

Examples of means for imparting particularly excellent surface hardness include a method of adjusting the concentration of the inorganic component and / or the inorganic component having a reactive functional group contained in the hard coat layer (C).
A preferable concentration range of the inorganic component and / or the inorganic component having a reactive functional group contained in the hard coat layer (C) is 10% by mass or more and 65% by mass or less. The lower limit of the preferred concentration is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 40% by mass or more. A concentration of 10% by mass or more is preferable because an effect of imparting excellent surface hardness to the hard coat layer (C) can be obtained. On the other hand, the upper limit value of the preferred concentration is preferably 65% by mass or less, more preferably 60% by mass or less, and particularly preferably 55% by mass or less. If the concentration is 65% by mass or less, the hard coat layer (C) can be filled with an inorganic component and / or an inorganic component having a reactive functional group most closely, and an excellent surface hardness can be obtained. It is preferable because it can be applied to the target.

As a method for forming the hard coat layer (C), for example, after coating the surface of the resin layer as a paint obtained by dissolving or dispersing the curable resin composition in an organic solvent, a cured film is obtained. Although there is a method of forming and laminating on the surface of the resin layer, it is not limited to this method.
A known method is used as a method of laminating with the resin layer. For example, laminating method using cover film, dip coating method, natural coating method, reverse coating method, comma coater method, roll coating method, spin coating method, wire bar method, extrusion method, curtain coating method, spray coating method, The gravure coat method etc. are mentioned. In addition, for example, a method of laminating the hard coat layer (C) on the resin layer using a transfer sheet in which the hard coat layer (C) is formed on the release layer may be employed.
In addition, various surface treatments such as corona treatment, plasma treatment and primer treatment can be performed on the surface of the resin layer for the purpose of improving the adhesion between the hard coat layer (C) and the resin layer.

The curable resin composition for forming the hard coat layer (C) is preferably made of an ultraviolet curable resin from the viewpoint of molding time and productivity, that is, one that is cured by irradiation with ultraviolet rays. Here, as a light source that emits ultraviolet rays, an electrodeless high-pressure mercury lamp, an electroded high-pressure mercury lamp, an electrodeless metal halide lamp, an electroded metal halide lamp, a xenon lamp, an ultra-high pressure mercury lamp, a mercury xenon lamp, or the like can be used. Among these, an electrodeless high-pressure mercury lamp is preferable because it is easy to obtain ultraviolet rays with high illuminance and is advantageous for curing an ultraviolet curable resin.
Further, in the ultraviolet curable resin, the added photopolymerization initiator absorbs ultraviolet rays and is excited and activated to cause a polymerization reaction, and a curing reaction of the ultraviolet curable resin occurs. Therefore, it is preferable to select a light source according to the photopolymerization initiator added to the ultraviolet curable resin, that is, according to the excitation wavelength of the photopolymerization initiator, which is advantageous for curing the ultraviolet curable resin.

(Photopolymerization initiator)
When the curable resin composition is made of an ultraviolet curable resin and is cured by irradiation with ultraviolet rays, a photopolymerization initiator is used as a curing agent. Examples of the photopolymerization initiator include benzyl, benzophenone and derivatives thereof, thioxanthones, benzyldimethyl ketals, α-hydroxyalkylphenones, α-hydroxyacetophenones, hydroxyketones, aminoalkylphenones, acylphosphine oxides. Etc. Of these, α-hydroxyalkylphenones are preferred because they hardly cause yellowing during curing and a transparent cured product is obtained. In addition, aminoalkylphenones are preferable because they have very high reactivity and a cured product having excellent hardness can be obtained. The said photoinitiator can be used individually by 1 type or in combination of 2 or more types. The addition amount of the photopolymerization initiator is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the curable resin.

Commercially available photopolymerization initiators can be used. Specific examples include “IRGACURE651”, “IRGACURE184”, “IRGACURE500”, “IRGACURE1000”, “IRGACURE2959”, “DAROCUR1173”, “IRGACURE127”, “IRGACURE907”. ”,“ IRGACURE 369 ”,“ IRGACURE 379 ”,“ IRGACURE 1700 ”,“ IRGACURE 1800 ”,“ IRGACURE 819 ”,“ IRGACURE 784 ”[The above IRGACURE (IRGACURE) series and DAROCUR (Darocur) series are BASF Japan products) Name], “KAYACUREITX”, “KAYACUREDETX-S”, “KAYA UREBP-100 "," KAYACUREBMS "," KAYACURE2-EAQ "[more KAYACURE (Kayacure) series, manufactured by Nippon Kayaku Co., Ltd. under the trade name], and others. Among these, examples of the above-mentioned α-hydroxyalkylphenones include “IRGACURE184”, while examples of the aminoalkylphenones include “IRGACURE907”, “IRGACURE369”, “IRGACURE379”. Can be mentioned.

(Surface conditioning component)
The curable resin composition forming the hard coat layer (C) can contain a leveling agent as a surface conditioning component. Examples of the leveling agent include silicone leveling agents and acrylic leveling agents. In particular, those having a reactive functional group at the terminal are preferable, and those having a reactive functional group having two or more functionalities are more preferable. preferable.
Specifically, polyether-modified polydimethylsiloxane having an acrylic group having double bonds at both ends (for example, trade names “BYK-UV 3500” and “BYK-UV 3530” manufactured by BYK Chemie Japan Co., Ltd.)) And a polyester-modified polydimethylsiloxane having an acrylic group having two double bonds at the end in total (trade name “BYK-UV 3570” manufactured by Big Chemie Japan Co., Ltd.). Among these, polyester-modified polydimethylsiloxane having an acrylic group that has a stable haze value and contributes to improvement of scratch resistance is particularly preferable.

(Other ingredients)
In addition to the curable resin component, the curable resin composition for forming the hard coat layer (C) includes, for example, a lubricant such as a silicon compound, a fluorine compound, or a mixed compound thereof, an antioxidant, and an ultraviolet absorber. Various additives such as an agent, an antistatic agent, a flame retardant such as a silicone compound, a filler, glass fiber, and an impact modifier can be contained within a range that does not impair the effects of the present invention.

When the curable resin composition is made of an ultraviolet curable resin and is cured by irradiating with ultraviolet rays, the resin composition has a high degree of transparency with respect to the ultraviolet rays. Because of the oxygen disorder), curing may be delayed on the surface of the resin composition. For this oxygen disorder, it is preferable to irradiate the resin composition with a nitrogen gas atmosphere by supplying nitrogen gas and then irradiate with ultraviolet rays, since the curing of the surface can proceed rapidly together with the inside of the resin composition. .

The thickness of the hard coat layer (C) is not particularly limited, but is preferably in the range of 1 to 30 μm, more preferably in the range of 3 to 25 μm, and in the range of 5 to 20 μm. More preferably, it is in the range of 7 to 15 μm. Here, it is preferable if the thickness of the hard coat layer (C) is in the above range because scratch resistance can be imparted and cracks due to stress are unlikely to occur. When the hard coat layer (C) is provided on both sides, the thickness of each hard coat layer may be the same or different, but both are in the range of 7 to 15 μm, and the acrylic resin layer (A) The thickness of the hard coat layer on the surface is preferably equal to or greater than the thickness of the hard coat layer on the surface of the polycarbonate resin layer (B).

One or more of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment is applied to one or both sides of the laminate having the hard coat layer (C) according to the present invention. be able to. Each processing method is not particularly limited, and a known method can be used. For example, a method of applying a reflection reducing coating, a method of depositing a dielectric thin film, a method of applying an antistatic coating, and the like can be exemplified.

(Assumed use)
As described above, the laminate of the present invention is excellent in economy by using a general-purpose material as a main raw material, and is excellent in transparency, impact resistance, surface hardness, and shape stability in a high temperature and high humidity environment. It can be applied to various uses such as a substrate material and a protective material, and the use is not particularly limited.
In particular, the laminate can be used as various substrate materials and protective materials. Specifically, portable display devices (mobile phone terminals, smartphones, portable electronic playground equipment, personal digital assistants, tablet devices, mobile PCs, etc.) and stationary display devices (LCD TVs, LCD monitors, desktop PCs, car navigation systems, It can be suitably used for automobile instruments and the like.
Furthermore, the laminate of the present invention may be given a shape by various processing methods. Specific examples include a method of heating and pressurizing using a mold, a pressure forming method, a vacuum forming method, and a roll homing method. By applying the shape, application to an image display device having a curved surface and various flexible devices can be expected. The above shape can be imparted in the same manner even when the laminate of the present invention has other layers such as the hard coat layer (C).

In the following, the present invention will be described in more detail with reference to examples. Various measured values and evaluations displayed in this specification were performed as follows.

(1) Glass transition temperature (Tg)
Using a differential scanning calorimeter manufactured by PerkinElmer Co., Ltd., trade name “Pyris1 DSC”, according to JIS K7121, about 10 mg of the sample was heated from −40 ° C. to 200 ° C. at a heating rate of 10 ° C./min. After holding at 200 ° C. for 1 minute, the temperature was lowered to −40 ° C. at a cooling rate of 10 ° C./min, and again from the thermogram measured when the temperature was raised to 200 ° C. at a heating rate of 10 ° C./min, the glass transition temperature (Tg ) (° C). In addition, the value of Tg was rounded off to the first decimal place.

(2) Total light transmittance A test piece of 50 mm square was cut out from the obtained laminate, the total light transmittance was measured according to JIS K7361-1, and the value was evaluated according to the following criteria.
(◎) Total light transmittance is 89% or more (○) Total light transmittance is 85% or more and less than 89% (×) Total light transmittance is less than 85%

(3) Pencil hardness The pencil hardness was measured on the surface to be measured with a load of 750 gf according to JIS K5600-5-4. The pencil hardness on the surface of the acrylic resin layer (A) is H or higher, and the pencil hardness on the surface of the polycarbonate resin layer (B) having the hard coat layer (C) is F or higher (O). .

(4) Warpage Evaluation A 100 mm square test piece (n = 3) was cut out from the obtained laminate, and first left for 24 hours in a temperature 23 ° C., humidity 50% RH environment. Next, each test piece was allowed to stand for 120 hours in a temperature of 85 ° C. and a humidity of 85% RH, and then left for 24 hours in a temperature of 23 ° C. and a humidity of 50% RH. Then, the test piece was allowed to stand on a surface plate. The height from the surface plate at the four corners was measured as the amount of warpage, and the average absolute value was evaluated according to the following criteria.
(◎) Warpage amount is 0.5mm or less (○) Warpage amount is more than 0.5mm, 1.5mm or less (x) Warpage amount is more than 1.5mm

(5) Adhesiveness Regarding the adhesiveness between the hard coat layer (C) on the surface of the laminate and other layers, a cross-cut test was conducted according to JIS K5600-5-6, and the hard coat layer was peeled off. The result was determined to be a pass (O).

(6) Scratch resistance evaluation The scratch resistance of the hard coat layer (C) was measured with the following apparatus and conditions, and the number of reciprocations until the scratch occurred was 500 or more and passed (O). .
・ Equipment: Friction fastness tester Gakushin type (manufactured by Daiei Scientific Instruments)
・ Steel wool count: # 0000
・ Test load: 1000gf
・ Test speed: 30 reciprocations / minute ・ Test stroke: 120 mm

The main raw materials used in Examples and Comparative Examples are described below.
(Acrylic resin (A1))
(A1-1); acrylic resin (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Acrypet VH001, density: 1.19 g / cm ³ , methyl methacrylate / methyl acrylate = 99/1% by mass, stereoregularity (Triad fraction): mm (9.2 mol%), mr (41.8 mol%), rr (49.0 mol%), Tg: 111 ° C., MFR (temperature: 230 ° C., load: 37.3 N) ): 2.0 g / 10 min)

(A1-2); acrylic resin (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumipex EX, density: 1.19 g / cm ³ , methyl methacrylate = 100% by mass, Tg: 106 ° C., MFR (temperature: 230) ° C, load: 37.3 N): 1.5 g / 10 min)

(Copolymer (A2))
(A2-1); copolymer (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: Regisphi R-100, density: 1.14 g / cm ³ , styrene / methyl methacrylate / maleic anhydride = 75/15 / 10% by mass, Tg: 127 ° C., MFR (temperature: 230 ° C., load: 37.3 N): 4.2 g / 10 min)

(A2-2); copolymer (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: Regisphi R-300, density: 1.12 g / cm ³ , styrene / methyl methacrylate / maleic anhydride = 84/5 / 11% by mass, Tg: 131 ° C., MFR (temperature: 230 ° C., load: 37.3 N): 4.3 / 10 min)

(Polycarbonate resin (B1))
(B1-1): polycarbonate resin (manufactured by Sumika Stylon Polycarbonate Co., Ltd., trade name: Caliber 301-4, density: 1.20 g / cm ³ , Tg: 149 ° C., MFR (temperature: 300 ° C., load: 11.8 N): 4.0 g / 10 min)

(B1-2); polycarbonate resin (manufactured by Sumika Stylon Polycarbonate Co., Ltd., trade name: Caliber 301-10, density: 1.20 g / cm ³ , Tg: 149 ° C., MFR (temperature: 300 ° C., load: 11.8N): 10.0 g / 10 min)

(B1-3); polycarbonate resin (manufactured by Sumika Stylon Polycarbonate Co., Ltd., trade name: Caliber 301-15, density: 1.20 g / cm ³ , Tg: 149 ° C., MFR (temperature: 300 ° C., load: 11.8 N): 15.0 g / 10 min)

(Modifier (B2))
(Polyester resin (B2-1))
(B2-1-1); polyester resin (manufactured by SK Chemical Co., Ltd., trade name: SKYGREEN J2003, density: 1.23 g / cm ³ , Tg: 87 ° C.)

(Acrylic resin (B2-2))
(B2-2-1); acrylic resin (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Methabrene H-880, phenyl methacrylate / methyl methacrylate = 34/66 mass%, weight average molecular weight: 14,000)

(Additive) (X)
(X-1); Phosphite antioxidant (manufactured by ADEKA, trade name: ADK STAB PEP-36)
(X-2); hydrolysis inhibitor (Nisshinbo Chemical Co., Ltd., trade name: Carbodilite LA-1)

(Other)
(P-1): MS resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name: Estyrene MS-600, density: 1.13 g / cm ³ , methyl methacrylate / styrene = 60/40 mass%, MFR (temperature : 230 ° C., load: 37.3 N): 5.0 g / 10 min)

<Example 1>
As shown in Table 1, as acrylic resin layer (A), 60 parts by mass of acrylic resin (A1-1), 40 parts by mass of copolymer (A2-1) and (X-1) 0. A resin composition mixed at a ratio of 15 parts by mass, and as a polycarbonate resin layer (B), 60 parts by mass of a polycarbonate resin (B1-1), 40 parts by mass of a polyester resin (B2-1-1) and an addition The resin compositions mixed at a ratio of 0.15 parts by weight of (X-1) and 0.10 parts by weight of (X-2) as an agent are supplied to separate extruders having a vent function and a filter function, respectively. It is melt-kneaded at a temperature of 240 to 265 ° C., coextruded with a 260 ° C. T-die so as to form a layered structure of (A) layer / (B) layer with a feed block, and then cast with a mirror roll at 95 ° C. Cooling, the total thickness is .70Mm, to give each layer thickness of the layer (A) / (B) layer = the laminate is 0.08 mm / 0.62 mm. The resulting laminate had good appearance and excellent flatness. The results of evaluation using the laminate are shown in Table 1.

<Examples 2 to 8>
As shown in Table 1, except that the resin composition of each layer was changed in Example 1, a laminate having a total thickness of 0.70 mm and excellent appearance and flatness was obtained. The extrusion temperature, mirror roll temperature, etc. were adjusted as appropriate according to the Tg and melt viscosity of each layer. The results of evaluation using the laminate are shown in Table 1.

<Comparative Example 1>
As shown in Table 1, the raw material of the acrylic resin layer (A) in Example 1 is not included in the copolymer (A-2), but in the resin composition part including only the acrylic resin (A1-1) alone. A laminated body having a total thickness of 0.70 mm and excellent appearance and flatness was obtained in the same manner except that it was changed. The results of evaluation using the laminate are shown in Table 1.

<Comparative example 2>
As shown in Table 1, in Example 1, the raw material of the acrylic resin layer (A) contains 15 parts by mass of the acrylic resin (A1-1) and 85 parts by mass of the copolymer (A2-1). A laminate having a total thickness of 0.70 mm was obtained in the same manner except that the product was changed to a product. However, since the adhesion between the acrylic resin layer (A) and the polycarbonate resin layer (B) was insufficient, the evaluation was stopped because it was easily peelable by hand.

<Comparative Example 3>
As shown in Table 1, in Example 1, the total thickness was set to be 0.00 except that the copolymer (A2-1) contained in the raw material of the acrylic resin layer (A) was changed to (P-1). A 70 mm laminate was obtained. However, since the compatibility between the acrylic resin (A1-1) and the MS resin (P-1) was poor, the acrylic resin layer (A) was cloudy and the evaluation was stopped.

<Example 9>
Organic / inorganic hybrid ultraviolet curable resin composition (product name “UVHC7800G”, manufactured by MOMENTIVE, containing inorganic silica containing reactive functional groups) on the surface of the acrylic resin layer (A) of the laminate obtained in Example 1 (Amount: 30 to 40% by mass) is applied using a metal bar coater, dried at 90 ° C. for 1 minute, exposed to an exposure dose of 500 mJ / cm ² using an ultraviolet irradiation device, and a hard coat having a thickness of 12 μm. A laminate having the layer (C) was obtained. Table 2 shows the results of evaluating the hard coat layer of the laminate.

<Examples 10 to 14>
As shown in Table 2, a laminate was obtained in the same manner except that the laminate used in Example 9 and the application surface and thickness of the hard coat layer were changed. Table 2 shows the results of evaluating the hard coat layer of the laminate. In addition, when apply | coating to both surfaces, the hard-coat layer was formed for each surface, and ultraviolet irradiation was similarly performed to each surface.

<Example 15>
In Example 8, 100 parts by mass of the polycarbonate resin (B1-3) contained in the raw material of the polycarbonate resin layer (B) was changed to 90 parts by mass of (B1-2) and 10 parts by mass of (B2-2-1). A laminate having a total thickness of 1.00 mm was obtained in the same manner except that the thickness of each layer was changed to (A) layer / (B) layer = 0.08 mm / 0.92 mm. The resulting laminate had good appearance and excellent flatness. Here, the pencil hardness of the polycarbonate resin layer (B) was improved from 2B to F by mixing the acrylic resin (B2-2-1). Next, as shown in Table 2, a laminate having a hard coat layer (C) was obtained in the same manner except that the laminate used in Example 9 and the application surface and thickness of the hard coat layer were changed. Table 2 shows the results of evaluating the hard coat layer of the laminate.

From Table 1, a laminate having an acrylic resin layer (A) on at least one side of a polycarbonate resin layer (B), the laminate containing the resin composition defined in the present invention in a specific range is transparent. It can be confirmed that it has excellent properties, surface hardness and shape stability under high temperature and high humidity environment (Examples 1 to 8). In addition, a laminate in which the absolute value of the difference between the glass transition temperature of the acrylic resin layer (A) and the glass transition temperature of the polycarbonate resin layer (B) is 5 ° C. or less has shape stability in a high temperature and high humidity environment. It can be confirmed that they are more excellent (Example 1, Examples 3 to 5).
On the other hand, it can be confirmed that the laminate outside the range defined in the present invention has one or more defects (Comparative Examples 1 to 3). If the acrylic resin layer (A) is a general-purpose acrylic resin alone, the shape stability under high temperature and high humidity environment is insufficient (Comparative Example 1), and the mixing ratio of the resin composition of the acrylic resin layer (A) is The adhesion between the layers is insufficient outside the specified range of the present invention (Comparative Example 2), and the copolymer mixed with the acrylic resin layer (A) is not the specified range of the present invention with the acrylic resin (A1). It can be confirmed that the compatibility is not expressed and the transparency is not obtained (Comparative Example 3).

From Table 2, it can be confirmed that the laminate of the present invention can impart surface hardness improvement and scratch resistance by having a hard coat layer (C) on the surface. Moreover, it can confirm that the hard-coat layer (C) of the laminated body surface of this invention is excellent also in adhesiveness with another layer (Acrylic resin layer (A) or a polycarbonate-type resin layer (B)). (Examples 9 to 15). The hard coat layer (C) applied to the outer surface side of the laminate of the present invention shares the function of developing excellent surface hardness, while the hard coat layer (C) applied to the inner surface side is used in the process. The function can be shared as an anti-scratch layer for preventing frictional scratches from entering the laminate during transportation or processing.

Claims (20)

1. A laminate having an acrylic resin layer (A) on at least one surface of a polycarbonate resin layer (B), wherein the acrylic resin layer (A) comprises an acrylic resin (A1) and an aromatic vinyl monomer unit. And a copolymer (A2) having a (meth) acrylic acid ester monomer unit and an unsaturated dicarboxylic anhydride monomer unit, and the mixing mass ratio thereof is (A1) / (A2) = 80. A laminate characterized by being from 20/20 to 80.
2. The acrylic resin (A1) has a methyl methacrylate monomer unit as a main component, and the molar ratio of the rr structure among mm, mr, and rr of triad fractions determined by nuclear magnetic resonance measurement ( ¹ H-NMR). The laminate according to claim 1, wherein is the highest.
3. The structural unit of the copolymer (A2) is 45 to 85% by mass of the aromatic vinyl monomer unit, 4 to 45% by mass of the (meth) acrylic acid ester monomer unit, and the unsaturated dicarboxylic acid anhydride unit. The laminate according to claim 1 or 2, wherein the unit is 8 to 20% by mass of a monomer unit.
4. 4. The mixing mass ratio of the acrylic resin (A1) and the copolymer (A2) is (A1) / (A2) = 80 to 55/20 to 45, The laminate according to claim 1.
5. 4. The mixing mass ratio between the acrylic resin (A1) and the copolymer (A2) is (A1) / (A2) = 50 to 20/50 to 80, The laminate according to claim 1.
6. The glass transition temperature of the acrylic resin layer (A) measured at a heating rate of 10 ° C./min using a differential scanning calorimeter is 100 to 140 ° C., and the glass of the polycarbonate resin layer (B) The laminate according to any one of claims 1 to 5, wherein an absolute value of a difference from the transition temperature is 20 ° C or less.
7. The glass transition temperature of the acrylic resin layer (A) measured at a heating rate of 10 ° C./min using a differential scanning calorimeter is 115 to 140 ° C., and the glass of the polycarbonate resin layer (B) The laminate according to any one of claims 1 to 5, wherein an absolute value of a difference from the transition temperature is 10 ° C or less.
8. The polycarbonate resin layer (B) contains a polycarbonate resin (B1) and at least one modifier (B2) selected from the following, according to any one of claims 1 to 7, The laminated body of description.
   Modifier (B2)
   (B2-1): As the carboxylic acid monomer (A) unit, 80 mol% or more of aromatic dicarboxylic acid and as the glycol monomer (B) unit, 40 mol% or more of 1,4-cyclohexanedimethanol are contained. Polyester resin composed of structural units (B2-2): acrylic copolymer comprising 5 to 80% by mass of aromatic (meth) acrylate monomer units and 95 to 20% by mass of methyl methacrylate monomer units
9. The laminate according to any one of claims 1 to 8, wherein a phosphite antioxidant is mixed in the acrylic resin layer (A).
10. The laminate according to any one of claims 1 to 9, wherein a carbodiimide compound is mixed in the polycarbonate resin layer (B).
11. The laminate according to any one of claims 1 to 10, wherein the acrylic resin layer (A) has a thickness of 0.01 to 0.25 mm.
12. When the total thickness of the acrylic resin layer (A) and the polycarbonate resin layer (B) is (T), the thickness ratio of the acrylic resin layer (A) 1 layer ((A) / (T)) The laminate according to any one of Claims 1 to 11, wherein is from 0.01 to 0.35.
13. The laminate according to any one of claims 1 to 12, wherein the laminate is co-extruded.
14. The laminate according to any one of claims 1 to 13, wherein a hard coat layer (C) is laminated on at least one surface of the laminate.
15. The laminate according to claim 14, wherein the surface of the hard coat layer (C) has a pencil hardness of 4H or more.
16. The laminate according to claim 14 or 15, wherein the hard coat layer (C) comprises an organic / inorganic hybrid curable resin composition.
17. The antireflection treatment, the antifouling treatment, the antistatic treatment, the weather resistance treatment and the antiglare treatment are performed on one side or both sides. The laminated body as described in.
18. A substrate material using the laminate according to any one of claims 1 to 17.
19. A protective material using the laminate according to any one of claims 1 to 17.
20. An image display device comprising the laminate according to any one of claims 1 to 17.