JP6693041B2 - Laminate - Google Patents

Description

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

  Conventionally, glass has been mainly used as a cover material for image display devices. However, glass is easily broken by impact and its weight is heavy, so replacement with a resin material is being considered. 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 in soundproof bulkheads, carports, signboards, glazing materials, lighting fixtures, etc. Its use is limited due to the drawback of being easily attached.

  For example, Patent Document 1 discloses a resin laminate obtained by subjecting a laminate obtained by co-extruding a polycarbonate resin and an acrylic resin to a hard coat treatment in order to improve this drawback.

  As a method of suppressing warpage, 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 of suppressing warpage, Patent Document 3 discloses a resin laminate in which the difference in glass transition temperature and the difference in water absorption rate between layers in which polycarbonate resins are laminated are defined.

JP, 2006-103169, A JP, 2010-167659, A WO2014 / 061817

In Patent Document 1, although the surface hardness is improved to some extent by the two-layer structure, in applications where environmental changes such as high temperature and high humidity occur, heat resistance represented by the glass transition temperature of polycarbonate resin and acrylic resin, There is a problem in that a difference in dimensional change occurs due to a difference in water absorption characteristics, and as a result, a large warp is likely to occur.
In Patent Document 2, the MS resin has a lower water absorption rate than the acrylic resin, so that the effect of improving the warp can be seen, but as described in the evaluation in Examples, the temperature of the environmental test is 40 ° C. and the humidity is 90%. RH is still insufficient as a condition of high temperature and high humidity. Further, the MS resin having a reduced water absorption rate by increasing the styrene content of the copolymerization component (40% by mass or more) is likely to have reduced heat resistance and also has poor compatibility with an acrylic resin.
In Patent Document 3, the effect of improving the warp is observed, but as described in the disclosure of the invention and the examples, the means for achieving the effect is to slightly stretch the laminated body depending on the speed ratio of the roll when cooling the laminate. Is an essential manufacturing method. There is a problem that heat shrinkage is imparted when the laminate is slightly stretched in the cooling process. Further, the modified polycarbonate resin used specifically is a special raw material, and there is a problem in economical efficiency.

  Therefore, an object of the present invention is to use a general-purpose material as a main raw material, which is excellent in economic efficiency, and which is used for a substrate material or a protective material, has transparency, impact resistance, surface hardness, and shape stability in a high temperature or high humidity environment. It is to provide a laminate having excellent properties.

As a result of intensive studies, the present inventors have made it possible to obtain a laminate having a specific acrylic resin layer on at least one surface of a polycarbonate resin layer, so that impact resistance, surface hardness, and high temperature or high humidity environment They have found that the shape stability is excellent, and have completed the present invention.
That is, according to the present invention, the following (1) to ( 18 ) are provided.
(1) A laminated body having an acrylic resin layer (A) on at least one surface of a polycarbonate resin layer (B), wherein the acrylic resin layer (A) and the acrylic resin (A1) and aromatic vinyl monomer Containing a copolymer (A2) having a body unit, a (meth) acrylic acid ester monomer unit and an unsaturated dicarboxylic acid anhydride monomer unit, and the mixing mass ratio thereof is (A1) / (A2) = 80. 55 / and 20 to 45, using a differential scanning calorimeter, the glass transition temperature of the glass transition temperature and the polycarbonate resin layer of the acrylic resin layer is measured at a heating rate of 10 ° C. / min (a) (B) The absolute value of the difference with is 20 degreeC or less, The laminated body characterized by the above-mentioned.
(2) The acrylic resin (A1) has a methyl methacrylate monomer unit as a main component, and among the triad fractions mm, mr, and rr determined by nuclear magnetic resonance measurement (1H-NMR), moles of rr structure The laminate according to (1) above, which has the highest ratio.
(3) The constituent unit of the copolymer (A2) is an aromatic vinyl monomer unit 45 to 85 mass%, a (meth) acrylic acid ester monomer unit 4 to 45 mass%, and an unsaturated dicarboxylic acid anhydride unit 8 -20 mass%, The laminated body as described in (1) or (2) above.
( 4 ) 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 above (1) to (). 3 ) The laminated body according to any one of 3 ).
( 5 ) Acrylic resin layer (A) having a glass transition temperature of 115 to 140 ° C. and a glass of polycarbonate resin layer (B) measured at a heating rate of 10 ° C./min using a differential scanning calorimeter The absolute value of the difference from the transition temperature is 10 ° C. or less, and the laminate according to any one of (1) to ( 4 ) above.
( 6 ) Any of the above (1) to ( 5 ), wherein the polycarbonate resin layer (B) contains the polycarbonate resin (B1) and at least one modifier (B2) selected from the following: The laminated body according to item 1.
Modifier (B2)
(B2-1): 80 mol% or more of aromatic dicarboxylic acid as a carboxylic acid monomer (a) unit and 40 mol% or more of 1,4-cyclohexanedimethanol as a glycol monomer (b) unit Polyester Resin (B2-2) Consisting of Structural Units: Acrylic Copolymer ( 7 ) Consisting of 5 to 80% by Mass of Aromatic (Meth) Acrylate Monomer Units and 95 to 20% by Mass of Methyl Methacrylate Monomer Units The laminate according to any one of (1) to ( 6 ) above, wherein a phosphite-based antioxidant is mixed in the acrylic resin layer (A).
( 8 ) The laminate according to any one of (1) to ( 7 ) above, wherein the polycarbonate resin layer (B) is mixed with a carbodiimide compound.
( 9 ) The laminate according to any one of (1) to ( 8 ) above, wherein the acrylic resin layer (A) has a thickness of 0.01 to 0.25 mm.
( 10 ) When the total thickness of the acrylic resin layer (A) and the polycarbonate resin layer (B) is (T), the thickness ratio of one acrylic resin layer (A) ((A) / (T)) Is 0.01 to 0.35, The laminated body as described in any one of said (1)-( 9 ) characterized by the above-mentioned.
( 11 ) The laminate according to any one of (1) to ( 10 ) above, which is coextrusion-molded.
( 12 ) The laminated body according to any one of (1) to ( 11 ) above, wherein the hard coat layer (C) is laminated on at least one surface of the laminated body.
( 13 ) The laminate as described in ( 12 ) above, wherein the surface of the hard coat layer (C) has a pencil hardness of 4H or more.
( 14 ) The laminate according to the above ( 12 ) or ( 13 ), wherein the hard coat layer (C) is composed of an organic / inorganic hybrid curable resin composition.
( 15 ) One or both of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment is applied to one side or both sides of the laminate and the laminate having the hard coat layer (C). The laminated body according to any one of ( 12 ) to ( 14 ) above.
( 16 ) A substrate material using the laminate according to any one of (1) to ( 15 ) above.
( 17 ) A protective material using the laminate according to any one of (1) to ( 15 ) above.
( 18 ) An image display device including the laminate according to any one of (1) to ( 15 ).

  According to the present invention, a laminate having excellent impact resistance, surface hardness and shape stability in a high temperature and high humidity environment is provided, and 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 preferably used for automobile instruments and the like).

Hereinafter, the present invention will be described in detail.
The present invention is a laminated body having an acrylic resin layer (A) on at least one surface of a polycarbonate resin layer (B).

<Acrylic resin layer (A)>
The acrylic resin layer (A) is a copolymer containing an acrylic resin (A1), an aromatic vinyl monomer unit, a (meth) acrylic acid ester monomer unit and an unsaturated dicarboxylic acid anhydride monomer unit. It is a layer containing the coalescence (A2).
The acrylic resin layer (A) shares the function of exhibiting surface hardness and heat resistance among the functions of the laminate. Therefore, the acrylic resin layer (A) may be laminated on both sides of a polycarbonate resin layer (B) described later, but it is necessary that it is laminated on at least one side. In the case of a display panel or the like, it is preferable that the acrylic resin layer (A) is 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 addition, in this specification, a (meth) acrylic acid ester monomer unit means an acrylic acid ester monomer unit or a methacrylic acid ester monomer unit. Examples of the monomer unit configured here include 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 Rate, dicyclopentenyloxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, acrylic (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acroyloxyethyl succinate, maleic acid 2 -(Meth) acryloyloxyethyl, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate , Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and the like. 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, a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and methyl acrylate or ethyl acrylate is used because of its compatibility with the copolymer (A2) and its industrial availability. Coalescence can be preferably used. The stereoregularity is also not particularly limited, but the stereostructure of the (meth) acrylic acid ester monomer unit is preferably a syndiotactic structure because the glass transition temperature is higher and the heat resistance is improved. Specifically, of the triad fractions mm, mr and rr, the one having the highest molar ratio of the rr structure can be preferably used. The triad fraction can be measured by a known method using a nuclear magnetic resonance analyzer ( ¹ H-NMR).

  As the acrylic resin (A1) used in the present invention, a commercially available product may be used, and specific examples include a product name “Acrypet” manufactured by Mitsubishi Rayon Co., Ltd. and a product manufactured by Sumitomo Chemical Co., Ltd. Examples thereof include the name "SUMIPEX" and the trade 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 acid 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-methylstyrene. Examples include units derived from each styrene-based monomer such as styrene and α-methyl-p-methylstyrene. These aromatic vinyl monomer units may be used alone or in combination of two or more. In the present invention, styrene units and α-methylstyrene units are preferred. The styrene unit is preferable because it is industrially easily available and economically excellent, and the α-methylstyrene unit is preferable because it can improve the glass transition temperature.

  As the (meth) acrylic acid ester monomer unit, each methacrylic acid ester monomer such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, dicyclopentanyl methacrylate, isobornyl methacrylate, etc. , And units derived from acrylic acid ester monomers 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 may be used alone or in combination of two or more. Here, in the present invention, a methyl methacrylate unit can be preferably used in view of compatibility with the acrylic resin (A1) and appearance.

  Examples of the unsaturated dicarboxylic acid anhydride monomer unit include units derived from each anhydride monomer such as maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, and aconitic acid anhydride. These unsaturated dicarboxylic acid anhydride monomer units may be used alone or in combination of two or more. Here, in the present invention, a maleic anhydride unit can be preferably used because of its 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. The anhydride unit is 8 to 20% by mass, more preferably the aromatic vinyl monomer unit 55 to 85% by mass, the (meth) acrylic acid ester monomer unit 5 to 30% by mass, the unsaturated dicarboxylic acid anhydride 10 -18% by mass.
Here, the constitutional unit of the copolymer (A2) can be qualitatively and quantitatively analyzed by a well-known method, for example, a nuclear magnetic resonance (NMR) measurement device or other instrumental analysis device.

  Here, when 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 obtained and the water absorption can be reduced, which is preferable. The content of the (meth) acrylic acid ester monomer unit is preferably 4% by mass or more, more preferably 5% by mass or more, since the compatibility with the acrylic resin (A1) is improved and the transparency is improved, which is preferable. Further, when the unsaturated dicarboxylic acid anhydride monomer unit is preferably 8% by mass or more, more preferably 10% by mass or more, the compatibility with the acrylic resin (A1) is improved and the transparency and heat resistance are improved. It is preferable because

  On the other hand, when the aromatic vinyl monomer unit is preferably 85% by mass or less, it is possible to improve heat resistance and reduce water absorption while maintaining the miscibility with the acrylic resin (A1). When the (meth) acrylic acid ester monomer unit is preferably 45% by mass or less, more preferably 30% by mass or less, it is possible to suppress water absorption while ensuring compatibility with the acrylic resin (A1). preferable. Further, when the unsaturated dicarboxylic acid anhydride unit is preferably 20% by mass or less, more preferably 18% by mass or less, the compatibility with the acrylic resin (A1) is ensured and the thermal stability is improved and the water absorption is improved. It is preferable because the property can be suppressed.

  The copolymer (A2) used in the present invention is a copolymerizable unit other than the aromatic vinyl monomer unit, the (meth) acrylic acid ester monomer unit, and the unsaturated dicarboxylic acid anhydride monomer unit. May be contained in the copolymer in a range that does not impair the effects of the present invention, and is preferably 5% by mass or less. Examples of the copolymerizable unit include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, vinylcarboxylic acid monomers such as acrylic acid and methacrylic acid, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide. , Units derived from each monomer such as N-alkylmaleimide monomer such as N-cyclohexylmaleimide, N-arylmaleimide monomer such as N-phenylmaleimide, N-methylphenylmaleimide and N-chlorophenylmaleimide Is mentioned. These copolymerizable units may 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) of 100,000 to 200,000 as measured by gel permeation chromatography (GPC). When the weight average molecular weight (Mw) is within this range, the acrylic resin layer (A) obtained by mixing with the acrylic resin (A1) is excellent in moldability and appearance, and is therefore preferable. From this viewpoint, the more preferable range of the weight average molecular weight (Mw) is 110,000 to 180,000.

  The method for producing the copolymer (A2) used in the present invention can be produced by a known polymerization method and is not particularly limited. For example, solution polymerization, bulk polymerization, etc. can be applied, and the polymerization process can also employ a batch system, a semi-batch system, a continuous system or the like as appropriate. In the present invention, a batch-type polymerization process can be preferably used in solution polymerization because there are few by-products and it is easy to adjust the molecular weight and control transparency.

  As the copolymer (A2) used in the present invention, a commercially available product may be used, and specific examples thereof are trade names “Regisphi R-100”, “Regisphi R-200” and “Regisphi R-200” manufactured by Denki Kagaku Kogyo Co., Ltd. "Regisphi R-300" and the like.

  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 acid anhydride monomer unit. Containing a copolymer (A2) having a mixing ratio of (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 interlayer adhesion with the polycarbonate resin layer (B) is excellent, and the surface hardness which is a characteristic of the acrylic resin. While maintaining transparency and transparency, improvement of heat resistance and suppression of water absorption are preferable. Further, when the surface hardness is important, (A1) / (A2) = 80 to 55/20 to 45 is preferable, and when the heat resistance improvement and the water absorption suppression are important, (A1) ) / (A2) = 50 to 20/50 to 80 is preferable.

  Various additives and other resins can be appropriately added to the acrylic resin layer (A) of the present invention as long as the effects of the present invention are not impaired. Here, examples of the additive include an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant, a flame retardant, and a colorant. Examples of other resins 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 mentioned.
Examples of the monophenol system include 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, and 2,6-di-tert-butyl-4-ethylphenol. As the bisphenol type, 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- 2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl} 2,4,9,10-tetraoxaspiro] 5,5-undecane can be exemplified.

  As the polymer type phenol type, 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-vidroxybenzyl) benzene, tetrakis- {methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxykisphenyl) 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 include 4'-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) trione, tocopherol (vitamin E) and the like.

  Examples of the sulfur type include dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiopropionate and the like.

Examples of the phosphite system include triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, 4,4'-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, and Click neopentane tetrayl bis (octadecyl phosphite), tris (mono and / or di) phenyl phosphite, diisodecyl pentaerythritol diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenathrene-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-pho Faphenanthrene, cyclic neopentanetetraylbis (2,4-di-tert-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6-di-tert-methylphenyl) phosphite, 2 , 2-methylenebis (4,6-tert-butylphenyl) octylphosphite and the like can be exemplified.
The said antioxidant can be used individually by 1 type or in combination of 2 or more types.

In the present invention, phenol-based and phosphite-based antioxidants such as polymer type phenol-based antioxidants are preferred from the viewpoint of the effect of antioxidants, thermal stability, and economical efficiency. Among them, phosphite-based antioxidants excellent in thermal decomposition resistance are preferred. Antioxidants are more preferred.
The addition amount of the antioxidant is in the range of 0.001 to 0.5 parts by mass, and 0.05 to 0.3 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 parts by mass.

(UV absorber)
As the ultraviolet absorber, various commercially available products can be applied, and various types such as benzophenone-based, benzotriazole-based, triazine-based, and salicylate-based can be used.
Examples of the benzophenone-based ultraviolet absorber 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 -Dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone and the like can be illustrated.

The benzotriazole-based UV absorber is a hydroxyphenyl-substituted benzotriazole compound, such as 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-t-butylphenyl) benzotriazole. 2- (2-hydroxy-3,5-dimethylphenyl) benzotriazole, 2- (2-methyl-4-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-3-methyl-5-t-butylphenyl) ) Benzotriazole, 2- (2-hydroxy-3,5-di-t-amylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole and the like can be illustrated.
Examples of the triazine-based ultraviolet absorber include 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol and 2- (4 , 6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyloxy) phenol can be exemplified.
Examples of salicylic acid ester-based compounds 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 amount of the ultraviolet absorber added is in the range of 0.3 to 5.0 parts by mass and 0.5 to 2.0 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 parts by mass.

(Light stabilizer)
A hindered amine-based light stabilizer can be preferably used as a light stabilizer that imparts weather resistance in addition to the above-mentioned ultraviolet absorber. The hindered amine light stabilizer does not absorb ultraviolet rays like an ultraviolet absorber, but when used in combination with an ultraviolet absorber, it shows a remarkable synergistic effect.

(Hindered amine light stabilizer)
Examples of the hindered amine light stabilizers include dimethyl succinate-1- (2-hydroxyethyl) -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- (1,2,2,2 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 addition amount of the hindered amine light stabilizer is in the range of 0.01 to 0.5 parts by mass, and 0.05 to 0 parts by mass, relative to 100 parts by mass of the resin composition constituting the acrylic resin layer (A). It is preferable to add 0.3 parts by mass.

<Polycarbonate resin layer (B)>
The polycarbonate resin layer (B) shares the function of exhibiting impact resistance and heat resistance among the functions of the laminate. Therefore, although the polycarbonate resin (B1) may be used alone as the polycarbonate resin layer (B), it may be used as a mixture 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. Further, it may be either a homopolymer or a copolymer with another copolymerizable monomer. Further, the structure may be a branched structure, a linear structure, or a mixture of a branched structure and a linear structure.
The polycarbonate resin (B1) used in the present invention may be produced by any known method such as a phosgene method, a transesterification method, or a pyridine method.

  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) may be used alone or in combination of two or more. When the weight average molecular weight is within the above range, impact resistance is ensured and extrusion moldability is good, which is preferable.

  A commercially available product may be used as the polycarbonate resin (B1) used in the present invention, and specific examples of the aromatic polycarbonate resin include “CALIBER” and “CALIBER” manufactured by Sumika Styron Polycarbonate Co., Ltd. SD POLYCA ", product name" Iupilon "manufactured by Mitsubishi Engineering Plastics Co., Ltd.," NOVAREX ", product name" Panlite "manufactured by Teijin Limited, etc. Can be illustrated. In addition, specific examples of the aliphatic polycarbonate-based resin include "DURABIO", trade name, manufactured by Mitsubishi Chemical Corporation.

(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 melt viscosity and improving hardness, and specifically, a specific polyester resin Examples include resin (B2-1) and specific acrylic resin (B2-2).

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

Here, the carboxylic acid monomer (a) unit of the polyester resin (B2-1) contains 80 mol% or more of an aromatic dicarboxylic acid. Here, 80 mol% or more of aromatic dicarboxylic acid in the carboxylic acid monomer (a) unit is preferable because the polyester resin (B2-1) obtained has sufficient heat resistance and mechanical strength. From such a viewpoint, it is more preferable that the aromatic dicarboxylic acid has a lower limit of 85 mol% or more and an upper limit of 100 mol% or less in the carboxylic acid monomer (a) unit. preferable.
The aromatic dicarboxylic acid is not particularly limited, and 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. The aromatic dicarboxylic acid ester is not particularly limited, and the above-mentioned aromatic dicarboxylic acid ester is preferable, and examples thereof include lower alkyl ester, aryl ester, carbonic acid ester, and acid halide. Further, the carboxylic acid monomer (a) unit may contain a small amount of an aliphatic dicarboxylic acid (usually in the range of less than 20 mol%). The aliphatic dicarboxylic acid is not particularly limited, 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. Acid, cyclopentanedicarboxylic acid, 4,4′-dicyclohexyldicarboxylic acid and the like can be mentioned. These carboxylic acid monomers (a) 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. The glycol used in the glycol monomer (b) is not particularly limited except the above-mentioned components, and ethylene glycol, diethylene glycol (including a by-product component), 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) may be used alone or in combination of two or more, and may impart color tone, transparency, heat resistance, impact resistance, etc. to the polyester resin as appropriate. However, ethylene glycol can be preferably used because the obtained polyester resin can be provided with thermal stability during molding, is inexpensive, and is easily available industrially.

  The 1,4-cyclohexanedimethanol used for the glycol monomer (b) mainly imparts impact resistance to the obtained polyester resin (B2-1) and is compatible with the polycarbonate resin (B1). Is to improve. Further, 1,4-cyclohexanedimethanol has two types of isomers, a cis type and a trans type, but any of them may be used. Here, when the content in the glycol monomer (b) unit is 40 mol% or more, the effect of imparting impact resistance to the obtained polyester resin (B2-1) is sufficient, and the polycarbonate type is also preferable. It is preferable because the compatibility with the resin (B1) is improved and the transparency is less likely to decrease. From this viewpoint, it is more preferable that 1,4-cyclohexanedimethanol has a lower limit of 50 mol% or more and an upper limit of 100 mol% or less in the glycol monomer (b) unit. Is preferable, and it is more preferable that the content is 80 mol% or less.

  As the polyester resin (B2-1), a commercially available product may be used, and specific examples include a product name “SKYGREEN J2003” manufactured by SK Chemical Co., Ltd., manufactured by Eastman Chemical Co., Ltd. An example of the product name is "Easter PCTG Copolyester 24635".

The mixing mass ratio of the polycarbonate resin (B1) and the polyester resin (B2-1) is not particularly limited, but (B1) / (B2-1) = 99 to 1/1 to 99 Is preferred, 95-5 / 5-95 is more preferred, and 90-10 / 10-90 is even more preferred. Since the mixed composition of both 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), which 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, and 120 It is particularly preferable that the temperature is ˜140 ° C. 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. Therefore, the temperature can be adjusted to about 100 to 140 ° C. Further, when 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, the temperature is 85 ° C. and the humidity is 85% RH. It is preferable because warpage of the laminate after the wet environment test can be suppressed. From this viewpoint, the absolute value of the difference is more preferably 20 ° C. or lower, further preferably 10 ° C. or lower, and particularly preferably 5 ° C. or lower. This is because the acrylic resin layer (A) in a high temperature and high humidity environment is likely to cause various strain relaxation phenomena due to a decrease in softening temperature due to water absorption, but if the absolute value of the difference is within the above range, It is considered that the dimensional change behavior of both layers becomes close under high temperature and high humidity environment, and as a result, warpage is suppressed.
In the present invention, the glass transition temperature is measured with a differential scanning calorimeter at a heating rate of 10 ° C./min according to JIS K7121, but other known instrumental analyzers, for example, dynamic viscoelasticity It can also be measured with a device or the like.

(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. ..
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, and phenyl methacrylate is more preferable, from the viewpoint of compatibility with the polycarbonate resin (B1).
The acrylic resin (B2-2) may 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, it is preferably 0.1 to 10 mass% in the acrylic resin (B2-2).

  When the aromatic (meth) acrylate monomer unit and the methyl methacrylate monomer unit are within the above ranges, compatibility with the polycarbonate resin (B1) and the effect of improving the surface hardness can be exhibited, which is preferable. From such a viewpoint, it is more preferable that the aromatic (meth) acrylate monomer unit is 10 to 70% by mass and the methyl methacrylate monomer unit is 90 to 30% by mass, and the aromatic (meth) acrylate monomer unit 25 to More preferably, it is 60% by mass and the methyl methacrylate monomer unit is 75 to 40% by mass.

  The acrylic resin (B2-2) preferably has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 5,000 to 30,000. 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 improved moldability, improved surface hardness, and appearance. It is preferable because it is excellent. From this viewpoint, the range of the weight average molecular weight (Mw) is more preferably 10,000 to 28,000.

  A commercially available product may be used as the acrylic resin (B2-2), and specific examples thereof include "METABLEN H-880" manufactured by Mitsubishi Rayon Co., Ltd.

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

  The resin composition constituting the polycarbonate resin layer (B) of the present invention can be appropriately blended with the above-mentioned various additives and other resins within a range that does not impair the effects of the present invention. Examples of additives include antioxidants, ultraviolet absorbers, light stabilizers, lubricants, flame retardants, colorants, and hydrolysis inhibitors.

(Hydrolysis inhibitor)
Examples of the hydrolysis inhibitor include a phenol compound, a carbodiimide compound monomer or polymer, and an oxazoline compound monomer or polymer. In the present invention, a carbodiimide compound monomer or polymer 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. Moreover, as n, an appropriate integer between 1 and 50 is usually selected. When n is an integer of 2 or more, Rs 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). Examples of the carbodiimide compound include carbodiimide), poly (diisopropylphenylenecarbodiimide), poly (methyl-diisopropylphenylenecarbodiimide), poly (triisopropylphenylenecarbodiimide), aromatic polycarbodiimide, and these monomers. The above carbodiimide compounds may be used alone or in combination of two or more. 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, and specific examples thereof include trade names “Stabaxol P”, “Stabaxol P100” manufactured by Rhein Chemie GmbH, and products manufactured by Nisshinbo Chemical Inc. Examples thereof 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, and 0.05 to 0. 0, based on 100 parts by mass of the resin composition constituting the polycarbonate resin layer (B). It is preferable to add 5 parts by mass.

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

(Thickness of laminated body)
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, 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, it 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. Within this range, the weight and rigidity are excellent and the shape stability in a high temperature and high humidity environment is excellent, which is preferable. In addition, when an adhesive layer or the like is laminated on the laminate of the present invention to protect it from stains or scratches on the surface of glass or the like, or when it is applied to an application to prevent scattering of broken pieces, etc. The thickness is preferably 0.6 mm, 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 the shape stability in a high temperature and high humidity environment. And so on. 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. It is more preferable that there is. When the total thickness of the acrylic resin layer (A) and the polycarbonate resin layer (B) is (T), the thickness ratio of one acrylic resin layer (A) ((A) / (T)) Is preferably 0.01 to 0.35, more preferably 0.05 to 0.30, and further preferably 0.07 to 0.20. When the thickness and the thickness ratio are within the above ranges, the surface hardness and impact resistance of the laminate are excellent and the shape stability in a high temperature and high humidity environment 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, more preferably 89% or more. The total light transmittance in the present invention is measured according to JIS K7361-1.

(Warp evaluation)
The warp evaluation of the laminate of the present invention is carried out as follows. That is, a 100 mm square test piece (n = 3) was cut out from the obtained laminated body, and first left in an environment of temperature 23 ° C. and humidity 50% RH for 24 hours. Next, each test piece was left in an environment of temperature 85 ° C. and humidity of 85% RH for 120 hours, then left in an environment of temperature 23 ° C. and humidity of 50% RH for 24 hours, and then the test piece was allowed to stand on a surface plate, The height of the four corners from the surface plate was measured as the amount of warpage, and the average of the absolute values was evaluated. By making the environmental conditions the same before and after being left in a high temperature and high humidity environment, only the effect in 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. Within the above range, the laminate can be used in a wider range of applications and environments, which is preferable.

In the present invention, the warp evaluation was performed under the temperature of 85 ° C. and the humidity of 85% RH. However, as the high temperature and high humidity environment, the conditions of the temperature of 60 ° C., the humidity of 90% RH, the temperature of 70 ° C., the humidity of 90% RH, etc. May be used.
Moreover, as a method of reducing the warp, a method of forming a film so as not to impart strain that adversely affects the production of the laminate, or a method of relaxing strain by annealing for several hours to several days in the vicinity of Tg can be exemplified. Specifically, it may be adjusted so as to reduce the heat shrinkage rate under the environmental conditions to be evaluated. Further, it can be adjusted by the thickness and type of coating on the front and back surfaces of the hard coat layer (C) described later.

(Method for manufacturing laminated body)
Next, a method for manufacturing the laminate of the present invention will be described, but the method is not particularly limited. As a film forming method, there is a known method, for example, a single screw extruder, a multi-screw extruder, a Banbury mixer, a kneader, and other melt mixing equipment, and the extrusion casting method using a T die is advantageous in terms of handleability and productivity. Can be preferably used. As a method for forming the laminate, a method in which the melt-kneaded resin is coextruded by a feed block or a T die having a multi-manifold can be preferably used. Further, in order to improve the appearance of the laminate, it is preferable to use a molding roll having a mirror-finished surface (such as a metal elastic roll or a polishing roll).
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 used, but is generally 300 ° C or lower, preferably 230 to 270 ° C. The forming roll has a temperature of approximately 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 an extruder for each layer preferably has a vent function and a filter function. The vent function is preferable because it can be utilized for drying the resin composition used for each layer, removing a trace 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 thereof include a leaf disc filter, a back disc filter, a cone type filter, a candle filter, and a cylindrical type filter. Above all, a leaf disk filter that can easily secure an effective filtration area is preferable. The filter function is preferable because foreign matters, minute gel lumps and the like can be removed, and a laminated body with less defective appearance can be obtained.

  The resin composition used in the present invention may be used by mixing the respective components in advance with a mixer such as a tumbler, a V-type blender, a Banbury mixer, an extruder, or the like. The components may be directly supplied, or the components weighed separately may be supplied to the respective supply ports of an extruder having two or more supply ports. Further, as a method of mixing various additives, a known method can be used. For example, (a) a masterbatch in which various additives are mixed with a suitable base resin in a high concentration (a typical content is about 3 to 60% by mass) is prepared separately, and the concentration is adjusted to the resin used. And a method of mixing various additives, and a method of directly mixing various additives with 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.
The surface hardness can be evaluated using the pencil hardness as one index. In the present invention, the pencil hardness of the surface to be measured was measured under a load of 750 g according to JIS K5600-5-4.
The pencil hardness of the surface of the acrylic resin layer (A) of the laminate of the present invention is preferably H or higher, more preferably 2H or higher, and particularly preferably 3H or higher. The pencil hardness of the surface of the hard coat layer (C) applied to the outer surface side is preferably 4H or higher, more preferably 5H or higher, and particularly preferably 7H or higher. When the pencil hardness is 4H or more, a laminate having excellent surface hardness can be provided. The pencil hardness of the surface of the hard coat layer (C) applied to the inner surface side is preferably F or higher, and more preferably H or higher. When the pencil hardness is F or more, it can function as a scratch-preventing layer for preventing a scratch on the laminate during transportation or processing in 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, when rubbing with # 0000 steel wool under a load of 1000 gf, it is preferable that the number of reciprocations before scratches be 20 or more. When the number of reciprocations until scratches occur on the surface when rubbing with the steel wool is 20 or more, a scratch-resistant laminate having excellent scratch resistance can be provided. From this viewpoint, the number of reciprocations until the surface is scratched is preferably 20 or more, more preferably 300 or more, and particularly preferably 500 or more.

(Hard coating agent)
The hard coating agent is not particularly limited in the present invention, but those which are cured by irradiation with energy rays such as electron beam, radiation, and ultraviolet rays, or which are cured by heating can be applied. In the present invention, from the viewpoint of molding time and productivity, it is preferably made of an ultraviolet curable resin.
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 thereof include vinyl ether compounds and oxetane compounds. These curable resins can be used alone or in combination of two or more. As the curable resin that imparts more excellent surface hardness, a polyfunctional acrylate compound, a polyfunctional urethane acrylate compound, a polyfunctional epoxy acrylate compound, a radical-polymerizable curable compound, an alkoxysilane, an alkylalkoxysilane, or the like Polymerizable curable compounds may be mentioned, and further, an organic / inorganic composite curable resin composition obtained by incorporating an inorganic component in the curable resin may be used.

As a curable resin composition that imparts particularly excellent surface hardness, an organic / inorganic hybrid curable resin composition can be mentioned. Examples of the organic / inorganic hybrid curable resin composition include a curable resin composition in which the curable resin contains an inorganic component having a reactive functional group.
By utilizing an inorganic component having such a reactive functional group, for example, the inorganic component is copolymerized and cross-linked with a radical-polymerizable monomer to simply add an inorganic component to an organic binder to form an organic-inorganic composite. As compared with the system curable resin composition, curing shrinkage is less likely to occur, and high surface hardness can be exhibited, which is preferable. Further, from the viewpoint of reduction in 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). The preferred 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 preferable concentration is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 40% by mass or more. When the concentration is 10% by mass or more, the effect of imparting excellent surface hardness to the hard coat layer (C) can be obtained, which is preferable. On the other hand, the upper limit of the preferable concentration is preferably 65% by mass or less, more preferably 60% by mass or less, and particularly preferably 55% by mass or less. When the concentration is 65% by mass or less, it becomes possible to close-pack the inorganic component and / or the inorganic component having a reactive functional group in the hard coat layer (C), resulting in excellent surface hardness. It is preferable because it can be added selectively.

As a method for forming the hard coat layer (C), for example, a coating film obtained by dissolving or dispersing the above-mentioned curable resin composition in an organic solvent is applied to the surface of the resin layer to form a cured film. There is a method of forming and laminating on the surface of the resin layer, but the method is not limited to this.
As a method for laminating with the resin layer, a known method is used. For example, laminating method using a 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, A gravure coating method and the like can be mentioned. In addition, for example, a method of laminating the hard coat layer (C) on the resin layer by using a transfer sheet in which the hard coat layer (C) is formed on the release layer may be adopted.
Further, for the purpose of improving the adhesion between the hard coat layer (C) and the resin layer, the surface of the resin layer may be subjected to various surface treatments such as corona treatment, plasma treatment and primer treatment.

The curable resin composition forming the hard coat layer (C) is preferably composed of an ultraviolet curable resin, that is, a composition curable by irradiation with ultraviolet rays from the viewpoint of molding time and productivity. Here, as the light source which emits ultraviolet rays, an electrodeless high pressure mercury lamp, an electrode high pressure mercury lamp, an electrodeless metal halide lamp, an electrode metal halide lamp, a xenon lamp, an ultrahigh pressure mercury lamp or a mercury xenon lamp can be used. Among them, the electrodeless high-pressure mercury lamp is preferable because it can easily obtain ultraviolet rays with high illuminance and is advantageous for curing the ultraviolet curable resin.
Further, in the ultraviolet curable resin, a photopolymerization initiator added absorbs ultraviolet rays and is excited and activated to cause a polymerization reaction, whereby 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, because it is advantageous for curing the ultraviolet curable resin.

(Photopolymerization initiator)
When the curable resin composition comprises 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 its derivatives, thioxanthones, benzyl dimethyl ketals, α-hydroxyalkylphenones, α-hydroxyacetophenones, hydroxyketones, aminoalkylphenones, acylphosphine oxides. And so on. Among them, α-hydroxyalkylphenones are preferable because they hardly cause yellowing upon curing and a transparent cured product is obtained. Further, aminoalkylphenones are preferable because they have extremely high reactivity and a cured product with excellent hardness can be obtained. The photopolymerization initiators may be used alone or in combination of two or more. 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.

  The photopolymerization initiator may be a commercially available product, and specific examples thereof include "IRGACURE 651", "IRGACURE 184", "IRGACURE 500", "IRGACURE 1000", "IRGACURE 2959", "DAROCUR 1173", "IRGACURE 127", and "IRGACURE 907". "," IRGACURE369 "," IRGACURE379 "," IRGACURE1700 "," IRGACURE1800 "," IRGACURE819 "," IRGACURE784 "[The above IRGACURE (Irgacure) series and DAROCUR (DAROCUR) products are BASF Japan products]. Name], "KAYACUREITX", "KAYACUREDETX-S", "KAYAC REBP-100 "," KAYACUREBMS "," KAYACURE2-EAQ "[more KAYACURE (Kayacure) series, manufactured by Nippon Kayaku Co., Ltd. under the trade name], and others. Of these, examples of the above-mentioned α-hydroxyalkylphenones include, for example, “IRGACURE184”, and examples of those belonging to the aminoalkylphenones include, for example, “IRGACURE907”, “IRGACURE369”, and “IRGACURE379”. Can be mentioned.

(Surface adjustment component)
The curable resin composition forming the hard coat layer (C) may include a leveling agent as a surface conditioning component. Examples of the leveling agent include silicone leveling agents and acrylic leveling agents. Particularly, those having a reactive functional group at the terminal are preferable, and those having a bifunctional or higher functional group are more preferable. preferable.
Specifically, a polyether-modified polydimethylsiloxane having an acrylic group having a double bond at both ends (for example, trade names "BYK-UV 3500" and "BYK-UV 3530" manufactured by BYK Japan KK). And polyester-modified polydimethylsiloxane having an acrylic group having two double bonds at the end and a total of four double bonds (trade name “BYK-UV 3570” manufactured by BYK Japan KK). Among these, polyester-modified polydimethylsiloxane having an acrylic group, which has a stable haze value and contributes to the improvement of scratch resistance, is particularly preferable.

(Other ingredients)
The curable resin composition forming the hard coat layer (C) includes, in addition to the curable resin component, for example, a lubricant such as a silicon compound, a fluorine compound, or a mixed compound thereof, an antioxidant, an ultraviolet absorber, and the like. Various additives such as agents, antistatic agents, flame retardants such as silicone compounds, fillers, glass fibers, impact modifiers, etc. 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 irradiation with ultraviolet rays, curing of the interior of the resin composition progresses rapidly because of its high transparency to ultraviolet rays, but the curing inhibitory action by oxygen ( Due to oxygen damage), the curing of the surface of the resin composition may be delayed. With respect to this oxygen damage, it is preferable to irradiate the resin composition with a nitrogen gas atmosphere around the resin composition in a nitrogen gas atmosphere and then to irradiate the resin composition with ultraviolet light so that the surface of the resin composition and the surface of the resin composition can be rapidly cured. ..

  The thickness of the hard coat layer (C) described above 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. It is more preferable that it is present, and it is particularly preferable that it is in the range of 7 to 15 μm. Here, if the thickness of the hard coat layer (C) is in the above range, scratch resistance can be imparted, and cracks due to stress are less likely to occur, which is preferable. 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 more than the thickness of the hard coat layer on the surface of the polycarbonate resin layer (B).

  The laminate of the present invention and the laminate having the hard coat layer (C) are subjected to any one or more of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment on one surface or both surfaces thereof. be able to. The method of each treatment is not particularly limited, and a known method can be used. For example, a method of applying a reflection reducing paint, a method of depositing a dielectric thin film, a method of applying an antistatic paint and the like can be exemplified.

(Assumed use)
As described above, the laminate of the present invention is excellent in economic efficiency by using a general-purpose material as a main raw material, and is used for a substrate material and a protective material, and has transparency, impact resistance, surface hardness, high temperature and high temperature. Since the laminate has excellent shape stability in a humid environment, it can be applied to various applications and 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 preferably used for automobile instruments and the like).
Further, the laminate of the present invention or the laminate having another layer such as the hard coat layer (C) may be given a shape by various processing methods. Specifically, a method of heating / pressurizing using a die, a pressure molding, a vacuum molding, a roll homing method and the like can be exemplified. By giving a shape, it can be expected to be applied to an image display device having a curved surface and various flexible devices.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In addition, 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 Perkin Elmer Co., Ltd., trade name “Pyris1 DSC”, according to JIS K7121, about 10 mg of a 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 the temperature was raised to 200 ° C. at a heating rate of 10 ° C./min. ) (° C.) was determined. In addition, the value of Tg was rounded off to the first decimal place.

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

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

(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 an environment of a temperature of 23 ° C. and a humidity of 50% RH. Next, each test piece was left in an environment of temperature 85 ° C. and humidity of 85% RH for 120 hours, then left in an environment of temperature 23 ° C. and humidity of 50% RH for 24 hours, and then the test piece was allowed to stand on a surface plate, The height from the surface plate of the four corners was measured as the amount of warp, and the average of the absolute values was evaluated according to the following criteria.
(A) Warpage amount is 0.5 mm or less (O) Warpage amount is more than 0.5 mm, 1.5 mm or less (X) Warpage amount is more than 1.5 mm

(5) Adhesion Regarding the adhesion between the hard coat layer (C) and the surface of the laminate, a cross-cut test was performed according to JIS K5600-5-6, and peeling of the hard coat layer was not observed. Passed (○).

(6) Evaluation of Scratch Resistance The scratch resistance of the hard coat layer (C) was measured by the following apparatus and conditions, and the number of reciprocations before scratches was 500 times or more was regarded as pass (◯). ..
・ Device: Friction fastness tester Gakushin type (manufactured by Daiei Kagaku Seiki Co., Ltd.)
・ 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 shown 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 mass%, stereoregularity (Triad fraction): mm (9.2 mol%), mr (41.8 mol%), rr (49.0 mol%), Tg: 111 ° C, MFR (temperature: 230 ° C, load: 37.3N) ): 2.0 g / 10 min)

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

(Copolymer (A2))
(A2-1); Copolymer (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: Resphi 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: Resphi 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 Styron 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 Styron Polycarbonate Co., Ltd., trade name: Caliber 301-10, density: 1.20 g / cm ³ , Tg: 149 ° C., MFR (temperature: 300 ° C., load: 11.8N): 10.0g / 10min)

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

(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: Metabrene H-880, phenyl methacrylate / methyl methacrylate = 34/66 mass%, weight average molecular weight: 14,000)

(Additive) (X)
(X-1); Phosphite-based antioxidant (manufactured by ADEKA, trade name: ADEKA 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 & Sumitomo Metal Corporation, trade name: Estyrene MS-600, density: 1.13 g / cm ³ , methyl methacrylate / styrene = 60/40 mass%, MFR (temperature : 230 ° C, load: 37.3N): 5.0g / 10min)

<Example 1>
As shown in Table 1, as the acrylic resin layer (A), 60 parts by mass of the acrylic resin (A1-1), 40 parts by mass of the copolymer (A2-1), and (X-1) 0. Resin composition mixed at a ratio of 15 parts by mass, and as the polycarbonate resin layer (B), 60 parts by mass of the polycarbonate resin (B1-1) and 40 parts by mass of the polyester resin (B2-1-1) and addition. The resin composition prepared by mixing 0.15 parts by mass of (X-1) and 0.10 parts by mass of (X-2) as an agent was supplied to separate extruders having a vent function and a filter function, respectively, and the resin temperature was adjusted. Melt kneading at 240 to 265 ° C., co-extrusion molding with a T die at 260 ° C. so as to have a laminated structure of (A) layer / (B) layer in a feed block, and then cast cooling with a mirror surface roll at 95 ° C. However, the total thickness is 0.70 m, to obtain each layer thickness of the layer (A) / (B) layer = the laminate is 0.08 mm / 0.62 mm. The obtained laminate had a good appearance and excellent flatness. Table 1 shows the results of evaluation using the laminate.

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

<Comparative Example 1>
As shown in Table 1, in the same manner as in Example 1, except that the acrylic resin layer (A) was changed to a single acrylic resin (A1-1), the total thickness was 0.70 mm and the appearance and flatness were excellent. A laminated body was obtained. Table 1 shows the results of evaluation using the laminate.

<Comparative example 2>
As shown in Table 1, as the acrylic resin layer (A) in Example 1, the resin composition was changed to 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 for the above. However, the adhesion between the acrylic resin layer (A) and the polycarbonate resin layer (B) was insufficient, so that the film could be easily peeled by hand and the evaluation was stopped.

<Comparative example 3>
As shown in Table 1, a laminate having a total thickness of 0.70 mm was prepared in the same manner as in Example 1 except that the copolymer (A2-1) was changed to (P-1) as the acrylic resin layer (A). Got the body However, since the acrylic resin (A1-1) and the MS resin (P-1) had poor compatibility, the acrylic resin layer (A) was clouded and the evaluation was stopped.

<Example 9>
Organic / inorganic hybrid UV curable resin composition (trade name "UVHC7800G" manufactured by MOMENTIVE, containing inorganic silica having a reactive functional group) on the surface of the acrylic resin layer (A) of the laminate obtained in Example 1. (Amount: 30-40% by mass) is applied using a metal bar coater, dried at 90 ° C. for 1 minute, and then exposed with an exposure amount of 500 mJ / cm ² using an ultraviolet irradiation device to obtain 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 as in Example 9, except that the coating surface and the thickness of the hard coat layer were changed. Table 2 shows the results of evaluating the hard coat layer of the laminate. When coating on both sides, a hard coat layer was formed on each side, and each side was similarly irradiated with ultraviolet rays.

<Example 15>
In Example 8, as the polycarbonate resin layer (B), 100 parts by mass of the polycarbonate resin (B1-3) was added to 90 parts by mass of (B1-2) and 10 parts by mass of (B2-2-1) resin composition. 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 obtained laminate had a 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). Then, as shown in Table 2, a laminate having a hard coat layer (C) was obtained in the same manner as in Example 9, except that the coating surface and the 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 the acrylic resin layer (A) on at least one surface of the polycarbonate resin layer (B), which contains the resin composition specified in the present invention in a specific range, is transparent. It can be confirmed that the material has excellent properties, surface hardness, and shape stability under a high temperature and high humidity environment (Examples 1 to 8). Further, the laminate having an absolute value of the glass transition temperature of the acrylic resin layer (A) and the glass transition temperature of the polycarbonate resin layer (B) of 5 ° C. or less has a shape stability in a high temperature and high humidity environment. It can be confirmed that it is more excellent (Example 1, Examples 3 to 5).
On the other hand, it can be confirmed that the laminate outside the range specified in the present invention has one or more defects (Comparative Examples 1 to 3). When the acrylic resin layer (A) is a general-purpose acrylic resin alone, the shape stability in a 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 Outside the range of the present invention, the adhesion between the layers is insufficient (Comparative Example 2), and the copolymer mixed with the acrylic resin layer (A) is not compatible with the acrylic resin (A1) outside the range of the present invention. It can be confirmed that compatibility is not exhibited and transparency is not obtained (Comparative Example 3).

  From Table 2, it can be confirmed that by coating the surface of the laminate of the present invention with the hard coat layer (C), the surface hardness can be improved and scratch resistance can be imparted. Further, it can be confirmed that the adhesion between the surface of the laminate of the present invention and the hard coat layer (C) is also excellent (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 exhibiting excellent surface hardness, while the hard coat layer (C) applied to the inner surface side is used in the process. It is possible to share the function of a scratch-preventing layer for preventing a scratch on the laminate during transportation or processing.

Claims (18)

A laminate having an acrylic resin layer (A) on at least one surface of a polycarbonate resin layer (B), the acrylic resin layer (A) comprising an acrylic resin (A1) and an aromatic vinyl monomer unit. It contains a copolymer (A2) having a (meth) acrylic acid ester monomer unit and an unsaturated dicarboxylic acid anhydride monomer unit, and its mixing mass ratio is (A1) / (A2) = 80 to 55 / 20 to 45 , and the difference between the glass transition temperature of the acrylic resin layer (A) and the glass transition temperature of the polycarbonate resin layer (B) measured with a differential scanning calorimeter at a heating rate of 10 ° C./min. Is 20 ° C. or less in absolute value. 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 the triad fractions determined by nuclear magnetic resonance measurement ( ¹ H-NMR) is The laminate according to claim 1, which is the highest one.   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 8 to 20% by mass of an unsaturated dicarboxylic acid anhydride unit. %, The laminated body according to claim 1 or 2. Using a differential scanning calorimeter, claim 1-3 where the glass transition temperature of the acrylic resin layer (A) as measured at a heating rate of 10 ° C. / min, characterized in that a 100 to 140 ° C. 1 The laminate according to item. The glass transition temperature of the acrylic resin layer (A) measured by a differential scanning calorimeter at a heating rate of 10 ° C./min is 115 to 140 ° C., and the glass transition temperature of the polycarbonate resin layer (B). stack of absolute value according to any one of claims 1 to 4, characterized in that at 10 ° C. or less of the difference between the. Polycarbonate-based resin layer (B) is according to any one of claims 1 to 5, characterized in that it contains at least one modifier (B2) selected from the following polycarbonate resin (B1) Laminate.
Modifier (B2)
(B2-1): 80 mol% or more of aromatic dicarboxylic acid as a carboxylic acid monomer (a) unit and 40 mol% or more of 1,4-cyclohexanedimethanol as a glycol monomer (b) unit Polyester Resin (B2-2) Consisting of Structural Units: Acrylic Copolymer Consisting of Aromatic (Meth) Acrylate Monomer Units 5-80% by Mass and Methyl Methacrylate Monomer Units 95-20% by Mass A phosphite type antioxidant is mixed with the acrylic resin layer (A), The laminated body according to any one of claims 1 to 7 . A carbodiimide compound is mixed in the polycarbonate resin layer (B), and the laminate according to any one of claims 1 to 8 . Acrylic thickness of the resin layer (A), the laminate according to any one of claims 1 to 8, characterized in that a 0.01 to 0.25 mm. When the total thickness of the acrylic resin layer (A) and the polycarbonate resin layer (B) is (T), the thickness ratio ((A) / (T)) of one acrylic resin layer (A) is 0. the laminate according to any one of claims 1 to 9, characterized in that a .01～0.35. Co-extrusion molding was carried out, The laminated body of any one of Claims 1-10 characterized by the above-mentioned. The laminate according to any one of claims 1 to 11, characterized in that said at least one surface hard coat layer of the laminate (C) are laminated. The laminate according to claim 12, wherein the surface of the hard coat layer (C) has a pencil hardness of 4H or more. The laminate according to claim 12 or 13, wherein the hard coat layer (C) is composed of an organic / inorganic hybrid curable resin composition. One or more of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment are applied to one or both surfaces of the laminate and the laminate having the hard coat layer (C). The laminated body according to any one of claims 12 to 14 . Substrate material using a laminate according to any one of claims 1 to 15. Protective material using a laminate according to any one of claims 1 to 15. An image display device comprising a laminate according to any one of claims 1 to 15.