JP6908083B2 - 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 in particular, it can be suitably used as a surface protective panel of an image display device and a cover material of a mobile phone, a smartphone, a tablet device, or the like. Regarding the laminate.

Conventionally, glass has been mainly used as a cover material for an image display device. However, since glass is easily broken by impact and is heavy, alternatives to resin materials are being considered. Here, the resin material is mainly required to have impact resistance, surface hardness, and shape stability in a high temperature or high humidity environment.

Polycarbonate resin plates are transparent and have excellent impact resistance and heat resistance, so they are used for soundproof bulkheads, carports, signboards, glazing materials, lighting equipment, etc., but they are scratched due to their low surface hardness. There is a drawback that it is easy to stick, and its use is limited.

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

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

Japanese Unexamined Patent Publication No. 2006-103169 Japanese Unexamined Patent Publication No. 2010-1676559 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, the heat resistance of the polycarbonate resin and the acrylic resin, which is mainly represented by the glass transition temperature, and There is a problem that a difference in dimensional change occurs due to a difference in water absorption characteristics and the like, 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. 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 of high temperature and high humidity. Further, the heat resistance of the MS resin whose water absorption rate is reduced by increasing the styrene content of the copolymerization component (40% by mass or more) tends to decrease, and the compatibility with the acrylic resin also decreases.
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 warp is substantially stretched by 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. In addition, the modified polycarbonate resin specifically used is a special raw material and has a problem in terms of economy.

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

As a result of diligent studies, the present inventors have made a laminate having a specific acrylic resin layer on at least one side of the polycarbonate resin layer, thereby providing impact resistance, surface hardness, and in a high temperature and high humidity environment. We have found that it is excellent in shape stability, and have completed the present invention.
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 side of the polycarbonate resin layer (B), wherein the acrylic resin layer (A) is an acrylic resin (A1) and a single amount of aromatic vinyl. It contains a copolymer (A2) having a body unit, a (meth) acrylic acid ester monomer unit and an unsaturated dicarboxylic acid anhydride monomer unit, and the mixed mass ratio thereof is (A1) / (A2) = 80. A laminate characterized by being ~ 20/20 ~ 80.
(2) The acrylic resin (A1) contains a methyl methacrylate monomer unit as a main component, and has a triad fraction of mm, mr, rr, which is determined by ^{nuclear magnetic resonance measurement (1 H-NMR), and has an rr structure.} The laminate according to (1) above, which has the highest molar ratio.
(3) The constituent unit of the copolymer (A2) is an aromatic vinyl monomer unit of 45 to 85% by mass, a (meth) acrylic acid ester monomer unit of 4 to 45% by mass, and an unsaturated dicarboxylic acid anhydride unit of 8. The laminate according to the above (1) or (2), which is characterized by having a content of ~ 20% by mass.
(4) The above (1) to (3), wherein the mixed 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 the above items.
(5) The above (1) to (3), wherein the mixed 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 the above items.
(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 temperature of the polycarbonate resin layer (B) is 100 to 140 ° C. 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) The glass of the acrylic resin layer (A) glass transition temperature 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 (1) to (5) above, wherein the absolute value of the difference from the transition temperature is 10 ° C. or less.
(8) Any of the above (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 laminate according to item 1.
Modifier (B2)
(B2-1): Contains 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) composed of structural units: Acrylic copolymer (9) composed of 5 to 80% by mass of aromatic (meth) acrylate monomer unit and 95 to 20% by mass of methyl methacrylate monomer unit. The laminate according to any one of (1) to (8) above, wherein the acrylic resin layer (A) is mixed with a phosphite-based antioxidant.
(10) The laminate according to any one of (1) to (9) above, wherein the carbodiimide compound is mixed in the polycarbonate resin layer (B).
(11) The laminate according to any one of (1) to (10) above, wherein the thickness of the acrylic resin layer (A) is 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 ((A) / (T)) of one layer of the acrylic resin layer (A) is , 0.01 to 0.35. The laminate according to any one of (1) to (11) above.
(13) The laminate according to any one of (1) to (12) above, which is coextruded.
(14) The laminate according to 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) above, wherein the pencil hardness of the surface of the hard coat layer (C) is 4H or more.
(16) The laminate according to (14) or (15) above, wherein the hard coat layer (C) is made of an organic / inorganic hybrid curable resin composition.
(17) 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 and the laminate having the hard coat layer (C). The laminate according to any one of the above (1) to (16).
(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 including the laminate according to any one of (1) to (17) above.

According to the present invention, a laminate having excellent impact resistance, surface hardness, and shape stability in a high temperature or high humidity environment is provided, and the laminate can be used as various substrate materials, protective materials, and the like. Specifically, portable display devices (mobile phone terminals, smartphones, portable electronic play equipment, mobile information terminals, tablet devices, mobile personal computers, etc.) and stationary display devices (LCD TVs, LCD monitors, desktop personal computers, car navigation systems, etc.) It can be suitably used for automobile instruments, etc.).

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

<Acrylic resin layer (A)>
The acrylic resin layer (A) has a copolymer weight having 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 a coalescence (A2).
The acrylic resin layer (A) shares the functions of the laminated body, particularly the function of exhibiting surface hardness and heat resistance. Therefore, the acrylic resin layer (A) may be laminated on both sides of the polycarbonate resin layer (B) described later, but it is necessary that the acrylic resin layer (A) 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 polymerized with 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 constituting here includes methyl methacrylate, methacrylic acid, acrylic acid, benzyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and 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) acroyloxyethyl succinate, 2- (meth) acroyloxyethyl maleate, 2- (Meta) acroyloxyethyl phthalate, 2- (meth) aclioil oxyethyl hexahydrophthalate, pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, Examples thereof include 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-based monomer units and vinyl-based monomer units.

Here, in the present invention, a homopolymer of methyl methacrylate or the co-weight of methyl methacrylate and methyl acrylate or ethyl acrylate because of compatibility with the copolymer (A2) and industrial availability. Coalescence can be preferably used. Further, the three-dimensional regularity is not particularly limited, but the three-dimensional structure of the (meth) acrylic acid ester monomer unit is preferable because the glass transition temperature is higher and the heat resistance is improved as the stereotactic structure is formed. Specifically, among 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 measuring device ( ^{1 H-NMR).}

As the acrylic resin (A1) used in the present invention, a commercially available product can be used, and specific examples thereof include a product name "Acrypet" manufactured by Mitsubishi Rayon Co., Ltd. and a product 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 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-methyl Examples thereof 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 preferable. The styrene unit is preferable because it is industrially easily available and is excellent in economy, and the α-methylstyrene unit is preferable because the glass transition temperature can be improved.

As the (meth) acrylic acid ester monomer unit, each methacrylate ester monomer such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, dicyclopentanyl methacrylate, and isobornyl methacrylate , 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, the methyl methacrylate unit can be preferably used from the viewpoint 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, the maleic anhydride unit can be preferably used because of its compatibility with the acrylic resin (A1) and its transparency.

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

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 the appearance is good when mixed with the acrylic resin (A1). Is preferable because water absorption can be reduced. When the (meth) acrylic acid ester monomer unit is preferably 4% by mass or more, more preferably 5% by mass or more, compatibility with the acrylic resin (A1) is improved and 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 to do so.

On the other hand, when the aromatic vinyl monomer unit is preferably 85% by mass or less, the heat resistance can be improved and the water absorption can be reduced while maintaining the mixing property with the acrylic resin (A1), which is preferable. When 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, when the unsaturated dicarboxylic acid anhydride unit is preferably 20% by mass or less, more preferably 18% by mass or less, the thermal stability is improved and water absorption is improved while ensuring compatibility with the acrylic resin (A1). It is preferable because it can suppress the sex.

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 as long as the effect of the present invention is not impaired, and is preferably 5% by mass or less. Examples of 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. , N-alkylmaleimide monomer such as N-cyclohexylmaleimide, N-arylmaleimide monomer such as N-phenylmaleimide, N-methylphenylmaleimide, N-chlorophenylmaleimide, etc. Can be mentioned. As these copolymerizable units, only one type may be used alone, or two or more types may be used in combination.

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). Here, when the weight average molecular weight (Mw) is in this range, the acrylic resin layer (A) obtained by mixing with the acrylic resin (A1) is excellent in moldability and appearance, which is preferable. From this point of view, 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 is not particularly limited as it can be produced by a known polymerization method. For example, solution polymerization, bulk polymerization and the like can be applied, and as the polymerization process, batch type, semi-batch type, continuous type and the like can be appropriately adopted. In the present invention, the batch polymerization process can be preferably used in solution polymerization because there are few by-products and it is easy to control the molecular weight adjustment and transparency.

As the copolymer (A2) used in the present invention, a commercially available product can be used, and specific examples thereof are the trade names "Registfy R-100", "Registfy R-200" and "Registfy R-100" manufactured by Denki Kagaku Kogyo Co., Ltd. “Registry R-300” and the like 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 acid anhydride monomer unit. The copolymer (A2) having the above is contained, and the mixed 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 interlayer adhesion with the polycarbonate resin layer (B) is excellent, and the surface hardness which is a feature of the acrylic resin is excellent. It is preferable because it improves heat resistance and suppresses water absorption while maintaining transparency. Further, when the surface hardness is emphasized, (A1) / (A2) = 80 to 55/20 to 45 is preferable, and when the improvement of heat resistance and the suppression of water absorption are emphasized, (A1). ) / (A2) = 50 to 20/50 to 80.

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 antioxidants, ultraviolet absorbers, light stabilizers, lubricants, flame retardants, colorants and the like. In addition, examples of other resins include a methyl methacrylate-maleic anhydride copolymer and the like.

(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 hydroxyanisol, and 2,6-di-tert-butyl-4-ethylphenol. As the bisphenol system, 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 and the like can be exemplified.

Examples of the high molecular weight phenol type include 1,1,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane and 1,3,5-trimethyl-2,4,6-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) 3,5-Di-tert-butyl-4-bidroxybenzyl) benzene, tetrakis- {methylene-3- (3', 5'-di-tert-butyl-4'-hydrokisphenyl) propionate} methane, bis {(3,3'-bis-4'-hydroxy-3'-tert-butylphenyl) butyric acid} glucole 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 the sulfur system include dilaurylthiodipropionate, dimyristylthiodipropionate, and distearylthiopropionate.

Phenylphosphite systems include triphenyl phosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, 4,4'-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, and cy. Crickneopentantetraylbis (octadecylphosphite), tris (mono and / or di) phenylphosphite, diisodecylpentaerythritol diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenaslen-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-phosphaphenanthrene, cyclic neopentantetraylbis (2,4-di-tert-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6-di) Examples thereof include -tert-methylphenyl) phosphite and 2,2-methylenebis (4,6-tert-butylphenyl) octylphosphite.
The above-mentioned antioxidant may be used alone or in combination of two or more.

In the present invention, phenolic and phosphite-based antioxidants such as polymer-type phenolic agents are preferable from the viewpoint of the effect of the antioxidant, thermal stability, economy, etc. 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 is 0.05 to 0.3. It is preferable to add by mass.

(UV absorber)
As the ultraviolet absorber, various commercially available products can be applied, and various types such as benzophenone type, benzotriazole type, triazine type, and salicylic acid ester type can be mentioned.
Examples of benzophenone-based ultraviolet absorbers include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 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 thereof include −dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′, 4,4′-tetrahydroxybenzophenone and the like.

Examples of the benzotriazole-based ultraviolet absorber include hydroxyphenyl-substituted benzotriazole compounds, 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 exemplified.
Examples of the triazine-based UV absorber include 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl] -5- (octyloxy) phenol and 2- (4). , 6-Diphenyl-1,3,5-triazine-2-yl) -5- (hexyloxy) phenol and the like can be exemplified.
Examples of the salicylic acid ester system include phenylsalicylate and p-octylphenylsalicylate.
The above-mentioned ultraviolet absorber may be used alone or in combination of two or more.
The amount of the ultraviolet absorber added 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), and is 0.5 to 2.0. It is preferable to add by mass.

(Light stabilizer)
As a light stabilizer that imparts weather resistance in addition to the above-mentioned ultraviolet absorber, a hindered amine-based light stabilizer can be preferably used. Hindered amine-based light stabilizers do not absorb UV rays like UV absorbers, but show a significant synergistic effect when used in combination with UV absorbers.

(Hindered amine light stabilizer)
Examples of the hindered amine-based photostabilizer include dimethyl-1- (2-hydroxyethyl) succinate-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate and 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-hydroxybenzyl) -2-n-butylmalate bis (1,2,2,6,6-pentamethyl-4-piperidyl) and the like can be exemplified.
The amount of the hindered amine-based 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 is 0.05 to 0. It is preferable to add 3 parts by mass.

<Polycarbonate resin layer (B)>
The polycarbonate-based resin layer (B) shares the functions of the laminated body, particularly the function of exhibiting impact resistance and heat resistance. Therefore, the polycarbonate-based resin layer (B) may use the polycarbonate-based resin (B1) alone, but may be mixed 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 also 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 the branched structure and the linear structure.
As the 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, and particularly preferably 22,000 to 28,000. Can be used. Only one type of polycarbonate resin (B1) can be used alone or in combination of two or more types. Here, when the weight average molecular weight is within the above range, impact resistance is ensured and extrusion moldability is also good, which is preferable.

As the polycarbonate resin (B1) used in the present invention, a commercially available product can also be used, and specific examples of the aromatic polycarbonate resin include the trade names "CALIBER" and "CALIBRE" manufactured by Sumika Stylon Polycarbonate Co., Ltd. SD Polycarbonate, Mitsubishi Engineering Plastics Co., Ltd. brand name "Iupilon", Novarex, Teijin Ltd. brand name "Panlite", etc. Can be exemplified. Further, as a specific example of the aliphatic polycarbonate resin, the 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, and specifically, a specific polyester type. 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) contains 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. It is a polyester resin composed of a constituent 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 aromatic dicarboxylic acid. Here, when the aromatic dicarboxylic acid is 80 mol% or more in the carboxylic acid monomer (a) unit, the heat resistance and mechanical strength of the obtained polyester resin (B2-1) are sufficient, which is preferable. From this point of view, the aromatic dicarboxylic acid is more preferably contained in the carboxylic acid monomer (a) unit at a lower limit of 85 mol% or more, and further preferably at an upper limit of 100 mol% or less. preferable.
The aromatic dicarboxylic acid is not particularly limited, and is terephthalic acid, isophthalic acid, naphthalene-1,4 or 2,6-dicarboxylic acid, anthracenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-. Examples thereof include diphenyl ether dicarboxylic acid, 5-sulfoisophthalic acid and sodium 3-sulfoisophthalate. The aromatic dicarboxylic acid may be subjected to polymerization as an ester thereof. 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 esters, aryl esters, carbonic acid esters, and acid halides. 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, and is oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, azelaic acid, dodecandioic acid, dimer acid, 1,3 or 1,4-cyclohexanedicarboxylic acid. Acids, cyclopentanedicarboxylic acids, 4,4'-dicyclohexyldicarboxylic acids 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 for the above-mentioned components, and is 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 can appropriately impart color tone, transparency, heat resistance, impact resistance, etc. to the polyester resin. However, ethylene glycol can be preferably used because it can impart thermal stability during molding of the obtained polyester resin and is inexpensive and 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-based resin is used. It is preferable because the compatibility with the resin (B1) is improved and the transparency is less likely to decrease. From this point of view, 1,4-cyclohexanedimethanol preferably contains 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 can be used, and specific examples thereof include the trade name "SKYGREEN J2003" manufactured by SK Chemical Co., Ltd. and Eastman Chemical Co., Ltd. The product name "Easter PCTG Polyester 24635" and the like can be exemplified.

The mixed 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 preferable, 95 to 5/5 to 95 is more preferable, and 90 to 10/10 to 90 is even more preferable. Since the mixed composition of both is compatible, it is preferable because the glass transition temperature of the polycarbonate resin (B1) and the glass transition temperature of the polyester resin (B2-1) can be arbitrarily adjusted.
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. 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. Thereby, it 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 the warp of the laminated body after the wet environment test can be suppressed. From this point of view, 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) tends to have various strain relaxation phenomena due to the softening temperature of the acrylic resin layer (A) being lowered by water absorption in a high temperature and high humidity environment, 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 to each other 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 at a heating rate of 10 ° C./min according to JIS K7121 using a differential scanning calorimeter, but other known instrument analyzers, such as dynamic viscoelasticity, are used. 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 an aromatic (meth) acrylate monomer unit and 95 to 20% by mass of a methyl methacrylate monomer unit. ..
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, and phenyl methacrylate is more preferable, from the viewpoint of compatibility with the polycarbonate resin (B1).
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, it is preferably 0.1 to 10% by mass in the acrylic resin (B2-2).

When the aromatic (meth) acrylate monomer unit and the methyl methacrylate monomer unit are within the above range, compatibility with the polycarbonate resin (B1) and the effect of improving the surface hardness can be exhibited, which is preferable. From this point of view, 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 is 25 to 70% by mass. It is more preferably 60% by mass and 75-40% by mass of the methyl methacrylate monomer unit.

The acrylic resin (B2-2) preferably has a polystyrene-equivalent 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 in this range, the compatibility with the polycarbonate resin (B1) is good, and the moldability, surface hardness improving effect, appearance, etc. of the obtained polycarbonate resin layer (B) are improved. It is preferable because it is excellent. From this point of view, 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, and specific examples thereof include the trade name "MATABREN 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 (B1) / (B2-2) = 99 to 65/1 to 35% by mass. Is preferable. Here, if the mixing ratio is within the range, the obtained polycarbonate resin layer (B) is preferable because it is excellent in moldability, surface hardness improving effect, appearance and the like. From this point of view, it is more preferable that (B1) / (B2-2) = 95 to 70/5 to 30% by mass.

The resin composition constituting the polycarbonate-based resin layer (B) of the present invention may be appropriately blended with the above-mentioned various additives and other resins as long as the effects of the present invention are not impaired. Here, examples of the additive include antioxidants, ultraviolet absorbers, light stabilizers, lubricants, flame retardants, colorants, hydrolysis inhibitors and the like.

(Anti-hydrolysis agent)
Examples of the hydrolysis inhibitor include a phenolic compound, a monomer or polymer of a carbodiimide compound, and a monomer or polymer of an oxazoline compound. 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 any of an aliphatic, alicyclic, or aromatic group. Also, for n, an appropriate integer between 1 and 50 is usually selected. 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-phenylene carbodiimide), poly (m-phenylene carbodiimide), and poly (trill). Carbodiimide), poly (diisopropylphenylene carbodiimide), poly (methyl-diisopropylphenylene carbodiimide), poly (triisopropylphenylene carbodiimide), aromatic polycarbodiimide and the like, and examples of these monomers are carbodiimide compounds. The carbodiimide compound 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.

Commercially available products can be used as the carbodiimide compound, and specific examples thereof include trade names "Stabaxol P" and "Stabaxol P100" manufactured by Rhein Chemie GmbH, and products manufactured by Nisshinbo Chemical Co., Ltd. Examples thereof include the names "Carbodilite HMV-8CA" and "Carbodilite LA-1".

The amount of the hydrolysis inhibitor added is in the range of 0.001 to 1.0 parts by mass with respect to 100 parts by mass of the resin composition constituting the polycarbonate resin layer (B), and is 0.05 to 0. 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 the polycarbonate resin layer (B). In the present invention, a hard coat layer (C), which will be described later, 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 the hard coat layer (C). , (C) / (A) / (B) / (A), (C) / (A) / (B) / (C) and (C) / (A) / (B) / (A) / ( C) can be exemplified. Here, 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 configurations (A) / (B), (C) / (A) / (B) and (C) / (A) / (B) / (C) are preferable. 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 arrange it on 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, more preferably 0.15 to 1.2 mm.
In addition, the total thickness has a preferable range depending on the application application of the laminate of the present invention. For example, when applied to a 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. It is more preferably 1 mm. Within this range, it is preferable because it is lightweight and rigid, and has excellent shape stability in a high temperature or high humidity environment. Further, when an adhesive layer or the like is laminated on the laminate of the present invention to protect the surface of glass or the like from dirt or scratches, or to prevent the scattering of broken debris or the like, 0.1 to 0 It 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 Affects such as. From this point of view, 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 to have. Further, when the total thickness of the acrylic resin layer (A) and the polycarbonate resin layer (B) described above is (T), the thickness ratio of one layer of the acrylic resin layer (A) ((A) / (T)). Is preferably 0.01 to 0.35, more preferably 0.05 to 0.30, and even more preferably 0.07 to 0.20. When the thickness is within the range of the thickness ratio, it is preferable because the surface hardness and impact resistance of the laminate and the shape stability in a high temperature and high humidity environment are excellent.

(Total light transmittance)
When the total light transmittance is used as an index of the 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 warp evaluation of the laminated body of the present invention was carried out as follows. That is, a 100 mm square test piece (n = 3) was cut out from the obtained laminate, and first, it was left to stand in an environment of a temperature of 23 ° C. and a humidity of 50% RH for 24 hours. Next, each test piece was left in a temperature of 85 ° C. and a humidity of 85% RH for 120 hours, then left in a temperature of 23 ° C. and a humidity of 50% RH for 24 hours, and then the test piece was allowed to stand on a surface plate. The heights from the surface plates at the four corners were 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 the product 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.

The warp evaluation was evaluated in the present invention under a temperature of 85 ° C. and a humidity of 85% RH, but the high temperature and high humidity environment includes conditions such as a temperature of 60 ° C. and a humidity of 90% RH, a temperature of 70 ° C., and a humidity of 90% RH. May be used.
Further, as a method for reducing the warp, a method of forming a film so as not to give a strain that adversely affects the production of the laminate, or a method of alleviating the strain by annealing in the vicinity of Tg for several hours to several days 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 according to the coating thickness and type of the hard coat layer (C) described later on the front and back surfaces.

(Manufacturing method of laminated body)
Next, the method for producing the laminate of the present invention will be described, but the method is not particularly limited. As a film-forming method, a known method such as a single-screw extruder, a multi-screw extruder, a Banbury mixer, a kneader or the like is provided, and an extrusion casting method using a T-die has aspects such as handleability and productivity. Can be suitably used from. As a method for forming the laminate, a method in which the melt-kneaded resin is co-extruded 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 laminated body, it is preferable to use a molding roll (metal elastic roll, polishing roll, etc.) whose surface is mirror-treated.
The molding temperature in the extrusion casting method using a T-die is appropriately adjusted depending on the flow characteristics, film-forming property, etc. of the resin composition used, but is generally 300 ° C. or lower, preferably 230 to 270 ° C. The molding 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 it is preferable that the extruder of each layer 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 laminated body having few defects such as air 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. Of these, a leaf disc filter that easily secures an effective filtration area is preferable. It is preferable because the filter function can remove foreign substances, minute gel lumps, and the like, and a laminated body having few appearance defects can be obtained.

In the resin composition used in the present invention, each component may be mixed in advance by a mixer such as a tumbler, a V-type blender, a Banbury mixer, or an extruder, or each component measured in a supply port of the extruder may be used. It may be supplied directly, or may be supplied separately to each supply port of an extruder having two or more supply ports. Further, as a method for mixing various additives, a known method can be used. For example, (a) a masterbatch in which various additives are mixed with an appropriate base resin at a high concentration (typically about 3 to 60% by mass) is separately prepared, and the concentration is added to the resin to be used. (B) A method of directly mixing various additives with the resin to be used, and the like.

<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, the surface hardness can be evaluated using the pencil hardness as an index. In the present invention, the pencil hardness of the surface to be measured was measured with a load of 750 g 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 more, more preferably 2H or more, and particularly preferably 3H or more. Further, with respect to the surface of the hard coat layer (C) applied to the outer surface side, the pencil hardness is preferably 4H or more, more preferably 5H or more, and particularly preferably 7H or more. When the pencil hardness is 4H or more, a laminate having an excellent surface hardness can be provided. Regarding 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. When the pencil hardness is F or more, it can function as a scratch prevention layer for preventing frictional scratches on the laminate during transportation and processing in the process.

Next, the scratch resistance of the surface of the hard coat layer (C) applied to the outer surface side can be evaluated using the steel wool test as one index. Here, when the steel wool of # 0000 is rubbed with a load of 1000 gf, the number of reciprocations until scratches are preferably 20 times or more. When 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 round trips 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 those that are cured by irradiating with energy rays such as electron beam, radiation, and ultraviolet rays, or those that are cured 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 an acrylate compound, a urethane acrylate compound, an epoxy acrylate compound, a carboxyl group-modified epoxy acrylate compound, a polyester acrylate compound, a copolymer acrylate, an alicyclic epoxy resin, and a glycidyl ether epoxy resin. Examples thereof include vinyl ether compounds and oxetane compounds. These curable resins may be used alone or in combination of two or more. Examples of the curable resin that imparts more excellent surface hardness include radical polymerization curable compounds such as polyfunctional acrylate compounds, polyfunctional urethane acrylate compounds, and polyfunctional epoxy acrylate compounds, and thermosetting compounds such as alkoxysilanes and alkylalkoxysilanes. A polymerization-based curable compound can be mentioned, and an organic-inorganic composite curable resin composition obtained by containing an inorganic component in the curable resin can also be used.

Examples of the curable resin composition that imparts particularly excellent surface hardness include an organic / inorganic hybrid curable resin composition. Examples of the organic / inorganic hybrid curable resin composition include those composed of the curable resin composition containing an inorganic component having a reactive functional group in the curable resin.
Using an inorganic component having such a reactive functional group, for example, the inorganic component is copolymerized and crosslinked with a radically polymerizable monomer, so that the organic binder simply contains the inorganic component. Compared with the radical 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 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.

As a means for imparting particularly excellent surface hardness, a method of adjusting the concentration of the inorganic component contained in the hard coat layer (C) and / or the inorganic component having a reactive functional group can be mentioned.
The range of preferable concentrations of the inorganic component contained in the hard coat layer (C) and / or the inorganic component having a reactive functional group 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, the hard coat layer (C) can be packed with the inorganic component and / or the inorganic component having a reactive functional group most densely, and an excellent surface hardness is effective. It is preferable because it can be given as a target.

As a method for forming the hard coat layer (C), for example, the above-mentioned curable resin composition is applied to the surface of the resin layer as a coating material dissolved or dispersed in an organic solvent, and then formed into 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 method.
A known method is used as the laminating method 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 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, various surface treatments such as corona treatment, plasma treatment and primer treatment can be performed on the surface of the resin layer.

The curable resin composition 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 irradiating with ultraviolet rays. Here, as the light source that emits ultraviolet rays, an electrodeless high pressure mercury lamp, an electrodeed high pressure mercury lamp, an electrodeless metal halide lamp, an electrodeed metal halide lamp, a xenon lamp, an ultrahigh pressure mercury lamp, a mercury xenon lamp, or the like can be used. Among them, the electrodeless high-pressure mercury lamp is preferable because it is easy to obtain high-intensity ultraviolet rays and is advantageous for curing the ultraviolet-curable resin.
Further, in the ultraviolet curable resin, the photopolymerization initiator added 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, because it 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 irradiating 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-hydroxyalkylphenone, α-hydroxyacetophenone, hydroxyketone, aminoalkylphenone, and acylphosphine oxide. And so on. Of these, α-hydroxyalkylphenones are preferable because they are less likely to cause yellowing during curing and a transparent cured product can be obtained. Further, aminoalkylphenones are preferable because they have very high reactivity and a cured product having excellent hardness can be obtained. The above photopolymerization initiator may be used alone or in combination of two or more. The amount of the photopolymerization initiator added is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the curable resin.

Commercially available products can be used as the photopolymerization initiator, and specific examples thereof include "IRGACURE651", "IRGACURE184", "IRGACURE500", "IRGACURE1000", "IRGACURE2959", "DAROCUR1173", "IRGACURE127", and "IRGACURE907". , "IRGACURE369", "IRGACURE379", "IRGACURE1700", "IRGACURE1800", "IRGACURE819", "IRGACURE784" Name], "KAYACUREITX", "KAYACUREDETX-S", "KAYACUREBP-100", "KAYACUREBMS", "KAYACURE2-EAQ" [The above KAYACURE series are trade names manufactured by Nippon Kayaku Co., Ltd.], etc. Can be exemplified. Among these, those belonging to the above-mentioned α-hydroxyalkylphenones can be mentioned, for example, "IRGACURE184", while those belonging to aminoalkylphenones are, for example, "IRGACURE907", "IRGACURE369", "IRGACURE379". Can be mentioned.

(Surface adjustment component)
The curable resin composition forming the hard coat layer (C) can contain a leveling agent as a surface adjusting component. Examples of the leveling agent include silicone-based leveling agents and acrylic-based leveling agents. In particular, those having a reactive functional group at the terminal are preferable, and those having a bifunctional or higher-functional reactive 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 Big Chemie Japan Co., Ltd.). Examples thereof include polyester-modified polydimethylsiloxane having an acrylic group having two double bonds at the ends, for a total of four (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)
The curable resin composition forming the hard coat layer (C) includes, in addition to the curable resin component, a lubricant such as a silicon-based compound, a fluorine-based compound, or a mixed compound thereof, an antioxidant, and ultraviolet absorption. Various additives such as agents, antistatic agents, flame retardant agents such as silicone compounds, fillers, glass fibers, and impact resistance modifiers 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 internal curing of the resin composition proceeds rapidly because of its high transparency to ultraviolet rays, but the curing inhibitory action by oxygen ( Curing may be delayed on the surface of the resin composition due to oxygen damage). For this oxygen disorder, it is preferable to irradiate the resin composition with ultraviolet rays after the surroundings of the resin composition are made to have a nitrogen gas atmosphere by supplying nitrogen gas, because the curing of the surface together with the inside of the resin composition can be rapidly advanced. ..

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. It is more preferably in the range of 7 to 15 μm, and particularly preferably in the range of 7 to 15 μm. Here, when the thickness of the hard coat layer (C) is within the above range, scratch resistance can be imparted and cracks due to stress are unlikely to occur, which is preferable. When the hard coat layers (C) are 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). It is preferable that the thickness of the hard coat layer on the surface is equal to or greater 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 or both sides 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 economy by using a general-purpose material as a main raw material, and is used as a substrate material or a protective material in terms of transparency, impact resistance, surface hardness, high temperature and high temperature. Since it is a laminated body having excellent shape stability in a moist environment, it can be applied to various uses and is not particularly limited.
In particular, the laminate can be used as various substrate materials, protective materials, and the like. Specifically, portable display devices (mobile phone terminals, smartphones, portable electronic play equipment, mobile information terminals, tablet devices, mobile personal computers, etc.) and stationary display devices (LCD TVs, LCD monitors, desktop personal computers, car navigation systems, etc.) It can be suitably used for automobile instruments, etc.).
Further, the laminate having another layer such as the laminate of the present invention or the hard coat layer (C) may be given a shape by various processing methods. Specifically, a method of heating and pressurizing using a mold, a compressed air molding, a vacuum forming method, 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. The various measured values and evaluations displayed in the present specification were performed as follows.

(1) Glass transition temperature (Tg)
Using a differential scanning calorimeter manufactured by PerkinElmer Co., Ltd., trade name "Pyris1 DSC", the temperature of about 10 mg of the sample was raised from -40 ° C to 200 ° C at a heating rate of 10 ° C / min according to JIS K7121. After holding at 200 ° C. for 1 minute, the temperature was lowered to −40 ° C. at a cooling rate of 10 ° C./min, and the temperature was raised again to 200 ° C. at a heating rate of 10 ° C./min. ) (° C) was calculated. The Tg value is rounded off to the first minority.

(2) Total light transmittance A 50 mm square test piece 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 g according to JIS K5600-5-4. The pencil hardness on the surface of the acrylic resin layer (A) was H or higher (○), and the pencil hardness on the surface of the polycarbonate resin layer (B) having the hard coat layer (C) was F or higher (○). ..

(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 of 23 ° C. and a humidity of 50% RH environment. Next, each test piece was left in a temperature of 85 ° C. and a humidity of 85% RH for 120 hours, then left in a temperature of 23 ° C. and a humidity of 50% RH for 24 hours, and then the test piece was allowed to stand on a surface plate. The heights from the surface plates at the four corners were measured as the amount of warpage, and the average value of the absolute values was evaluated according to the following criteria.
(◎) Warpage amount is 0.5 mm or less (○) Warp amount exceeds 0.5 mm, 1.5 mm or less (×) Warp amount exceeds 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 conducted in accordance with JIS K5600-5-6, and no peeling of the hard coat layer was observed. Passed (○).

(6) Scratch resistance evaluation The scratch resistance of the hard coat layer (C) was measured with the following equipment and conditions, and those with 500 or more round trips until scratches were accepted (○). ..
・ Equipment: Friction fastness tester Gakushin type (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.)
-Steel wool count: # 0000
・ Test load: 1000gf
・ Test speed: 30 round trips / 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 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) ): 2.0g / 10min)

(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: 37.3N): 1.5g / 10min)

(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: 37.3N): 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: 37.3N): 4.3 / 10min)

(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:) 11.8N): 4.0g / 10min)

(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): 10.0g / 10min)

(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:) 11.8N): 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, phenylmethacrylate / methylmethacrylate = 34/66% by mass, weight average molecular weight: 14,000)

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

(others)
(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, 60 parts by mass of the acrylic resin (A1-1) and 40 parts by mass of the copolymer (A2-1) as the acrylic resin layer (A) 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) and 40 parts by mass of a polyester resin (B2-1-1) are added. A resin composition mixed at a ratio of 0.15 parts by mass of (X-1) and 0.10 parts by mass of (X-2) as an agent is supplied to separate extruders having a vent function and a filter function, respectively, and the resin temperature is supplied. It is melt-kneaded at 240 to 265 ° C., co-extruded with a T-die at 260 ° C. so as to have a laminated structure of layers (A) / (B) with a feed block, and then cast-cooled with a mirror roll at 95 ° C. Then, a laminated body having a total thickness of 0.70 mm and a thickness of each layer (A) layer / (B) layer = 0.08 mm / 0.62 mm was obtained. The obtained laminate had a good appearance and was also excellent in flatness. The results of evaluation using the laminate are shown in Table 1.

<Examples 2 to 8>
As shown in Table 1, a laminate having a total thickness of 0.70 mm and excellent appearance and flatness was obtained in the same manner except that the resin composition of each layer was changed in Example 1. The extrusion temperature, mirror surface roll temperature, and the like were appropriately adjusted 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 total thickness is 0.70 mm and the appearance and flatness are excellent in the same manner except that the acrylic resin layer (A) is changed to the acrylic resin (A1-1) alone in Example 1. A laminate was obtained. The results of evaluation using the laminate are shown in Table 1.

<Comparative example 2>
As shown in Table 1, the acrylic resin layer (A) in Example 1 was changed to a resin composition of 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, since the adhesiveness between the layers of the acrylic resin layer (A) and the polycarbonate resin layer (B) was insufficient, the layers could be easily peeled off by hand, and the evaluation was discontinued.

<Comparative example 3>
As shown in Table 1, the acrylic resin layer (A) in Example 1 was laminated in the same manner with a total thickness of 0.70 mm except that the copolymer (A2-1) was changed to (P-1). I got a body. However, since the compatibility between the acrylic resin (A1-1) and the MS resin (P-1) was poor, the acrylic resin layer (A) became cloudy, and the evaluation was discontinued.

<Example 9>
An organic / inorganic hybrid ultraviolet curable resin composition (manufactured by MOMENTIVE, trade name "UVHC7800G", containing inorganic silica having a reactive functional group) is contained 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 ^{, exposed to an exposure amount of 500 mJ / cm 2} using an ultraviolet irradiation device, and a hard coat having a thickness of 12 μm. A laminate having a layer (C) was obtained. Table 2 shows the results of evaluating the hard coat layer of the laminated body.

<Examples 10 to 14>
As shown in Table 2, a laminated body was obtained in the same manner except that the coated surface and the thickness of the laminated body and the hard coat layer used in Example 9 were changed. Table 2 shows the results of evaluating the hard coat layer of the laminated body. When applied to 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-based resin layer (B), 100 parts by mass of the polycarbonate-based resin (B1-3) was added to the resin composition of 90 parts by mass of (B1-2) and 10 parts by mass of (B2-2-1). A laminated body 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 was also excellent in 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 the hard coat layer (C) was obtained in the same manner except that the coated surface and the thickness of the laminate and the hard coat layer used in Example 9 were changed. Table 2 shows the results of evaluating the hard coat layer of the laminated body.

From Table 1, the laminate having the acrylic resin layer (A) on at least one side of the polycarbonate resin layer (B) and containing the resin composition specified in the present invention in a specific range is transparent. It can be confirmed that the properties, surface hardness, and shape stability in a high temperature and high humidity environment are excellent (Examples 1 to 8). Further, the 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 it is superior (Example 1, Examples 3 to 5).
On the other hand, it can be confirmed that the laminated body outside the range specified 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 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 high. Adhesion between 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 different from the acrylic resin (A1) outside the specified range of the present invention. It can be confirmed that compatibility is not exhibited and transparency cannot be obtained (Comparative Example 3).

From Table 2, it can be confirmed that the surface hardness can be improved and the scratch resistance can be imparted by applying the hard coat layer (C) to the surface of the laminate of the present invention. 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 in the process. The function can be shared as a scratch prevention layer for preventing frictional scratches on the laminate during transportation and processing.

Claims (19)

A laminate having an acrylic resin layer (A) on at least one side of the polycarbonate resin layer (B), wherein the acrylic resin layer (A) is composed of 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 the mixed mass ratio thereof is (A1) / (A2) = 80 to 20 /. 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 20 to 80, and the glass transition temperature is 100 to 140 ° C., and the polycarbonate resin layer ( absolute value 30 ° C. der less of the difference between the glass transition temperature of B) is,
The acrylic resin (A1) contains a methyl methacrylate monomer unit as a main component, and the molar ratio of the rr structure among mm, mr, and r of the triad fraction determined by ^{nuclear magnetic resonance measurement (1 H-NMR) is} laminate characterized by highest ones der Rukoto. The constituent unit of the copolymer (A2) is an aromatic vinyl monomer unit of 45 to 85% by mass, a (meth) acrylic acid ester monomer unit of 4 to 45% by mass, and an unsaturated dicarboxylic acid anhydride unit of 8 to 20% by mass. laminate according to claim 1 Symbol mounting characterized in that it is a%. The laminate according to claim 1 or 2, wherein the mixed 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 or 2, wherein the mixed mass ratio of the acrylic resin (A1) and the copolymer (A2) is (A1) / (A2) = 50 to 20/50 to 80. 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 transition temperature of the polycarbonate resin layer (B). The laminate according to any one of claims 1 to 4 , wherein the absolute value of the difference from the above is 20 ° C. or less. 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 transition temperature of the polycarbonate resin layer (B). The laminate according to any one of claims 1 to 4 , wherein the absolute value of the difference from the above is 10 ° C. or less. The invention according to any one of claims 1 to 6 , wherein the polycarbonate-based resin layer (B) contains the polycarbonate-based resin (B1) and at least one modifier (B2) selected from the following. Laminated body.
Modifier (B2)
(B2-1): Contains 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) composed of structural units: Acrylic copolymer composed of 5 to 80% by mass of aromatic (meth) acrylate monomer unit and 95 to 20% by mass of methyl methacrylate monomer unit. The laminate according to any one of claims 1 to 7 , wherein a phosphite-based antioxidant is mixed in the acrylic resin layer (A). The laminate according to any one of claims 1 to 8 , wherein the carbodiimide compound is mixed in the polycarbonate resin layer (B). The laminate according to any one of claims 1 to 9 , wherein the thickness of the acrylic resin layer (A) is 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 layer of the acrylic resin layer (A) is 0. The laminate according to any one of claims 1 to 10 , wherein the thickness is 0.01 to 0.35. The laminate according to any one of claims 1 to 11, wherein the laminate is coextruded. The laminate according to any one of claims 1 to 12 , wherein the hard coat layer (C) is laminated on at least one surface of the laminate. The laminate according to claim 13, wherein the pencil hardness of the surface of the hard coat layer (C) is 4H or more. The laminate according to claim 13 or 14, wherein the hard coat layer (C) is made of an organic / inorganic hybrid curable resin composition. One or more of the antireflection treatment, the antifouling treatment, the antistatic treatment, the weather resistance treatment, and the antiglare treatment are applied to one or both sides of the laminate and the laminate having the hard coat layer (C). The laminate according to any one of claims 13 to 15 , characterized in that. A substrate material using the laminate according to any one of claims 1 to 16. A protective material using the laminate according to any one of claims 1 to 16. An image display device including the laminate according to any one of claims 1 to 16.