Antiglare laminate and method for manufacturing the same

Abstract

To provide: an antiglare laminate which has antiglare properties that achieve both image photobombing prevention performance and text garbling inhibition, and which has high abrasion resistance and excellent form stability; and a method for manufacturing the antiglare laminate.SOLUTION: The above problem can be solved by an antiglare laminate in which a base material layer including at least a polycarbonate resin (a1), a high hardness resin layer including a high hardness resin (B), and a hard coat layer are disposed in this order. An expanded interface area rate (Sdr) of the hard coat layer, an arithmetical average height (Sa), and an autocorrelation length (Sal) satisfy the following equations (i) to (iii): 0≤Sdr≤0.6 (i); 0≤Sa≤0.16 (ii); and 0≤Sal≤15.0 (iii).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an antiglare laminate and a manufacturing method thereof, and more particularly to an antiglare laminate having antiglare performance, high scratch resistance and excellent shape stability, which is used as a front panel of an in-vehicle liquid crystal display device, a mobile phone terminal, a personal computer, or a tablet PC, and a manufacturing method thereof. [Background technology]

[0002] Liquid crystal display devices are provided with a front panel for the purpose of protecting the liquid crystal panel, etc. Materials used for the front panel of conventional liquid crystal display devices include (meth)acrylic resins, such as polymethyl methacrylate (PMMA).

[0003] In recent years, sheets made of polycarbonate resin have been used as front panels because of their high impact resistance, heat resistance, secondary processability, light weight, transparency, etc. In particular, front panels in which a hard coat is applied to a multilayer sheet in which an acrylic resin is laminated on the surface of a polycarbonate resin sheet have surface hardness and scratch resistance comparable to conventional acrylic resins with hard coats, while also possessing the excellent impact resistance, heat resistance, processability, and transparency of polycarbonate resin, and are therefore widely used as front panels.

[0004] The front panel of a liquid crystal display device having the above-mentioned polycarbonate resin sheet is generally formed by melt extrusion together with an acrylic resin.

[0005] In liquid crystal display devices, an anti-reflection optical laminate is generally provided on the outermost surface. Such an anti-reflection optical laminate suppresses image glare and reduces reflectance by scattering or interfering with light.

[0006] As one of the anti-reflection optical laminates, an anti-glare film is known in which an anti-glare layer having an uneven surface is formed on the surface of a transparent substrate. This anti-glare film can prevent the deterioration of visibility due to the reflection of the outside light or the reflection of an image by scattering the outside light by the uneven surface. In addition, since this optical laminate is usually placed on the outermost surface of a liquid crystal display device, it is also required to impart hard coat properties to prevent scratches during handling.

[0007] In the display surfaces of liquid crystal display devices and organic electroluminescence (EL) display devices, a mixture of fine particles and a binder resin or a curable resin is usually applied to a substrate, and a fine uneven surface is formed on the surface to prevent regular reflection and prevent image reflection. However, when an uneven surface is provided to prevent image reflection, the scattering of transmitted light that travels straight increases, making the outlines of pixels unclear and causing blurred characters.

[0008] Furthermore, if fine particles are added to create surface irregularities, the fine particles on the outermost surface fall off during the scratch resistance test and act as an abrasive, resulting in a significant decrease in scratch resistance compared to when fine particles are not added, which is not preferred.

[0009] As described above, there has been no front panel for in-vehicle liquid crystal display devices, mobile phone terminals, personal computers, and tablet PCs that has excellent impact resistance, heat resistance, anti-glare properties that prevent image reflection and suppress blurred characters, high scratch resistance, and excellent shape stability. In Patent Document 1, fine particles are added to improve transmission clarity and reduce blurred characters. Adding fine particles improves pencil hardness, but is not preferable because it reduces scratch resistance. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Patent Publication 2010-160398 DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0011] The present invention aims to solve at least one of the above-mentioned problems in the prior art. Another object of the present invention is to provide an antiglare laminate having antiglare performance that combines anti-reflection performance and suppression of character blurring, high scratch resistance, and excellent shape stability, and a method for producing the same. [Means for solving the problem]

[0012] The above problems can be solved by the present invention. That is, the present invention is as follows. <1> An antiglare laminate comprising a substrate layer containing at least a polycarbonate resin (a1), a high-hardness resin layer containing a high-hardness resin (B), and a hard coat layer, which are arranged in this order, wherein the developed interface area ratio (Sdr), arithmetic mean height (Sa), and autocorrelation length (Sal) of the hard coat layer satisfy the following formulas (i) to (iii): 0≦Sdr≦0.6 (i) 0≦Sa≦0.16 (ii) 0≦Sal≦15.0 (iii) The antiglare laminate satisfies the above requirements. <2> The developed interface area ratio (Sdr), the arithmetic mean height (Sa), and the autocorrelation length (Sal) of the hard coat layer are expressed by the following formulas (iv) to (vi): 0≦Sdr≦0.3 (iv) 0.03≦Sa≦0.13 (v) 3.0≦Sal≦8.0 (vi) Satisfy the above <1> The antiglare laminate according to claim 1. <3> The antiglare laminate has a warpage change of 350 μm or less after being kept in an environment of a temperature of 85° C. and a relative humidity of 85% for 120 hours. <1> or <2> The antiglare laminate according to claim 1. <4> The thickness of the high-hardness resin layer is 10 to 250 μm. <1> ~ <3> 13. The antiglare laminate according to claim 12, <5> The total thickness of the base layer and the high-hardness resin layer is 100 to 3,000 μm. <1> ~ <4> 13. The antiglare laminate according to claim 12, <6> The hard coat layer does not contain organic particles and inorganic particles. <1> ~ <5> 13. The antiglare laminate according to claim 12, <7> The polycarbonate resin (a1) is represented by the following general formula (5): [ka] (In the formula, R 5 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms, R 6 each independently represents a hydrogen atom, a halogen, or an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms which may have a substituent, and n is an integer of 0 to 4, wherein the substituent is a halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. <1> ~ <6> 13. The antiglare laminate according to claim 12, <8> the above <1> ~ <7> 2. An in-vehicle display device comprising the antiglare laminate according to claim 1. <9> the above <1> ~ <7> 2. A touch panel front protection plate comprising the antiglare laminate according to any one of claims 1 to 11. <10> the above <1> ~ <7> 2. A front panel for office automation equipment, portable electronic equipment, or television, comprising the antiglare laminate according to any one of claims 1 to 11. <11> the above <1> ~ <7> A method for producing the antiglare laminate according to any one of the above, A patterned PET film is pressure-bonded to the surface of the hard coat layer to transfer the uneven shape, and the hard coat layer after the transfer has a structure represented by the following formulas (i) to (iii): 0≦Sdr≦0.6 (i) 0≦Sa≦0.16 (ii) 0≦Sal≦15.0 (iii) The manufacturing method as described above, comprising the step of: Effect of the Invention

[0013] According to the present invention, it is possible to provide an antiglare laminate having antiglare performance that combines the performance of preventing image reflection and the suppression of character blurring, high scratch resistance, and excellent shape stability, and a manufacturing method thereof. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] Hereinafter, the present invention will be described in detail by way of examples and working examples. However, the present invention is not limited to the illustrated examples and working examples, and can be modified in any manner without departing from the scope of the present invention.

[0015] The antiglare laminate of the present invention comprises a substrate layer containing at least a polycarbonate resin (a1), a high-hardness resin layer containing a high-hardness resin, and a hard coat layer, which are arranged in this order.

[0016] The order of lamination of the antiglare laminate is preferably substrate layer-high hardness resin layer-hard coat layer. The other surface of the substrate layer is not particularly specified. In one embodiment, a high hardness resin layer can be provided on the other surface of the substrate layer. In this case, the antiglare laminate has a configuration of high hardness resin layer-substrate layer-high hardness resin layer-hard coat layer. In one embodiment, a high hardness resin layer and a hard coat layer can be provided on the other surface of the substrate layer. In this case, the antiglare laminate has a configuration of hard coat layer-high hardness resin layer-substrate layer-high hardness resin layer-hard coat layer.

[0017] When the high-hardness layer is provided on both sides of the substrate layer, it is more preferable to use the same high-hardness layer on both sides for shape stability. When the hard coat layer is provided on both sides of the substrate, it is more preferable to provide the same hard coat layer on both sides for better shape stability. The substrate layer and the high-hardness resin layer, and the high-hardness resin layer and the hard coat layer may be directly laminated or may be laminated via other layers, but it is preferable to laminate them directly.

[0018] In one embodiment, the antiglare laminate can be used, for example, as a touch panel full-surface protection plate for in-vehicle display devices such as car navigation systems, center information displays (CIDs), rear seat entertainment (RSEs), and clusters, as well as front panels for office automation equipment, portable electronic devices, televisions, etc. For example, the front panel can be used alone as the front panel for a liquid crystal display device, but it may also be used as a front panel in a composite manner, for example by laminating it with another substrate such as a touch sensor.

[0019] Each of the components of the antiglare laminate of the present invention will be described below.

[0020] <Base material layer> The substrate layer contains a polycarbonate resin (a1). The substrate layer may further contain additives and the like.

[0021] [Polycarbonate resin (a1)] The polycarbonate resin (a1) is not particularly limited as long as it contains a carbonate bond, i.e., a -[OR-OCO]- unit (where R may contain an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and may have a straight-chain structure or a branched structure), in the molecular main chain, but it is particularly preferable to use a polycarbonate resin containing a structural unit of the following formula (4). By using such a polycarbonate resin, a resin laminate with excellent impact resistance can be obtained.

[0022] [ka]

[0023] Specifically, the polycarbonate resin (a1) may be an aromatic polycarbonate resin (for example, manufactured by Mitsubishi Engineering Plastics Corporation, product names: Iupilon S-2000, Iupilon S-1000, Iupilon E-2000), but is not limited thereto.

[0024] Furthermore, in recent years, there has been an increasing demand for bending the front panel as well, so it is preferable to use a monohydric phenol represented by the following general formula (5) as an end terminator for the polycarbonate resin (al).

[0025] [ka]

[0026] In the formula, R 5 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms; R 6 each independently represents a hydrogen atom, a halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 12 carbon atoms, and n is an integer from 0 to 4, where the substituent is a halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. In this specification, the "alkyl group" and the "alkenyl group" may be linear or branched, and may have a substituent.

[0027] More preferably, the monohydric phenol represented by general formula (5) is represented by the following general formula (6).

[0028] [ka]

[0029] In the formula, R 5 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms.

[0030] R in general formula (5) or general formula (6) 5 It is more preferable that the number of carbon atoms in R is within a specific numerical range. 5 The upper limit of the number of carbon atoms in R is preferably 36, more preferably 22, and particularly preferably 18. 5 The lower limit of the number of carbon atoms is preferably 8, and more preferably 12.

[0031] R in general formula (5) or general formula (6) 5 When the upper limit of the carbon number is appropriate, the solubility of the monohydric phenol (end terminator) in organic solvents tends to be high, which is preferable since it increases the productivity during the production of the polycarbonate resin.

[0032] As an example, R 5 If the carbon number of R is 36 or less, the productivity of polycarbonate resin production is high and the economic efficiency is good. 5 When the carbon number of the monohydric phenol is 22 or less, the monohydric phenol has excellent solubility in organic solvents, and the productivity in producing the polycarbonate resin can be extremely increased, resulting in improved economic efficiency.

[0033] R in general formula (5) or general formula (6) 5 When the lower limit of the carbon number is appropriate, the glass transition point of the polycarbonate resin is not too high, and suitable thermoformability is obtained, which is preferable.

[0034] For example, in general formula (6), R 5 When a monohydric phenol (terminal terminator) having an alkyl group having 16 carbon atoms is used as the terminal terminator, the glass transition temperature, melt fluidity, moldability, drawdown resistance, and solvent solubility of the monohydric phenol during production of the polycarbonate resin are excellent, and it is particularly preferable as the terminal terminator used for the polycarbonate resin of the present invention.

[0035] Among the monohydric phenols (end terminators) represented by general formula (5) or general formula (6), it is particularly preferable to use either or both of parahydroxybenzoic acid hexadecyl ester and parahydroxybenzoic acid 2-hexyldecyl ester as the end terminator.

[0036] The weight average molecular weight of the polycarbonate resin (a1) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000, and even more preferably 20,000 to 65,000. When the weight average molecular weight of the polycarbonate resin (a1) is 15,000 or more, it is preferable because the impact resistance can be increased. On the other hand, when the weight average molecular weight is 75,000 or less, it is preferable because the base layer can be formed with a small heat source and the thermal stability can be maintained even when the molding conditions become high temperature. In this specification, the weight average molecular weight is the weight average molecular weight measured by gel permeation chromatography (GPC) and converted into standard polystyrene.

[0037] The polycarbonate resin (a1) contained in the substrate layer may be one type or two or more types.

[0038] The content of the polycarbonate resin (a1) in the base layer is preferably 75 mass% or more, based on the total mass of the base layer, and from the viewpoint of improving impact resistance, is more preferably 90 mass% or more, and even more preferably 100 mass%.

[0039] [Additives] The substrate layer may further include an additive.

[0040] The additives may be any additive that is commonly used in antiglare laminates, including, for example, antioxidants, anticoloring agents, antistatic agents, release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, and reinforcing materials such as organic fillers and inorganic fillers.

[0041] The amount of the additive is preferably from 0 to 10 mass %, more preferably from 0 to 7 mass %, and particularly preferably from 0 to 5 mass %, relative to the total mass of the base layer.

[0042] The method for mixing the additive and the resin is not particularly limited, and may be a method of compounding the entire amount, a method of dry blending a master batch, a method of dry blending the entire amount, or the like.

[0043] [Base layer composition] The thickness of the substrate layer is preferably from 0.3 to 10 mm, more preferably from 0.3 to 5 mm, and particularly preferably from 0.3 to 3.5 mm.

[0044] <High hardness resin layer> The high-hardness resin layer includes a high-hardness resin. In addition, the high-hardness resin layer may further include additives, etc., as necessary. The high-hardness resin layer is provided between the substrate layer and the hard coat layer, so that an anti-glare laminate having high shape stability can be obtained. The high-hardness resin layer can have a function of increasing the hardness of the anti-glare laminate. In this specification, the high-hardness resin means a resin having a higher hardness than the polycarbonate resin serving as the substrate, and a pencil hardness of HB or more, preferably HB to 3H, more preferably H to 3H, and even more preferably 2H to 3H. The pencil hardness of the high-hardness resin layer is a result of evaluation by a pencil scratch hardness test conforming to JIS K 5600-5-4:1999. Specifically, a pencil is pressed against the surface of the high-hardness resin layer at an angle of 45 degrees with a load of 750 g, with gradually increasing hardness, and the hardness of the hardest pencil that does not cause a scratch is evaluated as the pencil hardness.

[0045] [High hardness resin] The high-hardness resin is not particularly limited, but preferably includes at least one selected from the group consisting of resins (B1) to (B6). Note that resins (B1) to (B6) may be referred to as resins (B1) to (B6) even in the case of a resin composition including a plurality of resins.

[0046] (Resin (B1)) Resin (B1) is a copolymer resin containing (meth)acrylic acid ester structural units (a) represented by the following general formula (1) and aliphatic vinyl structural units (b) represented by the following general formula (2). In this case, the resin (B1) (copolymer resin) may further contain other structural units. The total ratio of the (meth)acrylic acid ester structural units (a) and the aliphatic vinyl structural units (b) is 90 to 100 mol %, preferably 95 to 100 mol %, and more preferably 98 to 100 mol % of the total structural units of the copolymer resin. The ratio of the (meth)acrylic acid ester structural units (a) is 65 to 80 mol % of the total structural units of the copolymer resin. In this specification, (meth)acrylic refers to methacrylic and / or acrylic.

[0047] [ka]

[0048] In the formula, R 1 is a hydrogen atom or a methyl group, and is preferably a methyl group.

[0049] Also, R 2 is an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples include a methyl group, an ethyl group, a butyl group, a lauryl group, a stearyl group, a cyclohexyl group, and an isobornyl group. Of these, R 2 is preferably a methyl group or an ethyl group, and more preferably a methyl group.

[0050] In addition, R 2 is a methyl group or an ethyl group, the (meth)acrylic acid ester structural unit (a) represented by general formula (1) becomes a (meth)acrylic acid ester structural unit, and R 1 is a methyl group and R 2 When is a methyl group, the (meth)acrylic acid ester structural unit (a) represented by general formula (1) becomes a methyl methacrylate structural unit.

[0051] The (meth)acrylic acid ester structural unit (a) represented by the general formula (1) may be contained in the resin (B1) either alone or in combination of two or more kinds.

[0052] [ka]

[0053] In the formula, R 3 is a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

[0054] R 4 is a cyclohexyl group which may be substituted with a hydrocarbon group having 1 to 4 carbon atoms, and is preferably a cyclohexyl group having no substituent. In this specification, the "hydrocarbon group" may be linear, branched, or cyclic, and may have a substituent.

[0055] R 3 is a hydrogen atom, and R 4 is a cyclohexyl group, the aliphatic vinyl structural unit (b) represented by general formula (2) is a vinylcyclohexane structural unit.

[0056] The aliphatic vinyl structural unit (b) represented by general formula (2) may be contained in the resin (B1) either alone or in combination of two or more.

[0057] The other structural unit is not particularly limited, but may be a structural unit derived from an aromatic vinyl monomer containing an unhydrogenated aromatic double bond, which is generated in the process of producing the resin (B1) by polymerizing a (meth)acrylic acid ester monomer and an aromatic vinyl monomer and then hydrogenating the aromatic double bond derived from the aromatic vinyl monomer. A specific example of the other structural unit is a styrene structural unit.

[0058] The resin (B1) may contain only one type of other structural unit, or two or more types of other structural units.

[0059] The content of the (meth)acrylic acid ester structural unit (a) represented by the general formula (1) is 65 to 80 mol %, preferably 70 to 80 mol %, based on the total structural units of the resin (B1) (copolymer resin). When the content of the (meth)acrylic acid ester structural unit (a) is 65 mol % or more, a high-hardness resin layer having excellent adhesion to the base layer and excellent surface hardness can be obtained. On the other hand, when the content of the (meth)acrylic acid ester structural unit (a) is 80 mol % or less, it is preferable because the antiglare laminate is less likely to warp due to water absorption.

[0060] The content of the aliphatic vinyl structural unit (b) represented by the general formula (2) is preferably 20 to 35 mol %, more preferably 20 to 30 mol %, based on the total structural units of the resin (B1) (copolymer resin). If the content of the aliphatic vinyl structural unit (b) is 20 mol % or more, warping under high temperature and high humidity conditions can be prevented, which is preferable. On the other hand, if the content of the aliphatic vinyl structural unit (b) is 35 mol % or less, peeling at the interface with the base layer can be prevented, which is preferable.

[0061] The content of the other structural units is preferably 10 mol % or less, more preferably 5 mol % or less, and particularly preferably 2 mol % or less, based on all structural units of the resin (B1) (copolymer).

[0062] In this specification, the "copolymer" may have any of a random, block, and alternating copolymer structure.

[0063] The weight average molecular weight of the resin (B1) is not particularly limited, but from the viewpoints of strength and moldability, it is preferably from 50,000 to 400,000, and more preferably from 70,000 to 300,000.

[0064] The glass transition temperature of the resin (B1) is preferably 110 to 140°C, more preferably 110 to 135°C, and particularly preferably 110 to 130°C. A glass transition point of 110°C or higher is preferable because the resin sheet is less likely to deform or crack in a hot or humid heat environment. On the other hand, a glass transition point of 140°C or lower is preferable because the resin sheet is excellent in processability when molded by continuous thermal shaping using a mirror roll or a shaping roll, or batch-type thermal shaping using a mirror mold or a shaping mold. The glass transition temperature in the present invention is a temperature measured using a differential scanning calorimeter with a 10 mg sample at a heating rate of 10°C / min and calculated by the midpoint method.

[0065] Specific examples of the resin (B1) include Optimus 7500 and 6000 (manufactured by Mitsubishi Gas Chemical Co., Ltd.) The above-mentioned resin (B1) may be used alone or in combination of two or more kinds.

[0066] The method for producing the resin (B1) is not particularly limited, but it is preferable to use a resin obtained by polymerizing at least one type of (meth)acrylic acid ester monomer and at least one type of aromatic vinyl monomer, and then hydrogenating the aromatic double bond derived from the aromatic vinyl monomer.

[0067] The aromatic vinyl monomer is not particularly limited, but may be styrene, α-methylstyrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and derivatives thereof, etc. Among these, the aromatic vinyl monomer is preferably styrene.

[0068] The (meth)acrylic acid ester monomer and the aromatic vinyl monomer can be polymerized by a known method, for example, a bulk polymerization method or a solution polymerization method.

[0069] The bulk polymerization method is carried out by continuously supplying a monomer composition containing the above-mentioned monomers and a polymerization initiator to a complete mixing tank and continuously polymerizing the monomers at 100 to 180° C. The above-mentioned monomer composition may contain a chain transfer agent as necessary.

[0070] The polymerization initiator is not particularly limited, but examples thereof include organic peroxides such as t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, t-hexylpropoxyisopropyl monocarbonate, t-amylperoxy normal octoate, t-butylperoxyisopropyl monocarbonate, and di-t-butyl peroxide, and azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and 2,2'-azobis(2,4-dimethylvaleronitrile). These can be used alone or in combination of two or more.

[0071] The chain transfer agent is not particularly limited, but may be α-methylstyrene dimer.

[0072] Examples of solvents used in the solution polymerization method include hydrocarbon solvents such as toluene, xylene, cyclohexane, and methylcyclohexane, ester solvents such as ethyl acetate and methyl isobutyrate, ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as tetrahydrofuran and dioxane, and alcohol solvents such as methanol and isopropanol. These solvents may be used alone or in combination of two or more.

[0073] The solvent used in the hydrogenation reaction after polymerization of the (meth)acrylic acid ester monomer and the aromatic vinyl monomer may be the same as or different from the polymerization solvent described above. Examples of the solvent include hydrocarbon solvents such as cyclohexane and methylcyclohexane, ester solvents such as ethyl acetate and methyl isobutyrate, ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as tetrahydrofuran and dioxane, and alcohol solvents such as methanol and isopropanol.

[0074] After the (meth)acrylic acid ester monomer and the aromatic vinyl monomer are polymerized as described above, the aromatic double bond derived from the aromatic vinyl monomer is hydrogenated to obtain the resin (B1).

[0075] The hydrogenation method is not particularly limited, and known methods can be used. For example, the hydrogenation can be carried out in a batch or continuous flow manner at a hydrogen pressure of 3 to 30 MPa and a reaction temperature of 60 to 250°C. A reaction temperature of 60°C or higher is preferable because the reaction time is not too long. On the other hand, a reaction temperature of 250°C or lower is preferable because side reactions such as scission of molecular chains and hydrogenation of ester moieties do not occur or occur very little.

[0076] Examples of catalysts used in the hydrogenation reaction include solid catalysts in which metals such as nickel, palladium, platinum, cobalt, ruthenium, and rhodium, or oxides, salts, or complex compounds of these metals are supported on porous supports such as carbon, alumina, silica, silica-alumina, and diatomaceous earth.

[0077] It is preferable that 70% or more of the aromatic double bonds derived from the aromatic vinyl monomer are hydrogenated by the hydrogenation reaction. That is, the unhydrogenated ratio of the aromatic double bonds contained in the structural unit derived from the aromatic vinyl monomer is preferably less than 30%, more preferably less than 10%, and even more preferably less than 5%. If the unhydrogenated ratio is less than 30%, it is preferable because a resin with excellent transparency can be obtained. The structural unit of the unhydrogenated portion can be another structural unit in the resin (B1).

[0078] The resin (B1) can be blended with other resins as long as the transparency is not impaired. That is, the resin (B1) is a resin composition containing the above-mentioned copolymer and other resins. Examples of the other resins include methyl methacrylate-styrene copolymer resins, polymethyl methacrylate, polystyrene, polycarbonate, cycloolefin (co)polymer resins, acrylonitrile-styrene copolymer resins, acrylonitrile-butadiene-styrene copolymer resins, and various elastomers.

[0079] (Resin (B2)) Resin (B2) contains 35 to 65 mass%, preferably 40 to 60 mass%, of the resin (B1) and 35 to 65 mass%, preferably 40 to 60 mass%, of a styrene-unsaturated dicarboxylic acid copolymer (C). The styrene-unsaturated dicarboxylic acid copolymer (C) contains 65 to 90 mass% of a styrene-based structural unit (c1) and 10 to 35 mass% of an unsaturated dicarboxylic anhydride structural unit (c2). That is, resin (B2) is a resin composition containing two or more resins.

[0080] Resin (B1) The resin (B1) may be any of the above-mentioned resins, and may be used alone or in combination of two or more kinds.

[0081] Styrene-unsaturated dicarboxylic acid copolymer (C) The styrene-unsaturated dicarboxylic acid copolymer (C) contains a styrene structural unit (c1) and an unsaturated dicarboxylic acid anhydride structural unit (c2).

[0082] Styrene-based structural unit (c1) The styrene monomer is not particularly limited, and any known styrene monomer can be used. Specific examples of the styrene monomer include styrene, a-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and t-butylstyrene. Among these, styrene is particularly preferred from the viewpoint of compatibility. These styrene monomers may be used alone or in combination of two or more.

[0083] The content of the styrene-based structural unit (c1) is from 65 to 90 mass %, and preferably from 70 to 85 mass %, based on the total mass of the styrene-unsaturated dicarboxylic acid-based copolymer (C).

[0084] Unsaturated dicarboxylic acid anhydride structural unit (c2) The unsaturated dicarboxylic anhydride monomer is not particularly limited, and examples thereof include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid. Among these, maleic anhydride is preferred from the viewpoint of compatibility with styrene-based monomers. These unsaturated dicarboxylic anhydride monomers may be used alone or in combination of two or more.

[0085] The content of the unsaturated dicarboxylic anhydride structural unit (c2) is from 10 to 35% by mass, and preferably from 15 to 30% by mass, based on the total mass of the styrene-unsaturated dicarboxylic acid copolymer (C).

[0086] Specific examples of the styrene-unsaturated dicarboxylic acid copolymer (C) include XIBOND140, XIBOND160, XIRAN SO23110, and XIRAN SO26080 (manufactured by Polyscope). These styrene-unsaturated dicarboxylic acid copolymers (C) may be used alone or in combination of two or more.

[0087] (Resin (B3)) Resin (B3) contains 55-10% by mass of resin (D) containing a vinyl monomer, and 45-90% by mass of styrene-unsaturated dicarboxylic acid copolymer (E). The styrene-unsaturated dicarboxylic acid copolymer (E) contains 50-80% by mass of styrene structural units (e1), 10-30% by mass of unsaturated dicarboxylic acid structural units (e2), and 5-30% by mass of vinyl structural units (e3). In other words, resin (B3) is a resin composition containing two or more resins.

[0088] Resins containing vinyl monomers (D) The resin (D) containing a vinyl monomer is not particularly limited, but may be a homopolymer of a vinyl monomer such as acrylonitrile, methacrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, or 2-ethylhexyl methacrylate. Of these, the resin (D) containing a vinyl monomer preferably contains methyl methacrylate as a constituent unit. The resin (D) containing a vinyl monomer may be a polymer using one of the constituent units, or may be a copolymer using two or more of them in combination.

[0089] The weight average molecular weight of the resin (D) containing a vinyl monomer is preferably from 10,000 to 500,000, and more preferably from 50,000 to 300,000.

[0090] The above-mentioned resins (D) containing vinyl monomers may be used alone or in combination of two or more kinds.

[0091] Styrene-unsaturated dicarboxylic acid copolymer (E) The styrene-unsaturated dicarboxylic acid copolymer (E) contains a styrene structural unit (e1), an unsaturated dicarboxylic anhydride structural unit (e2), and a vinyl structural unit (e3).

[0092] Styrene-based structural unit (e1) The styrene monomer is not particularly limited, and any known styrene monomer can be used. Specific examples of the styrene monomer include styrene, a-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and t-butylstyrene. Among these, styrene is particularly preferred from the viewpoint of compatibility. These styrene monomers may be used alone or in combination of two or more.

[0093] The content of the styrene-based structural unit (e1) is from 50 to 80% by mass, and preferably from 50 to 75% by mass, based on the total mass of the styrene-unsaturated dicarboxylic acid-based copolymer (E).

[0094] Unsaturated dicarboxylic acid anhydride building block (e2) The unsaturated dicarboxylic anhydride monomer is not particularly limited, and examples thereof include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid. Among these, maleic anhydride is preferred from the viewpoint of compatibility with vinyl monomers. These unsaturated dicarboxylic anhydride monomers may be used alone or in combination of two or more.

[0095] The content of the unsaturated dicarboxylic anhydride structural unit (e2) is from 10 to 30% by mass, and preferably from 10 to 25% by mass, based on the total mass of the styrene-unsaturated dicarboxylic acid copolymer (E).

[0096] Vinyl building blocks (e3) The vinyl monomer is not particularly limited, but includes vinyl monomers such as acrylonitrile, methacrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate. Among these, methyl methacrylate (MMA) is preferred from the viewpoint of compatibility with the resin (D) containing the vinyl monomer. These vinyl monomers may be used alone or in combination of two or more.

[0097] The content of the vinyl structural unit (e3) is from 5 to 30 mass %, and preferably from 7 to 27 mass %, based on the total mass of the styrene-unsaturated dicarboxylic acid copolymer (E).

[0098] The weight average molecular weight of the styrene-unsaturated dicarboxylic acid copolymer (E) is preferably 50,000 to 200,000, and more preferably 80,000 to 200,000. When the weight average molecular weight is within the above range, compatibility with the resin (D) containing a vinyl monomer is good, and the effect of improving heat resistance is excellent, which is preferable.

[0099] Specific examples of the styrene-unsaturated dicarboxylic acid copolymer (E) include, but are not limited to, Resistify R100, R200, and R310 (manufactured by Denki Kagaku Kogyo Co., Ltd.), Delpet 980N (manufactured by Asahi Kasei Co., Ltd.), etc. The above-mentioned styrene-unsaturated dicarboxylic acid copolymer (E) may be used alone or in combination of two or more kinds.

[0100] (Resin (B4)) The resin (B4) is a resin copolymer (G) containing 5 to 20 mass% of styrene constituent units, 60 to 90 mass% of (meth)acrylic acid ester constituent units, and 5 to 20 mass% of N-substituted maleimide constituent units, or an alloy of the resin copolymer (G) and a styrene-unsaturated dicarboxylic acid copolymer (E).

[0101] ·Resin copolymer (G) The resin copolymer (G) contains a styrene structural unit, a (meth)acrylic acid ester structural unit, and an N-substituted maleimide structural unit.

[0102] Styrene building block The styrene monomer is not particularly limited, and any known styrene monomer can be used. Specific examples of the styrene monomer include styrene, a-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and t-butylstyrene. Among these, styrene is particularly preferred from the viewpoint of compatibility. These styrene monomers may be used alone or in combination of two or more.

[0103] The content of the styrene structural unit is from 5 to 20 mass %, preferably from 5 to 15 mass %, and more preferably from 5 to 10 mass %, based on the total mass of the resin (B4) (resin copolymer (G)).

[0104] (Meth)acrylic acid ester structural unit The (meth)acrylic acid ester monomer is not particularly limited, and examples thereof include acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, etc. Among these, methyl methacrylate is preferred. These (meth)acrylic acid ester monomers may be used alone or in combination of two or more.

[0105] The content of the (meth)acrylic acid ester structural unit is 60 to 90 mass %, preferably 70 to 90 mass %, and more preferably 80 to 90 mass %, based on the total mass of the resin (B4) (resin copolymer (G)).

[0106] N-Substituted Maleimide Building Blocks The N-substituted maleimide monomer is not particularly limited, and examples thereof include N-arylmaleimides such as N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, and N-tribromophenylmaleimide. Among these, N-phenylmaleimide is preferred from the viewpoint of compatibility with the (meth)acrylic acid structural unit. These N-substituted maleimide monomers may be used alone or in combination of two or more.

[0107] The content of the N-substituted maleimide structural unit is from 5 to 20 mass %, preferably from 5 to 15 mass %, and more preferably from 5 to 10 mass %, based on the total mass of the resin (B4) (resin copolymer (G)).

[0108] The weight average molecular weight of the resin copolymer (G) is preferably from 50,000 to 250,000, and more preferably from 100,000 to 200,000.

[0109] A specific example of the resin copolymer (G) is Delpet PM120N (manufactured by Asahi Kasei Chemical Corporation), but is not limited thereto.

[0110] The method for producing the resin copolymer (G) is not particularly limited, but it can be produced by solution polymerization, bulk polymerization, or the like.

[0111] Alloy The alloy is an alloy of the resin copolymer (G) and the styrene-unsaturated dicarboxylic acid copolymer (E).

[0112] In this case, it is preferable that the resin copolymer (G) and the styrene-unsaturated dicarboxylic acid copolymer (E) are alloyed together so as to have high glass transition temperatures.

[0113] The alloy may be produced by, but is not limited to, a method in which the alloy is melt-kneaded at a cylinder temperature of 240° C. using a twin-screw extruder with a screw diameter of 26 mm, extruded in the form of strands, and pelletized with a pelletizer.

[0114] (Resin (B5)) Resin (B5) contains a structural unit (H) represented by the following formula (3). Resin (B5) is preferably a copolymer further containing a structural unit (J) represented by the following formula (4). The copolymer may further contain other structural units.

[0115] [ka]

[0116] The content of the structural unit (H) represented by formula (3) is preferably 50 to 100 mol %, more preferably 60 to 100 mol %, and even more preferably 70 to 100 mol %, based on all structural units of the resin (B5).

[0117] [ka]

[0118] The content of the structural unit (J) represented by formula (4) is preferably 0 to 50 mol %, more preferably 0 to 40 mol %, and even more preferably 0 to 30 mol %, based on all structural units of the resin (B5).

[0119] The content of other structural units is preferably 10 mol % or less, more preferably 5 mol % or less, and particularly preferably 2 mol % or less, based on all structural units of the resin (B5).

[0120] The total content of the structural units (H) and (J) is preferably 90 to 100 mol %, more preferably 95 to 100 mol %, and even more preferably 98 to 100 mol %, based on all structural units in the resin (B5).

[0121] The weight average molecular weight of the resin (B5) is preferably from 15,000 to 75,000, more preferably from 20,000 to 70,000, and particularly preferably from 25,000 to 65,000.

[0122] Specific examples of the resin (B5) include, but are not limited to, Iupilon KH3410UR, KH3520UR, and KS3410UR (manufactured by Mitsubishi Engineering Plastics Corporation). The above-mentioned resin (B5) may be used alone or in combination of two or more kinds.

[0123] The method for producing resin (B5) is not particularly limited, but it can be produced by the same method as the method for producing polycarbonate resin (a1) described above, except that bisphenol C is used as the monomer.

[0124] (Resin (B6)) Resin (B6) contains 35 to 65 mass% of resin (D) containing a vinyl monomer, and 35 to 65 mass% of styrene-unsaturated dicarboxylic acid copolymer (C). The styrene-unsaturated dicarboxylic acid copolymer (C) contains 65 to 90 mass% of styrene structural units (c1) and 10 to 35 mass% of unsaturated dicarboxylic anhydride structural units (c2). In other words, resin (B6) is a resin composition containing two or more resins.

[0125] Resins containing vinyl monomers (D) The vinyl monomer-containing resin (D) may be the same as that described for the resin (B3) above. The vinyl monomer-containing resin (D) may be used alone or in combination of two or more kinds.

[0126] Styrene-unsaturated dicarboxylic acid copolymer (C) The styrene-unsaturated dicarboxylic acid copolymer (C) may be the same as that described in the above resin (B2). The styrene-unsaturated dicarboxylic acid copolymer (C) may be used alone or in combination of two or more kinds.

[0127] It is preferable that the high-hardness resin contains at least one selected from the group consisting of the above-mentioned resins (B1) to (B6), since this makes it possible to obtain an antiglare laminate having superior shape stability under high-temperature and high-humidity conditions.

[0128] [Additives] The high-hardness resin layer may contain an additive.

[0129] The additives are not particularly limited, and may be any additive that is commonly used in antiglare laminates.Specific examples include antioxidants, anticoloring agents, antistatic agents, release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, and reinforcing materials such as organic fillers and inorganic fillers.

[0130] The amount of the additive is preferably from 0 to 10% by mass, more preferably from 0 to 7% by mass, and particularly preferably from 0 to 5% by mass, based on the total mass of the high-hardness resin layer.

[0131] The method for mixing the additive and the resin is not particularly limited, and a method of compounding the entire amount, a method of dry blending a master batch, a method of dry blending the entire amount, or the like can be used.

[0132] [Structure of high-hardness resin layer] The thickness of the high-hardness resin layer is preferably 10 to 250 μm, more preferably 30 to 200 μm, and particularly preferably 60 to 150 μm. When the thickness of the high-hardness resin layer is 10 μm or more, the surface hardness is increased, which is preferable. On the other hand, when the thickness of the high-hardness resin layer is 250 μm or less, the impact resistance is increased, which is preferable.

[0133] [Lamination of high-hardness resin layer onto base layer] As described above, an additional layer may exist between the substrate layer and the high-hardness resin layer, but here, a case where a high-hardness resin layer is laminated on the substrate layer will be described.

[0134] The total thickness of the base layer and the high-hardness resin layer is preferably 100 to 3500 μm, more preferably 100 to 3000 μm, further preferably 500 to 3000 μm, and particularly preferably 1200 to 3000 μm. If the total thickness is 100 μm or more, the rigidity of the sheet can be maintained, which is preferable. On the other hand, if the total thickness is 3500 μm or less, it is preferable to prevent the sensitivity of the touch sensor from being deteriorated when a touch panel is installed under the sheet.

[0135] The ratio of the thickness of the base layer to the total thickness of the base layer and the high-hardness resin layer is preferably 75% to 99%, more preferably 80% to 99%, and particularly preferably 85% to 99%. By setting it in the above range, both hardness and impact resistance can be achieved.

[0136] The method of laminating the high-hardness resin layer on the substrate layer is not particularly limited, and examples thereof include a method of overlapping a substrate layer and a high-hardness resin layer formed separately and heating and pressing them together; a method of overlapping a substrate layer and a high-hardness resin layer formed separately and bonding them together with an adhesive; a method of co-extrusion molding the substrate layer and the high-hardness resin layer; a method of in-mold molding the substrate layer into a previously formed high-hardness resin layer to integrate them, etc. Among these, the co-extrusion molding method is preferred from the viewpoints of production cost and productivity.

[0137] The method of co-extrusion is not particularly limited. For example, in the feed block method, a high-hardness resin layer is arranged on one side of a base layer in a feed block, extruded into a sheet shape with a T-die, and then cooled while passing through a forming roll to form a desired laminate. In the multi-manifold method, a high-hardness resin layer is arranged on one side of a base layer in a multi-manifold die, extruded into a sheet shape, and then cooled while passing through a forming roll to form a desired laminate.

[0138] <Hard coat layer> The hard coat layer is not particularly limited, but is preferably an acrylic hard coat. In this specification, the term "acrylic hard coat" refers to a coating film formed by polymerizing a monomer, oligomer, or prepolymer containing a (meth)acryloyl group as a polymerizable group to form a crosslinked structure. The hard coat layer may further contain a UV absorber.

[0139] The hard coat layer is preferably free of organic particles and inorganic particles.By not including organic particles and inorganic particles, scratch resistance can be improved.As described later, the anti-glare treatment of the hard coat layer is carried out by transfer using a mold, so that the hard coat layer having a concave-convex shape can be formed without including organic particles and inorganic particles.

[0140] The content of the (meth)acrylic monomer is preferably 2 to 98 mass %, more preferably 5 to 50 mass %, and even more preferably 20 to 40 mass %, based on the total mass of the (meth)acrylic monomer, the (meth)acrylic oligomer, and the surface modifier.

[0141] The content of the (meth)acrylic oligomer is preferably 2 to 98 mass%, more preferably 50 to 95 mass%, and even more preferably 60 to 80 mass%, based on the total mass of the (meth)acrylic monomer, the (meth)acrylic oligomer, and the surface modifier.

[0142] Furthermore, the content of the surface modifier is preferably 0 to 15 mass %, more preferably 1 to 10 mass %, and even more preferably 2 to 5 mass %, based on the total mass of the (meth)acrylic monomer, the (meth)acrylic oligomer, and the surface modifier.

[0143] In addition, when a photopolymerization initiator is contained, the content of the photopolymerization initiator is preferably 0.001 to 7 parts by mass, more preferably 0.01 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the total of the (meth)acrylic monomer, the (meth)acrylic oligomer, and the surface modifier. In this specification, the photopolymerization initiator refers to a photoradical generator.

[0144] [(Meth)acrylic monomer] As the (meth)acrylic monomer, any monomer having a (meth)acryloyl group as a functional group in the molecule can be used, specifically, a monofunctional monomer, a difunctional monomer, or a trifunctional or higher functional monomer.

[0145] Examples of the monofunctional monomer include (meth)acrylic acid and (meth)acrylic acid esters.

[0146] Specific examples of bifunctional and / or trifunctional or higher (meth)acrylic monomers include diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, tetraethylene glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, polyethylene Examples of the monomer units include ethylene glycol diacrylate, 1,4-butanediol oligoacrylate, neopentyl glycol oligoacrylate, 1,6-hexanediol oligoacrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane propoxy tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glyceryl propoxy tri(meth)acrylate, trimethylolpropane trimethacrylate, trimethylolpropane ethylene oxide adduct triacrylate, glycerin propylene oxide adduct triacrylate, and pentaerythritol tetraacrylate.

[0147] The hard coat layer may contain one or more types of (meth)acrylic monomers.

[0148] [(Meth)acrylic oligomer] Examples of the (meth)acrylic oligomer include difunctional or higher polyfunctional urethane (meth)acrylate oligomers (hereinafter also referred to as "polyfunctional urethane (meth)acrylate oligomers"), difunctional or higher polyfunctional polyester (meth)acrylate oligomers (hereinafter also referred to as "polyfunctional polyester (meth)acrylate oligomers"), difunctional or higher polyfunctional epoxy (meth)acrylate oligomers (hereinafter also referred to as "polyfunctional epoxy (meth)acrylate oligomers").

[0149] Examples of the polyfunctional urethane (meth)acrylate oligomer include a urethane reaction product between a (meth)acrylate monomer having at least one (meth)acryloyloxy group and a hydroxyl group in one molecule and a polyisocyanate; a urethane reaction product between an isocyanate compound obtained by reacting a polyol with a polyisocyanate and a (meth)acrylate monomer having at least one (meth)acryloyloxy group and a hydroxyl group in one molecule; and the like.

[0150] Examples of the (meth)acrylate monomer having at least one (meth)acryloyloxy group and one hydroxyl group in one molecule used in the urethanization reaction include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate.

[0151] Examples of polyisocyanates used in the urethanization reaction include hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diisocyanates obtained by hydrogenating aromatic isocyanates among these isocyanates (for example, diisocyanates such as hydrogenated tolylene diisocyanate and hydrogenated xylylene diisocyanate), di- or tri-polyisocyanates such as triphenylmethane triisocyanate and dimethylene triphenyl triisocyanate, and polyisocyanates obtained by polymerizing diisocyanates.

[0152] Polyols used in the urethanization reaction generally include aromatic, aliphatic and alicyclic polyols as well as polyester polyols, polyether polyols and the like.

[0153] Typical aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, trimethylolethane, trimethylolpropane, dimethylolheptane, dimethylolpropionic acid, dimethylolbutyric acid, glycerin, hydrogenated bisphenol A, and the like.

[0154] The polyester polyol may be one obtained by the dehydration condensation reaction of the above-mentioned polyols with a polycarboxylic acid. Specific examples of the polycarboxylic acid include succinic acid, adipic acid, maleic acid, trimellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may be anhydrides.

[0155] Examples of the polyether polyol include polyalkylene glycols, as well as polyoxyalkylene-modified polyols obtained by reacting the above-mentioned polyols or phenols with alkylene oxides.

[0156] The polyfunctional polyester (meth)acrylate oligomer is obtained by a dehydration condensation reaction using (meth)acrylic acid, a polycarboxylic acid, and a polyol. Examples of polycarboxylic acids used in the dehydration condensation reaction include succinic acid, adipic acid, maleic acid, itaconic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may be anhydrides. Examples of polyols used in the dehydration condensation reaction include 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimethylolheptane, dimethylolpropionic acid, dimethylolbutyric acid, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0157] The polyfunctional epoxy (meth)acrylate oligomer is obtained by an addition reaction between a polyglycidyl ether and (meth)acrylic acid. Examples of the polyglycidyl ether include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and bisphenol A diglycidyl ether.

[0158] The hard coat layer may contain one or more types of (meth)acrylic oligomers.

[0159] [Surface modifier] The surface modifier is an agent that changes the surface performance of the hard coat layer, such as a leveling agent, an antistatic agent, a surfactant, a water- and oil-repellent agent, inorganic particles, or organic particles.

[0160] Examples of the leveling agent include polyether-modified polyalkylsiloxane, polyether-modified siloxane, polyester-modified hydroxyl-containing polyalkylsiloxane, polyether-modified polydimethylsiloxane having an alkyl group, modified polyether, and silicon-modified acrylic.

[0161] Examples of the antistatic agent include glycerin fatty acid ester monoglycerides, glycerin fatty acid ester organic acid monoglycerides, polyglycerin fatty acid esters, sorbitan fatty acid esters, cationic surfactants, and anionic surfactants.

[0162] Examples of the surfactant and the water / oil repellent agent include fluorine-containing surfactants and water / oil repellents such as an oligomer containing a fluorine-containing group and a lipophilic group, and an oligomer containing a fluorine-containing group, a hydrophilic group, a lipophilic group, and a UV-reactive group.

[0163] Examples of the inorganic particles include silica particles, alumina particles, zirconia particles, silver particles, and glass particles.

[0164] Examples of the organic particles include acrylic particles and silicon particles.

[0165] The hardcoat layer may contain one or more surface modifiers.

[0166] [Photopolymerization initiator] Examples of the photopolymerization initiator include monofunctional photopolymerization initiators.Specific examples include 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone [Darocure 2959: manufactured by Merck]; α-hydroxy-α,α'-dimethylacetophenone [Darocure 1173: manufactured by Merck]; acetophenone-based initiators such as methoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone [Irgacure-651], and 1-hydroxy-cyclohexylphenyl ketone; benzoin ether-based initiators such as benzoin ethyl ether and benzoin isopropyl ether; and other halogenated ketones, acylphosphinoxides, and acylphosphonates.These photopolymerization initiators may be used alone or in combination of two or more.

[0167] [UV absorber] Examples of UV absorbents include hydroxyphenyltriazines, benzotriazoles, and benzophenones. The UV absorbents may be used alone or in combination of two or more.

[0168] [Structure of hard coat layer] The thickness of the hard coat layer is preferably 1 to 40 μm, and more preferably 2 to 10 μm. When the thickness of the hard coat layer is 1 μm or more, sufficient hardness can be obtained, which is preferable. On the other hand, when the thickness of the hard coat layer is 40 μm or less, the occurrence of cracks during bending can be suppressed, which is preferable. The thickness of the hard coat layer can be measured by observing the cross section with a microscope or the like and measuring from the coating interface to the surface.

[0169] The pencil hardness of the hard coat layer surface is preferably HB or higher, more preferably H or higher, even more preferably 2H or higher, and particularly preferably 2H to 3H. The pencil hardness of the hard coat layer is a result of evaluation by a pencil scratch hardness test conforming to JIS K 5600-5-4:1999. Specifically, pencils of gradually increasing hardness were pressed against the surface of the hard coat layer at an angle of 45 degrees and a load of 750 g, and the hardness of the hardest pencil that did not leave a scratch was evaluated as the pencil hardness.

[0170] The hard coat layer has an uneven shape, so that an antiglare laminate having excellent antiglare properties and tactile feel can be obtained. Specifically, the hard coat layer has a developed interface area ratio (Sdr), an arithmetic mean height (Sa), and an autocorrelation length (Sal) that satisfy the following formulas (i) to (iii). In this specification, the developed interface area ratio (Sdr), the arithmetic mean height (Sa), and the autocorrelation length (Sal) are measured in accordance with ISO 25178-2:2012, as described in the examples described later.

[0171] 0≦Sdr≦0.6 (i) 0≦Sa≦0.16 (ii) 0≦Sal≦15.0 (iii)

[0172] Regarding the formula (i), the developed interface area ratio (Sdr) is an index of antiglare properties and correlates with haze. If Sdr exceeds 0.6, the light scattering becomes excessive, resulting in whitening and poor texture. It is more preferable that the formula (i) satisfies 0≦Sdr≦0.5, more preferably 0≦Sdr≦0.4, and particularly preferably 0≦Sdr≦0.3.

[0173] Regarding the formula (ii), the arithmetic mean height (Sa) is an index of antiglare properties and correlates with image clarity. If Sa exceeds 0.16, the light scattering becomes excessive, resulting in whitening and poor texture. The formula (ii) more preferably satisfies 0.01≦Sa≦0.15, even more preferably satisfies 0.02≦Sa≦0.14, and particularly preferably satisfies 0.03≦Sa≦0.13.

[0174] Regarding the formula (iii), the autocorrelation length (Sal) is an index of anti-glare properties and correlates with glare. In a high-definition display device with a fine pixel size, the conventional surface irregularity size leads to degradation of image quality such as glare on the screen and blurred characters. That is, in the case of a high-definition display device, the conventional surface irregularity size is close to the pixel size of a high-definition display in order of magnitude, and glare occurs due to the lens effect caused by the surface irregularity. In the conventional fine particle size, scattering increases near the straight transmitted light, making the outline of the pixel unclear and causing blurred characters. Furthermore, the intensity distribution of the transmitted scattered light depends on the size of the fine particles added, and with smaller fine particles, scattering around the straight transmitted light is reduced, reducing glare, but with larger fine particles, scattering around the straight transmitted light is increased, causing glare. When Sal exceeds 15.0, scattering increases near the straight transmitted light, increasing glare. Formula (iii) more preferably satisfies 1.0≦Sal≦12.0, even more preferably satisfies 2.0≦Sal≦10.0, and particularly preferably satisfies 3.0≦Sal≦8.0.

[0175] <Haze> The haze of the hard coat layer of the antiglare laminate of the present invention is preferably 30% or less, more preferably 25% or less, even more preferably 22% or less, and particularly preferably 21%. In this specification, the haze is a value measured in accordance with JIS K 7136:2000 using HR-100 type (manufactured by Murakami Color Research Laboratory).

[0176] <Glare> The glare in the hard coat layer of the antiglare laminate of the present invention is preferably 8% or less, more preferably 7% or less, even more preferably 6% or less, and particularly preferably 5% or less. In this specification, the uneven shape of the antiglare laminate is placed facing up on a 265ppi iPad6 (registered trademark) with green display (R:0, G:205, B:0), and an image is taken with Konica Minolta's Prometric Y29. Then, a 60mm x 60mm area is extracted from the captured screen, and the extracted image is divided into 9 areas using the Random Mura sequence of the analysis software "True Test". The glare value can be calculated for each of the 9 divided areas by "(display) luminance standard deviation / average luminance of evaluation range". It is preferable that the average of the glare values ​​calculated for each of the 9 areas is 2.0 or less when used as a front panel. The distance between the lens and the antiglare laminate was 500mm. Glare value calculation method: (Display) Luminance standard deviation / average luminance of evaluation range

[0177] <Imageability> One method for evaluating image reflection is the image clarity of reflection measured at a light incidence angle of 60° based on JIS K 7374. The optical comb widths are 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm. A narrower optical comb width results in a larger variation in values, whereas a wider optical comb width results in a smaller variation in values. Therefore, the optical comb width of 2.0 mm is preferred. The reflection clarity measured at a light incidence angle of 60° indicates that the larger the value, the easier it is for an image to be reflected, and the smaller the value, the less likely it is for an image to be reflected. In the present invention, the reflection clarity can be measured by the method described in the examples below.

[0178] In order to achieve both character blurring and image reflection performance, the uneven shape in the present invention preferably has a reflection clarity of 15% or more, more preferably 40% or more, and particularly preferably 50% or more, as measured at a light incidence angle of 60° using a 2.0 mm wide optical comb.

[0179] [Method of forming hard coat layer] The method for forming the hard coat layer is not particularly limited. For example, the hard coat layer can be formed by applying a hard coat liquid onto a layer (e.g., a high-hardness resin layer) located below the hard coat layer, and then photopolymerizing the hard coat layer.

[0180] The method of applying the hard coat liquid (polymerizable composition, reactive composition) is not particularly limited, and any known method can be used, such as spin coating, dipping, spraying, slide coating, bar coating, roll coating, gravure coating, meniscus coating, flexographic printing, screen printing, beat coating, and brushing.

[0181] The lamp used for light irradiation in photopolymerization has an emission distribution of 420 nm or less. Examples of such lamps include low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra-high pressure mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, and metal halide lamps. Among these, high pressure mercury lamps or metal halide lamps are preferred because they efficiently emit light in the active wavelength range of the photopolymerization initiator and do not emit a lot of short wavelength light that reduces the viscoelastic properties of the resulting polymer due to crosslinking, or long wavelength light that heats and evaporates the reaction composition.

[0182] The irradiation intensity of the lamp is a factor that determines the degree of polymerization of the resulting polymer, and is appropriately controlled for each performance of the target product. When a typical cleavage-type photopolymerization initiator having an acetophenone group is blended, the illuminance is 0.1 to 300 mW / cm 2 In particular, a metal halide lamp is used, and the illuminance is set to 10 to 40 mW / cm. 2 It is preferable to set the above.

[0183] The photopolymerization reaction is inhibited by oxygen in the air or oxygen dissolved in the reactive composition. Therefore, it is desirable to perform the light irradiation using a method that can eliminate the reaction inhibition caused by oxygen. One such method is a method in which the reactive composition is covered with a film made of polyethylene terephthalate or Teflon (registered trademark) to prevent contact with oxygen, and light is irradiated to the reactive composition through the film. In addition, the reactive composition may be irradiated with light through a light-transmitting window in an inert atmosphere in which oxygen is replaced with an inert gas such as nitrogen gas or carbon dioxide gas.

[0184] When the light irradiation is performed under an inert atmosphere, a certain amount of inert gas is always introduced to keep the oxygen concentration of the atmosphere at a low level. The introduction of this inert gas generates an airflow on the surface of the reactive composition, causing monomer evaporation. In order to suppress the level of monomer evaporation, the airflow speed of the inert gas is preferably 1 m / sec or less, more preferably 0.1 m / sec or less, as a relative speed to the laminate coated with the hard coat liquid moving under the inert gas atmosphere. By setting the airflow speed within the above range, monomer evaporation due to airflow is substantially suppressed.

[0185] In order to improve the adhesion of the hard coat layer, the coated surface may be pretreated by known methods such as sandblasting, solvent treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone treatment, ultraviolet treatment, and primer treatment using a resin composition.

[0186] The method of forming unevenness on the hard coat layer (anti-glare treatment) is not particularly limited, but a method using a mold is preferred. For example, a high-hardness resin layer, a coating film obtained by applying a reactive composition, and a mold are laminated in this order. Then, the reactive composition is photopolymerized and the mold is removed. The photopolymer of the reactive composition (hard coat layer) has a shape that reflects the rough surface of the mold at the contact surface with the mold. That is, the anti-glare treatment of the hard coat layer is performed by transfer using a mold.

[0187] The mold is not particularly limited as long as it transmits UV light, and glass, transparent resin, etc. are used. In one embodiment, the mold is a mold in which a transparent film and a transparent resin having a rough surface are laminated. The transparent film is PET film. The transparent resin having a rough surface is acrylic resin, etc. In this case, the rough surface of the transparent resin is not particularly limited, and may be formed by adding particles (organic particles, inorganic particles, etc.) to the transparent resin, may be formed by etching the transparent resin, or may be formed by printing and curing the transparent resin. The shape of the rough surface is not particularly limited, but is preferably a pattern from the viewpoint of use in applications such as liquid crystal panels. The surface (uneven shape) of the hard coat layer can be controlled by controlling the type of mold used (material, surface haze, thickness, shape, etc.), the amount of particles added, etc. Thereby, a hard coat layer satisfying the above-mentioned formulas (i) to (iii) can be formed. In addition, it is preferable to form a hard coat layer that further satisfies the above-mentioned formulas (iv) to (vi).

[0188] Among the above-mentioned methods for forming the hard coat layer, it is preferable to transfer the uneven shape by pressing a patterned PET film. That is, according to one embodiment of the present invention, a method for manufacturing an antiglare laminate is provided. In this case, the manufacturing method includes a step of pressing a patterned PET film onto the surface of the hard coat layer to transfer the uneven shape. As the patterned PET film, for example, PTH, PTHA, or PTHZ of Emblet manufactured by Unitika, or PF11 or PF23 of low glare AG film manufactured by Daicel can be used. As an example of a method for producing a patterned PET film that is preferably used in the method for producing an antiglare laminate of the present invention, the coating liquid is applied to a PET (polyethylene terephthalate) film so that the dry film thickness is 2.0 to 4.0 μm, and the film is dried at 70 to 90° C. for 1 to 3 minutes. After that, the film is cured by irradiating it with ultraviolet light at a line speed of 1.0 to 3.0 m / min using a conveyor equipped with a high-pressure mercury lamp with a light source distance of 12 cm and an output of 80 W / cm at a line speed of 1.0 to 3.0 m / min, thereby producing a patterned PET film. The coating liquid preferably contains an organic solvent such as methyl ethyl ketone (MEK), an acrylic ultraviolet curing resin, silica fine particles, and a photoinitiator. The content of these components is preferably 70 to 80 parts by mass of the organic solvent such as methyl ethyl ketone (MEK), 19 to 29 parts by mass of the acrylic ultraviolet curing resin, 0.2 to 1.0 parts by mass of silica fine particles (average particle size 3.5 to 5.0 μm), and 2.0 to 4.0 parts by mass of the photoinitiator. This makes it possible to form a hard coat layer that satisfies the above-mentioned formulas (i) to (iii).

[0189] <Physical properties of antiglare laminate> In one embodiment, the antiglare laminate preferably has high shape stability. Specifically, the change in warp after 120 hours of storage in an environment of 85°C temperature and 85% relative humidity is preferably 350 μm or less, more preferably 250 μm or less, even more preferably 175 μm or less, and particularly preferably 75 μm or less. If the change in warp is 350 μm or less, it is preferable because it can be used suitably even in a high-temperature and high-humidity environment. High shape stability can be obtained by using a high-hardness resin layer. By interposing a high-hardness resin layer between the substrate layer and the hard coat layer, the shape of the antiglare laminate is stable even in a high-temperature and high-humidity environment. Shape stability can also be controlled by appropriately changing the materials of the substrate layer and the hard coat layer, the difference in glass transition temperature (Tg) between the substrate layer and the high-hardness resin layer, the difference in hardness, the difference in glass transition temperature (Tg) between the high-hardness resin layer and the hard coat layer, the difference in hardness, etc.

[0190] <Application> The antiglare laminate of the present invention is excellent in antiglare properties and tactile feel, and is therefore used as a protective plate or front panel for a liquid crystal surface, as described above. In one embodiment, an in-vehicle display device including the antiglare laminate is provided. In another embodiment, a touch panel front protective plate including the antiglare laminate is provided. In yet another embodiment, a front panel for an office automation device, a portable electronic device, or a television is provided. EXAMPLES

[0191] The following examples of the present invention are given, but the present invention is not limited to the embodiments of the examples.

[0192] <Surface roughness measurement> Using a confocal laser microscope "OLS 5000" manufactured by Olympus Corporation, the surface of the hard coat layer having an uneven surface was measured for the developed interface area ratio (Sdr), arithmetic mean height (Sa), and autocorrelation length (Sal) under the following conditions in accordance with ISO 25178-2:2012.

[0193] [Developed interface area ratio (Sdr)] Observation conditions Objective lens: 20x Acquisition mode: Precision priority Measurement area: 645μm×645μm Analysis conditions Correction: Remove spike noise and tilt Arithmetic mean height (Sa) Observation conditions Objective lens: 20x Acquisition mode: Precision priority Measurement area: 645μm×645μm Analysis conditions Correction: Remove spike noise and tilt [Autocorrelation length (Sal)] Observation conditions Objective lens: 100x Acquisition mode: Precision priority Measurement area: 129μm×129μm Analysis conditions Correction: Remove spike noise and tilt

[0194] <Haze> The haze was calculated using "HR-100" manufactured by Murakami Color Research Laboratory according to the method defined in JIS K 7136:2000.

[0195] <Reflection clarity (image clarity)> Measurements were performed using Suga Test Instruments' "ICM 1T" in accordance with JIS K7374, with the optical comb set so that the flow direction of the antiglare laminate was parallel to the direction of the comb teeth. A 2.0 mm optical comb was used to measure the image clarity of the reflection at an incident angle of 60°, and this was taken as the reflection clarity. Measurements were performed by applying black tape (black vinyl tape model 117BLA, manufactured by 3M Japan Co., Ltd.) to the back of the uneven surface to suppress back reflection.

[0196] <Glare> The uneven shape of the antiglare laminate was placed upward on an iPad6 (registered trademark) with a 265 ppi green display (R: 0, G: 205, B: 0). After taking an image with a Konica Minolta Prometric Y29, a 60 mm × 60 mm area was extracted from the captured screen. The extracted image was divided into nine parts using the Random Mura sequence of the analysis software "True Test", and the value of the unevenness was calculated for each of the nine divided regions by "(display) luminance standard deviation / average luminance of the evaluation range". It is preferable that the average of the unevenness values calculated for each of the nine regions is 2.0 or less when used as the front panel. The distance between the lens and the antiglare laminate was 500 mm. · Method for calculating the value of unevenness: (display) luminance standard deviation / average luminance of the evaluation range

[0197] <SW hardness> For the hard coat layer having the uneven shape of the antiglare laminate, using a steel wool #0000 made by Nippon Steel Wool, 100 g / cm 2 The degree of damage when reciprocated 15 times under a load was visually observed and evaluated on a 10 - point scale. It was described as RANK1 - RANK10. The measurement was performed twice, and when different results were obtained, the range was taken as the measurement result.

[0198] RANK1: No damage (equivalent to inorganic glass) RANK2: 1 - 5 scratches RANK3: 6 - 10 scratches RANK4: 11 - 15 scratches RANK5: 16 - 20 scratches RANK6: 21 - 25 scratches RANK7: 26 - 30 scratches RANK8: 31 - 40 scratches RANK9: 41 or more scratches (equivalent to polymethacrylic acid) RANK10: 41 or more scratches (equivalent to polycarbonate)

[0199] <Shape stability> A test piece (antiglare laminate) was cut to 100 mm x 60 mm. The cut test piece was set in a two-point support holder and placed in an environmental tester set at a temperature of 23% and a relative humidity of 50% for more than 24 hours to condition it, and then the warpage was measured (before treatment). Next, the test piece was set in the holder and placed in an environmental tester set at a temperature of 85°C and a relative humidity of 85%, and held in that state for 120 hours. The holder was then moved into an environmental tester set at a temperature of 23% and a relative humidity of 50%, and the warpage was measured again after holding in that state for 4 hours (after treatment). The warpage was measured using a three-dimensional shape measuring machine (KS-1000 manufactured by KEYENCE) equipped with an electric stage, and the taken-out test piece was placed horizontally in a convex state, scanned at 1 mm intervals, and the swelling in the center was measured as the warpage. The absolute value of the difference in the amount of warpage before and after treatment, i.e. |(Warpage after processing)-(Warpage before processing)| was evaluated as shape stability.

[0200] [Example 1] <Laminate> A synthetic resin laminate was formed using a multi-layer extrusion device having a single screw extruder with a shaft diameter of 35 mm, a single screw extruder with a shaft diameter of 65 mm, a feed block connected to all the extruders, and a T-die connected to the feed block. Mitsubishi Gas Chemical's Optimas 7500 was continuously introduced as the high-hardness resin (B1) into the single screw extruder with a shaft diameter of 35 mm, and extruded under the conditions of a cylinder temperature of 240°C and a discharge rate of 2.6 kg / h. Polycarbonate resin (manufactured by Mitsubishi Engineering Plastics Corporation, product name: Iupilon S-1000) was continuously introduced into the single screw extruder with a shaft diameter of 65 mm, and extruded at a cylinder temperature of 280°C and a discharge rate of 50.0 kg / h. The feed block connected to all the extruders was equipped with two-type, two-layer distribution pins, and the high-hardness resin (B1) and polycarbonate resin were introduced and laminated at a temperature of 270°C. The sheet was extruded into a sheet shape through a T-die connected to the upstream at a temperature of 270°C, and cooled while transferring a mirror surface with three mirror-finishing rolls whose temperatures were 120°C, 130°C, and 190°C from the upstream side, to obtain a laminate of a high-hardness resin (B1) layer (high-hardness resin layer) and a polycarbonate resin layer (base layer). The thickness of the obtained laminate was 1.0 mm, and the thickness of the high-hardness resin (B1) layer was 60 μm near the center.

[0201] The Optimas 7500 manufactured by Mitsubishi Gas Chemical Company, used as the high hardness resin (B1), is a copolymer resin containing the (meth)acrylic acid ester structural unit (a) represented by the general formula (1) and the aliphatic vinyl structural unit (b) represented by the general formula (2). In this case, the total ratio of the (meth)acrylic acid ester structural unit (a) and the aliphatic vinyl structural unit (b) is 99 mol % of the total structural units of the copolymer resin, and the ratio of the (meth)acrylic acid ester structural unit (a) is 75 mol % of the total structural units of the copolymer resin.

[0202] <Photocurable resin composition (Y-1)> A photocurable resin composition (Y-1) was obtained by adding 3 parts by mass of photoinitiator I-184 (manufactured by BASF Ltd. [compound name: 1-hydroxycyclohexyl phenyl ketone]) to 100 parts by mass of a mixture of 60% by mass of U6HA (hexafunctional urethane acrylate oligomer, manufactured by Shin-Nakamura Chemical Co., Ltd.), 35% by mass of #260 (1,9-nonanediol diacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and 5% by mass of a fluorine-based leveling agent.

[0203] <Patterned PET film (Z-1)> Coating solution (i) was prepared by mixing and stirring 77 parts by mass of MEK with 22.7 parts by mass of acrylic ultraviolet-curing resin (100% solids, product name: Light Acrylate DPE-6A; manufactured by Kyoeisha Chemical Co., Ltd.), 0.3 parts by mass of silica fine particles (NP-30, average particle size 4 μm, manufactured by AGC Si-Tech Co., Ltd.), and 3 parts by mass of photoinitiator (product name Omnirad184; manufactured by IGM Resins) as external additives. Next, coating solution (i) was applied to a PET (polyethylene terephthalate) film so that the dry film thickness was 2.5 μm, and after drying at 80°C for 2 minutes, it was irradiated with ultraviolet light at a line speed of 1.5 m / min on a conveyor equipped with a high-pressure mercury lamp with a light source distance of 12 cm and an output of 80 W / cm, and cured to produce a patterned PET film (Z-1).

[0204] A photocurable resin composition (Y-1) was applied to the high-hardness resin (B1) layer of the laminate of the high-hardness resin (B1) layer (high-hardness resin layer) and the polycarbonate resin layer (base layer) using a bar coater so that the coating thickness after curing was 5 to 10 μm, and the patterned PET film (Z-1) was covered and pressed so that the patterned surface of the film was in contact with the coating liquid. Then, the film was cured by irradiating with a metal halide lamp (20 mW / cm) at a light source distance of 12 cm for 30 seconds, and the patterned PET film was peeled off to obtain an antiglare laminate having a rough hard coat layer on the high-hardness resin layer (B1).

[0205] [Example 2] An antiglare laminate was produced in the same manner as in Example 1, except that the high-hardness resin (B1) was replaced with the following high-hardness resin (B3).

[0206] The high-hardness resin (B3) was prepared as follows. That is, 75% by mass of Resisfy R100 (manufactured by Denki Kagaku Kogyo Co., Ltd.) was charged as a styrene-unsaturated dicarboxylic acid copolymer (E) and 25% by mass of Parapet HR-L (manufactured by Kuraray Co., Ltd.), a methyl methacrylate resin, was charged as a resin (D) containing a vinyl monomer, and mixed in a blender for 30 minutes. Next, using an extruder with a screw diameter of 26 mm (manufactured by Toshiba Machine Co., Ltd., TEM-26SS, L / D ≒ 40), the mixture was melt-kneaded at a cylinder temperature of 230°C, extruded into a strand shape, and pelletized with a pelletizer to obtain the high-hardness resin (B3). The pelletization was performed stably.

[0207] [Example 3] An antiglare laminate was produced in the same manner as in Example 1, except that the high hardness resin (B6) below was used instead of the high hardness resin (B1).

[0208] The high-hardness resin (B6) was prepared as follows. That is, 50% by mass of XIBOND160 (manufactured by Polyscope) as a styrene-unsaturated dicarboxylic acid copolymer (C) and 50% by mass of Parapet HR-L (manufactured by Kuraray), a methyl methacrylate resin, as a resin (D) containing a vinyl monomer were charged and mixed in a blender for 30 minutes. Next, using an extruder with a screw diameter of 26 mm (manufactured by Toshiba Machine, TEM-26SS, L / D≒40), the mixture was melt-kneaded at a cylinder temperature of 230°C, extruded into a strand shape, and pelletized with a pelletizer to obtain the high-hardness resin (B6). The pelletization was performed stably.

[0209] [Example 4] An antiglare laminate was produced in the same manner as in Example 1, except that the following patterned PET film (Z-2) was used instead of the patterned PET film (Z-1).

[0210] <Patterned PET film (Z-2)> A patterned PET film (Z-2) was produced by using the following coating liquid (ii) instead of the coating liquid (i).

[0211] The coating liquid (ii) was prepared by mixing and stirring 77 parts by mass of MEK with 22.6 parts by mass of an acrylic ultraviolet-curable resin (100% solids, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.), 0.4 parts by mass of silica fine particles (NP-30, average particle size 4 μm, manufactured by AGC Si-Tech Co., Ltd.), and 3 parts by mass of a photoinitiator (product name Omnirad184, manufactured by IGM Resins) added externally.

[0212] [Example 5] An antiglare laminate was produced in the same manner as in Example 1, except that the patterned PET film (Z-1) was replaced with the following patterned PET film (Z-3).

[0213] <Patterned PET film (Z-3)> A patterned PET film (Z-3) was produced by using the following coating liquid (iii) instead of the coating liquid (i).

[0214] The coating liquid (iii) was prepared by mixing and stirring 77 parts by mass of MEK, 22.8 parts by mass of an acrylic ultraviolet-curable resin (100% solid content, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.), 0.2 parts by mass of silica fine particles (NP-30, average particle size 4 μm, manufactured by AGC Si-Tech Co., Ltd.), and 3 parts by mass of a photoinitiator (product name Omnirad184, manufactured by IGM Resins) added externally.

[0215] [Example 6] An antiglare laminate was produced in the same manner as in Example 1, except that the following patterned PET film (Z-4) was used instead of the patterned PET film (Z-1).

[0216] <Patterned PET film (Z-4)> A patterned PET film (Z-4) was produced by using the following coating liquid (iv) instead of the coating liquid (i).

[0217] The coating liquid (iv) was prepared by mixing and stirring 71.5 parts by mass of MEK, 27.7 parts by mass of an acrylic ultraviolet-curable resin (100% solids, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.), 0.8 parts by mass of silica fine particles (NP-30, average particle size 4 μm, manufactured by AGC Si-Tech Co., Ltd.), and 3 parts by mass of a photoinitiator (product name Omnirad184, manufactured by IGM Resins) added externally.

[0218] [Example 7] An antiglare laminate was produced in the same manner as in Example 1, except that the following patterned PET film (Z-5) was used instead of the patterned PET film (Z-1).

[0219] <Patterned PET film (Z-5)> A patterned PET film (Z-5) was produced by using the following coating liquid (v) instead of the coating liquid (i).

[0220] The coating liquid (v) was prepared by mixing and stirring 80 parts by mass of MEK with 19.4 parts by mass of an acrylic ultraviolet-curable resin (100% solids, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.), 0.6 parts by mass of silica fine particles (NP-30, average particle size 4 μm, manufactured by AGC Si-Tech Co., Ltd.), and 3 parts by mass of a photoinitiator (product name Omnirad184, manufactured by IGM Resins) added externally.

[0221] [Example 8] An antiglare laminate was produced in the same manner as in Example 1, except that the following patterned PET film (Z-6) was used instead of the patterned PET film (Z-1).

[0222] <Patterned PET film (Z-6)> Instead of the coating liquid (i), the following coating liquid (vi) was used to prepare a patterned PET film (Z-6) having a dry film thickness of 4.0 μm.

[0223] The coating liquid (vi) was prepared by mixing and stirring 80 parts by mass of MEK, 19.4 parts by mass of an acrylic ultraviolet-curable resin (100% solid content, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.), 0.6 parts by mass of silica fine particles (NP-30, average particle size 4 μm, manufactured by AGC Si-Tech Co., Ltd.), and 3 parts by mass of a photoinitiator (product name Omnirad184, manufactured by IGM Resins) added externally.

[0224] [Example 9] An antiglare laminate was produced in the same manner as in Example 1, except that the high hardness resin (B1) was replaced with a high hardness resin, methyl methacrylate resin Parapet HR-L (manufactured by Kuraray, weight average molecular weight: 90,000, pencil hardness: 2H).

[0225] [Comparative Example 1] An antiglare laminate was produced in the same manner as in Example 1, except that the following patterned PET film (Z-7) was used instead of the patterned PET film (Z-1).

[0226] <Patterned PET film (Z-7)> A patterned PET film (Z-7) was produced by using the following coating liquid (vii) instead of the coating liquid (i).

[0227] The coating liquid (vii) was prepared by mixing and stirring 71.5 parts by mass of MEK, 27.0 parts by mass of an acrylic ultraviolet-curable resin (100% solid content, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.), 1.5 parts by mass of silica fine particles (NP-30, average particle size 4 μm, manufactured by AGC Si-Tech Co., Ltd.), and 3 parts by mass of a photoinitiator (product name Omnirad184, manufactured by IGM Resins) added externally.

[0228] [Comparative Example 2] An antiglare laminate was produced in the same manner as in Example 1, except that the following patterned PET film (Z-8) was used instead of the patterned PET film (Z-1).

[0229] <Patterned PET film (Z-8)> A patterned PET film (Z-8) was produced by using the following coating liquid (viii) instead of the coating liquid (i).

[0230] The coating liquid (viii) was prepared by mixing and stirring 90.0 parts by mass of MEK, 9.5 parts by mass of an acrylic ultraviolet-curable resin (100% solid content, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.), 0.5 parts by mass of silica fine particles (NP-30, average particle size 4 μm, manufactured by AGC Si-Tech Co., Ltd.), and 3 parts by mass of a photoinitiator (product name Omnirad184, manufactured by IGM Resins) added externally.

[0231] [Comparative Example 3] An antiglare laminate was produced in the same manner as in Example 1, except that the patterned PET film (Z-1) was replaced with Nakajima Kogyo's C-50 G-100 (Z-9).

[0232] [Comparative Example 4] An antiglare laminate was produced in the same manner as in Example 1, except that the hard coat layer was formed as follows.

[0233] That is, 50 parts by mass of MEK, 50 parts by mass of an acrylic ultraviolet-curable resin (100% solids product: Light Acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.), 0.3 parts by mass of silica microparticles (octylsilane-treated fumed silica, average primary particle diameter 1.9 μm, product name: SE6050-SYB manufactured by Admatechs Co., Ltd.), and 3 parts by mass of a photoinitiator (product name Irgacure 184 manufactured by Toyotetsu Chemiplas Co., Ltd.) were mixed and stirred to prepare a photocurable composition (Y-2).

[0234] A photocurable composition (Y-2) was applied onto the high-hardness resin layer using a bar coater so that the coating thickness after curing was 2.5 μm, and then dried for 2 minutes at 80° C. The coating was cured by irradiating with a metal halide lamp (20 mW / cm) for 30 seconds at a light source distance of 12 cm while purging with nitrogen, to obtain an antiglare laminate.

[0235] The antiglare laminates obtained in Examples 1 to 9 and Comparative Examples 1 to 4 are shown in Table 1 below.

[0236] [Table 1]

[0237] In addition, the developed interface area ratio (Sdr), arithmetic mean height (Sa), autocorrelation length (Sal), haze, image clarity, glare, SW hardness, and shape stability were evaluated in Examples 1 to 9 and Comparative Examples 1 to 4. The obtained results are shown in Table 2 below.

[0238] [Table 2]

[0239] As is clear from the results in Table 2, Examples 1 to 9 have excellent antiglare properties because Sdr, Sa, and Sal satisfy the formulas (i) to (iii). In addition, Examples 1 to 8, which used high-hardness resins (B1), (B3), or (B6), were also confirmed to have excellent shape stability.

[0240] On the other hand, in Comparative Examples 1 and 2, the antiglare properties were insufficient because Sdr and Sa did not satisfy the formulas (i) and (ii). It was also confirmed that the antiglare properties were insufficient from the viewpoints of haze and image clarity.

[0241] In Comparative Example 3, Sa and Sal did not satisfy the formulas (ii) and (iii), and therefore the antiglare property was insufficient. It was also confirmed that the antiglare property was insufficient from the viewpoints of image clarity and glare.

[0242] Furthermore, in Comparative Example 4, Sdr does not satisfy formula (i), so the antiglare property is insufficient. It was also confirmed that the antiglare property was insufficient from the viewpoint of glare. It was confirmed that the glare was large because the hard coat layer contained silica fine particles, and the SW hardness was insufficient.

Claims

1. An antiglare laminate in which a base material layer containing at least a polycarbonate resin (a1), a high-hardness resin layer containing a high-hardness resin (B), and a hard coat layer are arranged in this order, wherein the developed interface area ratio (Sdr), arithmetic mean height (Sa), and autocorrelation length (Sal) of the hard coat layer satisfy the following formulas (i) to (iii): 0 ≤ Sdr ≤ 0.6 (i) 0 ≤ Sa ≤ 0.16 (ii) 0 ≤ Sal ≤ 15.0 (iii) An antiglare laminate that satisfies these conditions.

2. The developed interface area ratio (Sdr), arithmetic mean height (Sa), and autocorrelation length (Sal) of the hard coat layer satisfy the following formulas (iv) to (vi): 0 ≤ Sdr ≤ 0.3 (iv) 0.03 ≤ Sa ≤ 0.13 (v) 3.0 ≤ Sal ≤ 8.0 (vi) The antiglare laminate according to Claim 1 that satisfies these conditions.

3. The antiglare laminate according to Claim 1, wherein the amount of change in warpage after the antiglare laminate is held in an environment of 85°C and 85% relative humidity for 120 hours is 350 μm or less.

4. The antiglare laminate according to Claim 1, wherein the thickness of the high-hardness resin layer is 10 to 250 μm.

5. The antiglare laminate according to Claim 1, wherein the total thickness of the base material layer and the high-hardness resin layer is 100 to 3,000 μm.

6. The antiglare laminate according to Claim 1, wherein the hard coat layer does not contain organic particles and inorganic particles.

7. The polycarbonate resin (a1) has the following general formula (5): 【Chemical 1】 (In the formula, R ５ represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms, and R ６ each independently represents a hydrogen atom, a halogen, or an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms which may have a substituent, n is an integer of 0 to 4, and here, the substituent is a halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.) The antiglare laminate according to claim 1, comprising a component derived from a monohydric phenol represented by the formula.

8. An in-vehicle display device including the antiglare laminate according to any one of Claims 1 to 7.

9. A touch panel front protection plate including the antiglare laminate according to any one of Claims 1 to 7.

10. A front panel for OA equipment, portable electronic equipment, or a television including the antiglare laminate according to any one of Claims 1 to 7.

11. A method for manufacturing the antiglare laminate according to any one of Claims 1 to 7, wherein a patterned PET film is pressure-bonded to the surface of the hard coat layer to transfer the uneven shape, and the hard coat layer after transfer satisfies the following formulas (i) to (iii): 0 ≤ Sdr ≤ 0.6 (i) 0 ≤ Sa ≤ 0.16 (ii) 0 ≤ Sal ≤ 15.0 (iii) The manufacturing method including a step of ensuring that these conditions are satisfied.

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