Antiglare laminate and manufacturing method thereof

Abstract

To provide an antiglare laminate having antiglare property which achieves both a prevention performance of image reflection and suppression of character blurring and having high excoriation resistance and also excellent morphological stability, and a manufacturing method thereof.SOLUTION: The above problem is solved by an antiglare laminate where a substrate 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 arranged in this order, wherein a root-mean-square gradient (Sdq) and a root-mean-square height (Sq) of the hard coat layer respectively satisfy the following (i) and (ii): 0.010≤Sdq≤0.10 (i), 0.040≤Sq≤0.40 (ii).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an antiglare laminate and a manufacturing method thereof. More specifically, the present invention relates to an antiglare laminate that has antiglare performance, high scratch resistance, and excellent shape stability, and is used as a front protective plate for in-vehicle liquid crystal display devices, mobile phone terminals, personal computers, tablet PCs, etc., and a manufacturing method thereof. [Background technology]

[0002] Liquid crystal display devices are provided with a front panel to protect 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 made of a multilayer sheet in which an acrylic resin is laminated on the surface of a polycarbonate resin sheet and then hard-coated have been widely adopted as front panels because they have surface hardness and scratch resistance comparable to conventional hard-coated acrylic resins while also possessing the excellent impact resistance, heat resistance, processability, and transparency of polycarbonate resin. The front panel of a liquid crystal display device having the polycarbonate resin sheet is generally formed by melt extrusion together with an acrylic resin.

[0004] In liquid crystal display devices, an anti-reflection optical laminate is generally provided on the outermost surface, which suppresses image glare and reduces reflectance by scattering or interfering with light.

[0005] One known example of an anti-reflection optical laminate is an anti-glare film in which an anti-glare layer having an uneven surface is formed on the surface of a transparent substrate. This anti-glare film scatters external light using the uneven surface, preventing a decrease in visibility due to reflection of external light or glare of images. Furthermore, since this optical laminate is usually placed on the outermost surface of a liquid crystal display device, it is also required to have a hard coating property to prevent scratches during handling.

[0006] 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 to prevent specular reflection and prevent image glare. However, when an uneven surface is applied to prevent image glare, the scattering of transmitted light that travels straight ahead increases, making the outlines of pixels unclear and causing blurred characters.

[0007] Furthermore, if fine particles are added to create surface irregularities, the fine particles on the outermost surface will 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.

[0008] As described above, there has been no front panel for in-vehicle liquid crystal display devices, mobile phone terminals, personal computers, tablet PCs, etc. 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 undesirable because it reduces scratch resistance.

[0009] Furthermore, Patent Document 2 describes an antiglare laminate having antiglare performance that combines the performance of preventing image reflection and suppressing blurred characters, but claim 1 specifies that the haze specified in JIS K 7136 is 15% or more. If the haze exceeds 15%, the laminate gives a whitish impression when used in an in-vehicle liquid crystal display device, which leads to a decrease in visibility. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Patent Publication No. 2010-160398 [Patent Document 2] WO2020 / 203359 DISCLOSURE OF THE INVENTION [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 the performance of preventing image reflection and suppressing 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 described below. 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, arranged in this order, wherein the root-mean-square gradient (Sdq) and root-mean-square height (Sq) of the hard coat layer are expressed by the following formulas (i) and (ii), respectively: 0.010≦Sdq≦0.10 (i) 0.040≦Sq≦0.40 (ii) An antiglare laminate that satisfies the above requirements. <2> The root mean square gradient (Sdq) and root mean square height (Sq) of the hard coat layer are expressed by the following formulas (iii) and (iv), respectively: 0.035≦Sdq≦0.06 (iii) 0.20≦Sq≦0.35 (iv) 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> 10. The antiglare laminate according to any one of the preceding items. <5> The total thickness of the base layer and the high-hardness resin layer is 100 to 3,000 μm. <1> ~ <4> 10. The antiglare laminate according to any one of the preceding items. <6> The hard coat layer does not contain organic particles or inorganic particles. <1> ~ <5> 10. The antiglare laminate according to any one of the preceding items. <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, 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, 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> 10. The antiglare laminate according to any one of the preceding items. <8> the above <1> ~ <7> 10. An in-vehicle display device comprising the antiglare laminate according to any one of claims 1 to 9. <9> the above <1> ~ <7> 10. A touch panel front protection plate comprising the antiglare laminate according to any one of claims 1 to 9. <10> the above <1> ~ <7> 1. A front panel for office automation equipment, portable electronic devices, or televisions, comprising the antiglare laminate according to any one of claims 1 to 9. <11> the above <1> ~ <7> A method for producing the antiglare laminate according to any one of the above, A patterned PET film is pressed onto the surface of the hard coat layer to transfer the unevenness, and the hard coat layer after the transfer has a structure represented by the following formulas (i) and (ii): 0.010≦Sdq≦0.10 (i) 0.040≦Sq≦0.40 (ii) The manufacturing method as described above, comprising the step of satisfying the above. [Effects 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 method for producing the same. DETAILED DESCRIPTION OF THE INVENTION

[0014] Hereinafter, the present invention will be described in detail by way of examples and working examples, but the present invention is not limited to the illustrated examples and working examples, and can be carried out by any method as long as it does not significantly deviate from the content 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 (B), and a hard coat layer, which are arranged in this order.

[0016] The order of lamination of the anti-glare 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 anti-glare laminate has a configuration of high-hardness resin layer-substrate layer-high-hardness resin layer-hard coat layer. In another 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 anti-glare laminate has a configuration of hard coat layer-high-hardness resin layer-substrate layer-high-hardness resin layer-hard coat layer.

[0017] When high-hardness resin layers are provided on both sides of the substrate layer, it is more desirable to use the same high-hardness resin layers on both sides in terms of shape stability. Also, when hard coat layers are provided on both sides of the substrate, it is more desirable to provide similar hard coat layers on both sides in terms of improving shape stability. Note that the substrate layer and the high-hardness resin layer, and the high-hardness resin layer and the hard coat layer, may be laminated directly or via another layer, but it is preferable that they are laminated directly.

[0018] In one embodiment, the antiglare laminate can be used, for example, as a front protective plate for touch panels of in-vehicle display devices such as car navigation systems, center information displays (CIDs), rear seat entertainment devices (RSEs), and clusters, as well as front panels for office automation equipment, portable electronic devices, and televisions. Furthermore, for example, the front panel can be used alone as the front panel of a liquid crystal display device, but it may also be used as a composite front panel by, for example, 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) and may further contain additives.

[0021] [Polycarbonate resin (a1)] The polycarbonate resin (a1) is not particularly limited as long as it contains a carbonate bond, i.e., an -[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 linear or branched structure), in the molecular main chain. However, 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, aromatic polycarbonate resins (for example, manufactured by Mitsubishi Engineering Plastics Corporation, trade names: Iupilon S-2000, Iupilon S-1000, Iupilon E-2000) can be used as the polycarbonate resin (a1), but the polycarbonate resin is not limited thereto.

[0024] Furthermore, in recent years, there has been an increasing demand for bending the front panel as well, and therefore 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, and 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. 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.

[0030] 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 polycarbonate resin.

[0031] As an example, R 5 If the number of carbon atoms in R is 36 or less, the productivity and economy of producing polycarbonate resin are high. 5 When the carbon number of the monohydric phenol is 22 or less, the monohydric phenol has particularly excellent solubility in organic solvents, and the productivity in producing the polycarbonate resin can be significantly increased, resulting in improved economic efficiency.

[0032] R in general formula (5) or general formula (6) 5 When the lower limit of the number of carbon atoms is appropriate, the glass transition point of the polycarbonate resin is not too high, and the polycarbonate resin has favorable thermoformability, which is preferable.

[0033] For example, in general formula (6), R 5 When a monohydric phenol (terminal terminator) having an alkyl group of 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 polycarbonate resin production are excellent, and it is particularly preferable as a terminal terminator to be used for the polycarbonate resin of the present invention.

[0034] 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.

[0035] 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. A weight-average molecular weight of 15,000 or more of the polycarbonate resin (a1) is preferred because it can improve impact resistance. On the other hand, a weight-average molecular weight of 75,000 or less is preferred because it allows the substrate layer to be formed with a small heat source and maintains thermal stability even under high-temperature molding conditions. 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.

[0036] The polycarbonate resin (a1) contained in the substrate layer may be one type or two or more types. The content of the polycarbonate resin (a1) in the base layer is preferably 75% by mass or more, and from the viewpoint of improving impact resistance, more preferably 90% by mass or more, and even more preferably 100% by mass, based on the total mass of the base layer.

[0037] [Additives] The substrate layer may further contain an additive. The additives may be those commonly used in antiglare laminates, such as 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.

[0038] The amount of the additive is preferably 0 to 10% by mass, more preferably 0 to 7% by mass, and particularly preferably 0 to 5% by mass, relative to the total mass of the base layer.

[0039] The method for mixing the additive and the resin is not particularly limited, and methods such as compounding the entire amount, dry blending a master batch, and dry blending the entire amount can be used.

[0040] [Base layer composition] The thickness of the substrate layer is preferably 0.1 to 3.5 mm, more preferably 0.3 to 3 mm, and particularly preferably 1.2 to 3 mm.

[0041] <High hardness resin layer> The high-hardness resin layer contains a high-hardness resin. The high-hardness resin layer may further contain additives, etc., as needed. By providing the high-hardness resin layer between the substrate layer and the hard coat layer, an anti-glare laminate with high shape stability can be obtained. The high-hardness resin layer may also have functions such as increasing the hardness of the anti-glare laminate. In this specification, a high-hardness resin refers to a resin that is harder than the polycarbonate resin used as the substrate, and has a pencil hardness of HB or higher, 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 evaluated using a pencil scratch hardness test in accordance with JIS K 5600-5-4:1999. Specifically, pencils of gradually increasing hardness are pressed against the surface of the high-hardness resin layer at an angle of 45 degrees with a load of 750 g, and the hardness of the hardest pencil that does not leave a scratch is evaluated as the pencil hardness.

[0042] [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 containing multiple types of resins.

[0043] (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 proportion 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 all structural units in the copolymer resin. The proportion of the (meth)acrylic acid ester structural units (a) is 65 to 80 mol % of all structural units in the copolymer resin. In this specification, (meth)acrylic refers to methacrylic and / or acrylic.

[0044] [ka]

[0045] In the formula, R 1 is a hydrogen atom or a methyl group, preferably a methyl group. 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, more preferably a methyl group.

[0046] In addition, R 2 is a methyl group or an ethyl group, the (meth)acrylate structural unit (a) represented by general formula (1) becomes a (meth)acrylate 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.

[0047] 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.

[0048] [ka]

[0049] In the formula, R 3 is a hydrogen atom or a methyl group, and is preferably a hydrogen atom. R 4 is a cyclohexyl group which may be substituted with a hydrocarbon group having 1 to 4 carbon atoms, and is preferably an unsubstituted cyclohexyl group. In this specification, the "hydrocarbon group" may be linear, branched, or cyclic, and may have a substituent.

[0050] 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.

[0051] 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.

[0052] The other structural units are not particularly limited, but examples thereof include structural units derived from aromatic vinyl monomers containing unhydrogenated aromatic double bonds, which are generated in the process of producing resin (B1) by polymerizing a (meth)acrylic acid ester monomer with an aromatic vinyl monomer and then hydrogenating the aromatic double bonds derived from the aromatic vinyl monomer.Specific examples of the other structural units include styrene structural units.

[0053] The resin (B1) may contain only one type of other structural unit, or two or more types.

[0054] The content of the (meth)acrylic acid ester structural unit (a) represented by general formula (1) is 65 to 80 mol %, preferably 70 to 80 mol %, based on all 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 substrate 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, warping due to water absorption of the antiglare laminate is unlikely to occur, which is preferable.

[0055] The content of the aliphatic vinyl structural unit (b) represented by 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). A content of the aliphatic vinyl structural unit (b) of 20 mol % or more is preferred because warping under high temperature and high humidity conditions can be prevented. On the other hand, a content of the aliphatic vinyl structural unit (b) of 35 mol % or less is preferred because peeling at the interface with the base layer can be prevented.

[0056] 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).

[0057] In this specification, the "copolymer" may have any of a random, block, and alternating copolymer structure.

[0058] There are no particular restrictions on the weight average molecular weight of the resin (B1), 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.

[0059] The glass transition temperature of resin (B1) is preferably 110 to 140°C, more preferably 110 to 135°C, and particularly preferably 110 to 130°C. A glass transition temperature of 110°C or higher is preferred 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 temperature of 140°C or lower is preferred because it provides excellent processability when molded by continuous thermal shaping using a mirrored roll or a shaping roll, or batch-type thermal shaping using a mirrored mold or a shaping mold. The glass transition temperature in the present invention is the 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.

[0060] Specific examples of the resin (B1) include Optimus 7500 and 6000 (manufactured by Mitsubishi Gas Chemical Co., Ltd.) The above-mentioned resins (B1) may be used alone or in combination of two or more.

[0061] The method for producing the resin (B1) is not particularly limited, but a resin obtained by polymerizing at least one (meth)acrylic acid ester monomer and at least one aromatic vinyl monomer, and then hydrogenating the aromatic double bond derived from the aromatic vinyl monomer, is suitable.

[0062] The aromatic vinyl monomer is not particularly limited, but examples thereof include styrene, α-methylstyrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and derivatives thereof. Among these, the aromatic vinyl monomer is preferably styrene.

[0063] The (meth)acrylic acid ester monomer and the aromatic vinyl monomer can be polymerized by a known method, such as bulk polymerization or solution polymerization.

[0064] 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 needed.

[0065] 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 may be used alone or in combination of two or more.

[0066] The chain transfer agent is not particularly limited, but may include α-methylstyrene dimer.

[0067] Examples of solvents used in solution polymerization 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.

[0068] 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, and examples thereof 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.

[0069] After polymerizing the (meth)acrylic acid ester monomer and the aromatic vinyl monomer as described above, the aromatic double bond derived from the aromatic vinyl monomer is hydrogenated to obtain the resin (B1).

[0070] 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 system 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 preferred because the reaction time is not too long. On the other hand, a reaction temperature of 250°C or lower is preferred because side reactions such as scission of molecular chains and hydrogenation of ester moieties do not occur or occur very little.

[0071] 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.

[0072] 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 units derived from the aromatic vinyl monomer is preferably less than 30%, more preferably less than 10%, and even more preferably less than 5%. An unhydrogenated ratio of less than 30% is preferable because a resin with excellent transparency can be obtained. The structural units of the unhydrogenated portion can become other structural units in the resin (B1).

[0073] The resin (B1) can be blended with other resins as long as 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.

[0074] (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). Furthermore, the styrene-unsaturated dicarboxylic acid copolymer (C) contains 65 to 90 mass% of styrene-based structural units (c1) and 10 to 35 mass% of unsaturated dicarboxylic acid anhydride structural units (c2). In other words, resin (B2) is a resin composition containing two or more resins.

[0075] Resin (B1) The resin (B1) may be any of those mentioned above, and may be used alone or in combination of two or more kinds.

[0076] 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).

[0077] Styrenic structural unit (c1) The styrene-based monomer is not particularly limited, and any known styrene-based monomer can be used. Specific examples of the styrene-based 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-based monomers may be used alone or in combination of two or more.

[0078] The content of the styrene-based structural unit (c1) is from 65 to 90% by mass, and preferably from 70 to 85% by mass, based on the total mass of the styrene-unsaturated dicarboxylic acid copolymer (C).

[0079] Unsaturated dicarboxylic acid anhydride structural unit (c2) The unsaturated dicarboxylic acid anhydride monomer is not particularly limited, but examples thereof include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid. Among these, maleic acid anhydride is preferred from the viewpoint of compatibility with styrene-based monomers. These unsaturated dicarboxylic acid anhydride monomers may be used alone or in combination of two or more.

[0080] The content of the unsaturated dicarboxylic anhydride structural unit (c2) is 10 to 35 mass %, and preferably 15 to 30 mass %, based on the total mass of the styrene-unsaturated dicarboxylic acid copolymer (C).

[0081] 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.

[0082] (Resin (B3)) Resin (B3) contains 55 to 10 mass% of resin (D) containing a vinyl monomer and 45 to 90 mass% of styrene-unsaturated dicarboxylic acid copolymer (E). The styrene-unsaturated dicarboxylic acid copolymer (E) contains 50 to 80 mass% of styrene structural units (e1), 10 to 30 mass% of unsaturated dicarboxylic acid structural units (e2), and 5 to 30 mass% of vinyl structural units (e3). In other words, resin (B3) is a resin composition containing two or more resins.

[0083] Resins containing vinyl monomers (D) The vinyl-based monomer-containing resin (D) is not particularly limited, but examples thereof include homopolymers of vinyl-based 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. Of these, the vinyl-based monomer-containing resin (D) preferably contains methyl methacrylate as a structural unit. The vinyl-based monomer-containing resin (D) may be a polymer using one of the structural units, or a copolymer using two or more of them in combination.

[0084] The weight average molecular weight of the resin (D) containing a vinyl monomer is preferably 10,000 to 500,000, and more preferably 50,000 to 300,000.

[0085] The above-mentioned resins (D) containing vinyl monomers may be used alone or in combination of two or more kinds.

[0086] Styrene-unsaturated dicarboxylic acid copolymer (E) The styrene-unsaturated dicarboxylic acid copolymer (E) contains a styrene structural unit (e1), an unsaturated dicarboxylic acid anhydride structural unit (e2), and a vinyl structural unit (e3).

[0087] Styrene-based structural unit (e1) The styrene-based monomer is not particularly limited, and any known styrene-based monomer can be used. Specific examples of the styrene-based 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-based monomers may be used alone or in combination of two or more.

[0088] The content of the styrene-based structural unit (e1) is 50 to 80% by mass, and preferably 50 to 75% by mass, based on the total mass of the styrene-unsaturated dicarboxylic acid copolymer (E).

[0089] Unsaturated dicarboxylic acid anhydride structural unit (e2) The unsaturated dicarboxylic acid anhydride monomer is not particularly limited, but 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 acid anhydride monomers may be used alone or in combination of two or more.

[0090] The content of the unsaturated dicarboxylic anhydride structural unit (e2) is 10 to 30% by mass, and preferably 10 to 25% by mass, based on the total mass of the styrene-unsaturated dicarboxylic acid copolymer (E).

[0091] Vinyl structural unit (e3) The vinyl monomer is not particularly limited, but examples thereof include 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.

[0092] The content of the vinyl structural unit (e3) is from 5 to 30% by mass, and preferably from 7 to 27% by mass, based on the total mass of the styrene-unsaturated dicarboxylic acid copolymer (E).

[0093] The weight-average molecular weight of the styrene-unsaturated dicarboxylic acid copolymer (E) is preferably 50,000 to 200,000, 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.

[0094] 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.

[0095] (Resin (B4)) The resin (B4) is a resin copolymer (G) containing 5 to 20 mass% of styrene structural units, 60 to 90 mass% of (meth)acrylic acid ester structural units, and 5 to 20 mass% of N-substituted maleimide structural units, or an alloy of the resin copolymer (G) and a styrene-unsaturated dicarboxylic acid copolymer (E).

[0096] ·Resin copolymer (G) The resin copolymer (G) contains styrene structural units, (meth)acrylic acid ester structural units, and N-substituted maleimide structural units.

[0097] Styrene building block The styrene-based monomer is not particularly limited, and any known styrene-based monomer can be used. Specific examples of the styrene-based 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-based monomers may be used alone or in combination of two or more.

[0098] The content of styrene structural units is 5 to 20 mass %, preferably 5 to 15 mass %, and more preferably 5 to 10 mass %, based on the total mass of the resin (B4) (resin copolymer (G)).

[0099] (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, and 2-ethylhexyl methacrylate. Of these, methyl methacrylate is preferred. These (meth)acrylic acid ester monomers may be used alone or in combination of two or more.

[0100] 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)).

[0101] N-substituted maleimide building blocks The N-substituted maleimide monomer is not particularly limited, and examples thereof include N-aryl maleimides 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.

[0102] The content of the N-substituted maleimide structural unit is 5 to 20 mass %, preferably 5 to 15 mass %, and more preferably 5 to 10 mass %, relative to the total mass of the resin (B4) (resin copolymer (G)).

[0103] The weight average molecular weight of the resin copolymer (G) is preferably 50,000 to 250,000, more preferably 100,000 to 200,000.

[0104] A specific example of the resin copolymer (G) is Delpet PM120N (manufactured by Asahi Kasei Chemical Corporation), but is not limited to this.

[0105] 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.

[0106] Alloy The alloy is an alloy of the resin copolymer (G) and the styrene-unsaturated dicarboxylic acid copolymer (E). 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.

[0107] The alloy may be produced by any method, including, but not limited to, melt-kneading the mixture at a cylinder temperature of 240°C using a twin-screw extruder with a screw diameter of 26 mm, extruding the mixture in the form of strands, and pelletizing the strands with a pelletizer.

[0108] (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.

[0109] [ka]

[0110] 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).

[0111] [ka]

[0112] 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).

[0113] 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).

[0114] The total content of the structural units (H) and (J) relative to all structural units in the resin (B5) is preferably 90 to 100 mol %, more preferably 95 to 100 mol %, and even more preferably 98 to 100 mol %.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] (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 acid anhydride structural units (c2). In other words, resin (B6) is a resin composition containing two or more resins.

[0119] Resins containing vinyl monomers (D) The vinyl-based monomer-containing resin (D) may be the same as that described for the resin (B3) above. The vinyl-based monomer-containing resin (D) may be used alone or in combination of two or more.

[0120] Styrene-unsaturated dicarboxylic acid copolymer (C) The styrene-unsaturated dicarboxylic acid copolymer (C) may be the same as that described for the resin (B2) above. The styrene-unsaturated dicarboxylic acid copolymer (C) may be used alone or in combination of two or more.

[0121] 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 that is more excellent in shape stability under high-temperature and high-humidity conditions.

[0122] [Additives] The high-hardness resin layer may contain an additive. The additives are not particularly limited, and those commonly used in antiglare laminates can be used, 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.

[0123] The amount of the additive is preferably 0 to 10% by mass, more preferably 0 to 7% by mass, and particularly preferably 0 to 5% by mass, relative to the total mass of the high-hardness resin layer.

[0124] The method for mixing the additive and the resin is not particularly limited, and methods such as compounding the entire amount, dry blending a master batch, and dry blending the entire amount can be used.

[0125] [Configuration 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. A thickness of 10 μm or more is preferable because the surface hardness is high. On the other hand, a thickness of 250 μm or less is preferable because the impact resistance is high.

[0126] [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.

[0127] 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, even more preferably 500 to 3000 μm, and particularly preferably 1200 to 3000 μm. A total thickness of 100 μm or more is preferable because it allows the rigidity of the sheet to be maintained. On the other hand, a total thickness of 3500 μm or less is preferable because it prevents a decrease in the sensitivity of the touch sensor when a touch panel is installed under the sheet.

[0128] 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 within the above range, both hardness and impact resistance can be achieved.

[0129] The method for laminating the high-hardness resin layer on the base layer is not particularly limited, and examples thereof include a method in which a base layer and a high-hardness resin layer that have been formed separately are superimposed on each other and then heated and pressed together; a method in which a base layer and a high-hardness resin layer that have been formed separately are superimposed on each other and then bonded together with an adhesive; a method in which the base layer and the high-hardness resin layer are co-extruded; a method in which the base layer is integrated into a pre-formed high-hardness resin layer by in-mold molding, etc. Of these, the co-extrusion molding method is preferred from the viewpoints of production cost and productivity.

[0130] The co-extrusion method is not particularly limited. For example, in the feed block method, a high-hardness resin layer is placed on one side of a substrate layer in a feed block, and the layer is extruded into a sheet using 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 placed on one side of a substrate layer in a multi-manifold die, and then extruded into a sheet, and then cooled while passing through a forming roll to form a desired laminate.

[0131] <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.

[0132] The hard coat layer preferably does not contain organic particles or inorganic particles. By not containing organic particles or inorganic particles, scratch resistance can be improved. As will be described later, by performing the antiglare treatment of the hard coat layer by transfer using a mold, it is possible to form a hard coat layer having an uneven shape without containing organic particles or inorganic particles.

[0133] 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.

[0134] 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 %, relative to the total mass of the (meth)acrylic monomer, the (meth)acrylic oligomer, and the surface modifier.

[0135] 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 %, relative to the total mass of the (meth)acrylic monomer, the (meth)acrylic oligomer, and the surface modifier.

[0136] 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.

[0137] [(Meth)acrylic monomers] Any (meth)acrylic monomer can be used as long as it has a (meth)acryloyl group as a functional group in the molecule, specifically, a monofunctional monomer, a difunctional monomer, or a trifunctional or higher functional monomer.

[0138] Examples of the monofunctional monomer include (meth)acrylic acid and (meth)acrylic acid esters.

[0139] 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 copolymer 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.

[0140] The hard coat layer may contain one or more types of (meth)acrylic monomers.

[0141] [(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"), and difunctional or higher polyfunctional epoxy (meth)acrylate oligomers (hereinafter also referred to as "polyfunctional epoxy (meth)acrylate oligomers").

[0142] Examples of the polyfunctional urethane (meth)acrylate oligomer include a urethane reaction product of a (meth)acrylate monomer having at least one (meth)acryloyloxy group and a hydroxyl group in one molecule and a polyisocyanate; and a urethane reaction product of 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.

[0143] Examples of the (meth)acrylate monomer having at least one (meth)acryloyloxy group and one hydroxyl group per 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.

[0144] 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.

[0145] Polyols used in the urethanization reaction generally include aromatic, aliphatic and alicyclic polyols, as well as polyester polyols and polyether polyols.

[0146] 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.

[0147] The polyester polyol may be obtained by a dehydration condensation reaction between the above-mentioned polyols and 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.

[0148] Examples of polyether polyols include polyalkylene glycols, as well as polyoxyalkylene-modified polyols obtained by reacting the above-mentioned polyols or phenols with alkylene oxides.

[0149] 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 also 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.

[0150] 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.

[0151] The hard coat layer may contain one or more types of (meth)acrylic oligomers.

[0152] [Surface modifier] The surface modifiers are agents that change the surface properties of the hard coat layer, such as leveling agents, antistatic agents, surfactants, water and oil repellents, inorganic particles, and organic particles.

[0153] Examples of the leveling agent include polyether-modified polyalkylsiloxane, polyether-modified siloxane, polyester-modified hydroxyl group-containing polyalkylsiloxane, polyether-modified polydimethylsiloxane having an alkyl group, modified polyether, and silicon-modified acrylic.

[0154] 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.

[0155] 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.

[0156] Examples of the inorganic particles include silica particles, alumina particles, zirconia particles, silver particles, and glass particles.

[0157] Examples of the organic particles include acrylic particles and silicon particles.

[0158] The hard coat layer may contain one or more types of surface modifiers.

[0159] [Photopolymerization initiator] Examples of the photopolymerization initiator include monofunctional photopolymerization initiators. Specific examples include acetophenone-based initiators such as 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone [Darocure 2959: manufactured by Merck]; α-hydroxy-α,α'-dimethylacetophenone [Darocure 1173: manufactured by Merck]; methoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone [Irgacure 651], and 1-hydroxycyclohexylphenyl ketone; benzoin ether-based initiators such as benzoin ethyl ether and benzoin isopropyl ether; and halogenated ketones, acylphosphinoxides, and acylphosphonates. These photopolymerization initiators may be used alone or in combination of two or more.

[0160] [UV absorber] Examples of UV absorbents include hydroxyphenyltriazines, benzotriazoles, and benzophenones. These UV absorbents may be used alone or in combination of two or more.

[0161] [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. A hard coat layer thickness of 1 μm or more is preferable because sufficient hardness can be obtained. On the other hand, a hard coat layer thickness of 40 μm or less is preferable because it can suppress the occurrence of cracks during bending. 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.

[0162] 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 the result of evaluation by a pencil scratch hardness test in accordance with 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.

[0163] The hard coat layer has an uneven surface, which allows the production of an antiglare laminate having excellent antiglare properties and a pleasant feel to the touch. Specifically, the hard coat layer has a root-mean-square gradient (Sdq) and a root-mean-square height (Sq) that satisfy the following formulas (i) and (ii), respectively. In this specification, the root-mean-square gradient (Sdq) and the root-mean-square height (Sq) are measured in accordance with ISO 25178-2:2012, as described in the examples below.

[0164] 0.010≦Sdq≦0.10 (i) 0.040≦Sq≦0.40 (ii)

[0165] Regarding the formula (i), the root mean square gradient (Sdq) is an index of antiglare properties and correlates with haze. If Sdq exceeds 0.10, excessive light scattering occurs, resulting in whitening and a poor texture. Formula (i) more preferably satisfies 0.020≦Sdq≦0.08, even more preferably 0.030≦Sdq≦0.07, and particularly preferably 0.035≦Sdq≦0.06.

[0166] Regarding the formula (ii), the root mean square height (Sq) is an index of antiglare properties and correlates with image clarity. If Sq exceeds 0.40, excessive light scattering results in whitening and a poor texture. Formula (ii) more preferably satisfies 0.050≦Sq≦0.38, even more preferably 0.10≦Sq≦0.37, and particularly preferably 0.20≦Sq≦0.35.

[0167] <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 an HR-100 model (manufactured by Murakami Color Research Laboratory).

[0168] <Imageability> One method for evaluating image reflection is the image clarity of reflection measured at a light incident 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 greater variation in values, whereas a wider optical comb width results in less variation in values, so an optical comb width of 2.0 mm is preferred. The reflection clarity measured at a light incident 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.

[0169] 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 incident angle of 60° using a 2.0 mm wide optical comb.

[0170] [Method for forming hard coat layer] The method for forming the hard coat layer is not particularly limited, but 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 liquid.

[0171] The method for applying the hard coating liquid (polymerizable composition, reactive composition) is not particularly limited, and known methods 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 spraying.

[0172] The lamp used for light irradiation in photopolymerization has an emission distribution with a light wavelength of 420 nm or less. Examples 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 and metal halide lamps are preferred because they efficiently emit light in the active wavelength range of the photopolymerization initiator and do not emit much short-wavelength light that would reduce the viscoelastic properties of the resulting polymer due to crosslinking, or long-wavelength light that would heat and evaporate the reaction composition.

[0173] The irradiation intensity of the lamp is a factor that determines the degree of polymerization of the resulting polymer, and is appropriately controlled depending on the performance of the target product. When a typical cleavage-type photopolymerization initiator having an acetophenone group is blended, the irradiance is 0.1 to 300 mW / cm. 2 In particular, when a metal halide lamp is used, the illuminance is set to 10 to 40 mW / cm. 2 It is preferable to set the following.

[0174] The photopolymerization reaction is inhibited by oxygen in the air or oxygen dissolved in the reactive composition. Therefore, it is desirable to carry out light irradiation using a method that can eliminate reaction inhibition by oxygen. One such method is to cover the reactive composition with a film made of polyethylene terephthalate or Teflon to prevent contact with oxygen, and then irradiate the reactive composition with light through the film. Alternatively, the reactive composition may be irradiated with light through a light-transmitting window in an inert atmosphere in which oxygen has been replaced with an inert gas such as nitrogen gas or carbon dioxide gas.

[0175] When light irradiation is performed in an inert atmosphere, a certain amount of inert gas is always introduced to maintain a low oxygen concentration in the atmosphere. The introduction of this inert gas generates an airflow on the surface of the reactive composition, causing monomer evaporation. To suppress the level of monomer evaporation, the airflow velocity of the inert gas is preferably 1 m / sec or less, more preferably 0.1 m / sec or less, relative to the laminate coated with the hard coat liquid moving under the inert gas atmosphere. By setting the airflow velocity within the above range, monomer evaporation due to the airflow can be substantially suppressed.

[0176] 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 with a resin composition.

[0177] The method for forming the 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 first laminated in this order. Next, the reactive composition is photopolymerized and the mold is demolded. The photopolymer of the reactive composition (hard coat layer) will have a shape that reflects the rough surface of the mold at the surface that comes into contact with the mold. In other words, this method involves performing the anti-glare treatment of the hard coat layer by transfer using a mold.

[0178] The mold is not particularly limited as long as it transmits UV light, and glass, transparent resin, etc. can be used. In one embodiment, the mold is a mold in which a transparent film and a transparent resin having a rough surface are laminated. Examples of the transparent film include PET film. Examples of the transparent resin having a rough surface include acrylic resin. 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, by etching the transparent resin, or by printing and curing the transparent resin. The shape of the rough surface is not particularly limited, but from the perspective of use in applications such as liquid crystal panels, a patterned surface is preferable. 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. This allows for the formation of a hard coat layer that satisfies the above-mentioned formulas (i) and (ii). Furthermore, it is preferable for the formation of a hard coat layer that further satisfies the above-mentioned formulas (iii) and (iv).

[0179] Among the methods for forming the hard coat layer described above, it is preferable to transfer the unevenness by pressing a patterned PET film. That is, according to one embodiment of the present invention, a method for producing an antiglare laminate is provided. In this case, the production method includes a step of pressing a patterned PET film onto the surface of the hard coat layer to transfer the unevenness. Note that, as the patterned PET film, for example, PTH, PTHA, or PTHZ from Emblet manufactured by Unitika, or PF11 or PF23 from Daicel's low-glare AG film 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 patterned PET film can be produced by applying a coating liquid to a PET (polyethylene terephthalate) film so that the dry film thickness is 1.0 to 4.0 μm, drying at 70 to 90°C for 1 to 3 minutes, and then curing the film 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. The coating liquid preferably contains an organic solvent such as methyl ethyl ketone (MEK), an acrylic UV-curable resin, silica particles, and a photoinitiator. The content of these components is preferably 70 to 80 parts by weight of the organic solvent such as methyl ethyl ketone (MEK), 19 to 29 parts by weight of the acrylic UV-curable resin, 0.2 to 1.0 parts by weight of silica particles (average particle size 3.5 to 5.0 μm), and 2.0 to 4.0 parts by weight of the photoinitiator. This allows the formation of a hard coat layer that satisfies the above-mentioned formulas (i) and (ii).

[0180] <Physical properties of antiglare laminate> In one embodiment, the antiglare laminate preferably has high shape stability. Specifically, after 120 hours of storage in an environment with a temperature of 85°C and a relative humidity of 85%, the change in warpage 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. A change in warpage of 350 μm or less is preferable because it can be used even in high-temperature, high-humidity environments. High shape stability can be achieved by using a high-hardness resin layer. The presence of a high-hardness resin layer between the substrate layer and the hard coat layer stabilizes the shape of the antiglare laminate even in high-temperature, high-humidity environments. 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) or hardness between the substrate layer and the high-hardness resin layer, or the difference in glass transition temperature (Tg) or hardness between the high-hardness resin layer and the hard coat layer.

[0181] <Application> The antiglare laminate of the present invention has excellent antiglare properties and a pleasant feel to the touch, and is therefore used as a protective plate or front panel for a liquid crystal display screen, as described above. In one embodiment, an in-vehicle display device including the antiglare laminate is provided. In another embodiment, a front panel for a touch panel 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. [Example]

[0182] Examples of the present invention will be shown below, but the present invention is not limited to these examples.

[0183] <Surface roughness measurement> Using a confocal laser microscope "OLS 5000" manufactured by Olympus Corporation, the root mean square gradient (Sdq) and root mean square height (Sq) of the surface of the hard coat layer having an uneven surface were measured according to ISO 25178-2:2012 under the following conditions.

[0184] Root Mean Square Gradient (Sdq) Observation conditions Objective lens: 20x Acquisition mode: Precision priority Measurement area: 645 μm x 645 μm Analysis conditions Correction: Remove spike noise and tilt Root Mean Square Height (Sq) Observation conditions Objective lens: 20x Acquisition mode: Precision priority Measurement area: 645 μm x 645 μm Analysis conditions Correction: Remove spike noise and tilt

[0185] <Haze> The haze was calculated using "HM-150N" manufactured by Murakami Color Research Laboratory according to the method specified in JIS K 7136:2000.

[0186] <Reflectance sharpness (imaging property)> Using the "ICM 1T" manufactured by Suga Test Instruments Co., Ltd., based on JIS K7374, the measurement was carried out with the flow direction of the antiglare laminate and the direction of the teeth of the optical comb being parallel. Among the optical combs, the reflectance of the image of the reflection measured at an incident angle of light of 60° using a 2.0 mm optical comb was defined as the reflectance sharpness. The measurement was performed by suppressing the back reflection by attaching a black tape (black vinyl tape model number 117BLA manufactured by 3M Japan Co., Ltd.) to the back surface of the uneven surface.

[0187] <SW hardness> For the hard coat layer having the uneven shape of the antiglare laminate, using steel wool #0000 made of Nippon Steel Wool, at a load of 100 g / cm 2 The degree of damage when reciprocated 15 times was visually observed and evaluated in 10 grades. 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.

[0188] RANK1: No damage (equivalent to inorganic glass) RANK2: 1 - 5 scratches RANK3: 6 -​​​​​​​​​​​​​​​​​​​A test piece (antiglare laminate) was cut to a size of 100 mm x 60 mm. The cut test piece was placed 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 at least 24 hours to condition it, after which the warpage was measured (before treatment). Next, the test piece was placed 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 the environmental tester set at a temperature of 23% and a relative humidity of 50%, and held in that state for 4 hours, after which the warpage was measured again (after treatment). The warpage was measured using a three-dimensional shape measuring machine (KEYENCE KS-1000) equipped with an electric stage. The removed test piece was placed horizontally with a convex shape upward, 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.

[0190] [Example 1] <Laminate> A synthetic resin laminate was molded using a multilayer extrusion device equipped with a 35mm single-screw extruder, a 65mm single-screw extruder, a feedblock connected to all extruders, and a T-die connected to the feedblock. Mitsubishi Gas Chemical's Optimas 7500 high-hardness resin (B1) was continuously introduced into the 35mm single-screw extruder and extruded at a cylinder temperature of 240°C and a discharge rate of 2.6 kg / h. Polycarbonate resin (Mitsubishi Engineering Plastics Corporation, trade name: Iupilon S-1000) was continuously introduced into the 65mm single-screw extruder and extruded at a cylinder temperature of 280°C and a discharge rate of 50.0 kg / h. The feedblock connected to all extruders was equipped with a two-type, two-layer distributor pin, and the high-hardness resin (B1) and polycarbonate resin were introduced and laminated at a temperature of 270°C. The extruded sheet was then extruded into a sheet through a T-die connected to the die at 270°C, and cooled while transferring a mirror finish using three mirror-finish rolls set at temperatures of 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 (substrate layer). The thickness of the obtained laminate was 1.0 mm, and the thickness of the high-hardness resin (B1) layer near the center was 60 μm.

[0191] The Optimas 7500 manufactured by Mitsubishi Gas Chemical Company, used as the high-hardness resin (B1), is a copolymer resin containing (meth)acrylic acid ester structural units (a) represented by the general formula (1) and aliphatic vinyl structural units (b) represented by the general formula (2). The total proportion of the (meth)acrylic acid ester structural units (a) and the aliphatic vinyl structural units (b) is 99 mol % of all structural units of the copolymer resin, and the proportion of the (meth)acrylic acid ester structural units (a) is 75 mol % of all structural units of the copolymer resin.

[0192] <Photocurable resin composition (Y-1)> 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, 3 parts by mass of photoinitiator I-184 (manufactured by BASF Ltd. [compound name: 1-hydroxycyclohexylphenyl ketone]) was added to obtain a photocurable resin composition (Y-1).

[0193] <Patterned PET film (Z-1)> Coating solution (i) was prepared by mixing 81 parts by weight of MEK with 18.8 parts by weight of an acrylic UV-curable resin (100% solids, product name: Light Acrylate DPE-6A; manufactured by Kyoeisha Chemical Co., Ltd.), 0.2 parts by weight of silica microparticles (NP-30, average particle size 4 μm, manufactured by AGC Si-Tech Co., Ltd.), and 3 parts by weight of an externally added photoinitiator (product name: Omnirad 184; manufactured by IGM Resins). Next, coating solution (i) was applied to a PET (polyethylene terephthalate) film to a dry film thickness of 1.4 μm. After drying at 80 °C for 2 minutes, the film was cured by UV irradiation 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 at a line speed of 1.5 m / min to produce a patterned PET film (Z-1).

[0194] A photocurable resin composition (Y-1) was applied to the high-hardness resin (B1) layer of a laminate of a high-hardness resin (B1) layer (high-hardness resin layer) and a polycarbonate resin layer (substrate layer) using a bar coater so that the cured coating thickness would be 5 to 10 μm, and the patterned PET film (Z-1) was covered and pressed so that the patterned surface of the film came into contact with the coating liquid. The film was then cured by irradiating it with a metal halide lamp (20 mW / cm) from a light source distance of 12 cm for 30 seconds, and the patterned PET film was peeled off to obtain an antiglare laminate comprising a textured hard coat layer on the high-hardness resin layer (B1).

[0195] [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). The high-hardness resin (B3) was prepared as follows. Specifically, 75% by mass of Resisfy R100 (manufactured by Denki Kagaku Kogyo Co., Ltd.) was used as the styrene-unsaturated dicarboxylic acid copolymer (E) and 25% by mass of Parapet HR-L (manufactured by Kuraray Co., Ltd.), a methyl methacrylate resin, was used as the vinyl monomer-containing resin (D). The mixture was then mixed in a blender for 30 minutes. The mixture was then melt-kneaded at a cylinder temperature of 230°C using an extruder with a 26 mm screw diameter (Toshiba Machine Co., Ltd., TEM-26SS, L / D ≒ 40), extruded into strands, and pelletized in a pelletizer to obtain the high-hardness resin (B3). Pelletization was stable.

[0196] [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). The high-hardness resin (B6) was prepared as follows. 50% by mass of XIBOND160 (Polyscope) as the styrene-unsaturated dicarboxylic acid copolymer (C) and 50% by mass of Parapet HR-L (Kuraray), a methyl methacrylate resin, as the vinyl monomer-containing resin (D) were charged and mixed in a blender for 30 minutes. The mixture was then melt-kneaded at a cylinder temperature of 230°C using an extruder with a 26 mm screw diameter (Toshiba Machine, TEM-26SS, L / D ≒ 40), extruded into strands, and pelletized in a pelletizer to obtain the high-hardness resin (B6). Pelletization was stable.

[0197] [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). <Patterned PET film (Z-2)> A patterned PET film (Z-2) was produced using the following coating liquid (ii) instead of the coating liquid (i). Coating liquid (ii) was prepared by mixing and stirring 85 parts by mass of MEK, 14.9 parts by mass of an acrylic ultraviolet-curable resin (100% solids, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.), 0.1 parts by mass of silica microparticles (NP-30, average particle size 4 μm, manufactured by AGC Si-Tech Co., Ltd.), and 3 parts by mass of an externally added photoinitiator (product name Omnirad184, manufactured by IGM Resins).

[0198] [Example 5] An antiglare laminate was produced in the same manner as in Example 1, except that the following patterned PET film (Z-3) was used instead of the patterned PET film (Z-1). <Patterned PET film (Z-3)> A patterned PET film (Z-3) was produced using the following coating liquid (iii) instead of the coating liquid (i). Coating liquid (iii) was prepared by mixing and stirring 76 parts by mass of MEK, 23.8 parts by mass of an acrylic ultraviolet-curable resin (100% solids, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.), 0.2 parts by mass of silica microparticles (NP-30, average particle size 4 μm, manufactured by AGC Si-Tech Co., Ltd.), and 3 parts by mass of an externally added photoinitiator (product name Omnirad184, manufactured by IGM Resins).

[0199] [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). <Patterned PET film (Z-4)> A patterned PET film (Z-4) was produced using the following coating liquid (iv) instead of the coating liquid (i). 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 microparticles (NP-30, average particle size 4 μm, manufactured by AGC Si-Tech Co., Ltd.), and 3 parts by mass of an externally added photoinitiator (product name Omnirad184, manufactured by IGM Resins).

[0200] [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). <Patterned PET film (Z-5)> A patterned PET film (Z-5) was produced using the following coating liquid (v) instead of the coating liquid (i). The coating liquid (v) was prepared by mixing and stirring 80 parts by mass of MEK, 19.9 parts by mass of an acrylic ultraviolet-curable resin (100% solids, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.), 0.1 parts by mass of silica microparticles (NP-30, average particle size 4 μm, manufactured by AGC Si-Tech Co., Ltd.), and 3 parts by mass of an externally added photoinitiator (product name Omnirad184, manufactured by IGM Resins).

[0201] [Example 8] 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).

[0202] [Comparative Example 1] 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). <Patterned PET film (Z-6)> A patterned PET film (Z-6) was produced using the following coating liquid (vi) instead of the coating liquid (i). The coating liquid (vi) was prepared by mixing and stirring 90 parts by mass of MEK, 9.5 parts by mass of an acrylic ultraviolet-curable resin (100% solids, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.), 0.5 parts by mass of silica microparticles (NP-30, average particle size 4 μm, manufactured by AGC Si-Tech Co., Ltd.), and 3 parts by mass of an externally added photoinitiator (product name Omnirad184, manufactured by IGM Resins).

[0203] Comparative Example 2 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). <Patterned PET film (Z-7)> A patterned PET film (Z-7) was produced using the following coating liquid (vii) instead of the coating liquid (i). Coating liquid (vii) was prepared by mixing and stirring 90 parts by mass of MEK, 9.8 parts by mass of an acrylic ultraviolet-curable resin (100% solids, product name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.), 0.2 parts by mass of silica microparticles (NP-30, average particle size 4 μm, manufactured by AGC Si-Tech Co., Ltd.), and 3 parts by mass of an externally added photoinitiator (product name Omnirad184, manufactured by IGM Resins).

[0204] Comparative Example 3 An antiglare laminate was produced in the same manner as in Example 1, except that Cosmoshine A4295 (Z-8) manufactured by Toyobo was used as the patterned PET film instead of the patterned PET film (Z-1).

[0205] 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. That is, 85 parts by mass of MEK was mixed and stirred with 15.7 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 Toyota Tsusho Chemiplas Co., Ltd.), to prepare a photocurable composition (Y-2). Photocurable composition (Y-2) was applied onto the high-hardness resin layer using a bar coater so that the coating thickness after curing would be 1.4 μm, and then dried for 2 minutes at 80° C. While purging with nitrogen, the coating was cured by irradiating it with a metal halide lamp (20 mW / cm) from a light source distance of 12 cm for 30 seconds to obtain an antiglare laminate.

[0206] The antiglare laminates obtained in Examples 1 to 8 and Comparative Examples 1 to 4 are shown in Table 1 below.

[0207] [Table 1]

[0208] Furthermore, the root mean square gradient (Sdq), root mean square height (Sq), haze, image clarity, SW hardness, and shape stability were evaluated for Examples 1 to 8 and Comparative Examples 1 to 4. The obtained results are shown in Table 2 below.

[0209] [Table 2]

[0210] As is clear from the results in Table 2, Examples 1 to 8 have excellent antiglare properties because Sdq and Sq satisfy the formulas (i) and (ii), respectively. Furthermore, Examples 1 to 7, which used high-hardness resins (B1), (B3), or (B6), were also confirmed to have excellent shape stability. On the other hand, in Comparative Examples 1 and 2, Sdq and Sq did not satisfy the formulas (i) and (ii), respectively, and therefore the haze value was high and the visibility was poor due to excessive light scattering. In Comparative Example 3, Sdq and Sq did not satisfy the formulas (i) and (ii), respectively, and therefore the image clarity was high and the antiglare properties were insufficient. In Comparative Example 4, Sdq and Sq did not satisfy the formulas (i) and (ii), respectively, so the haze value was high and the visibility was poor due to excessive light scattering. In addition, it was confirmed that the SW hardness was insufficient because the hard coat layer contained silica fine particles.

Claims

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 arranged in this order, wherein the root-mean-square gradient (Sdq) and root-mean-square height (Sq) of the hard coat layer satisfy the following formulas (i) and (ii), respectively: 0.010≦Sdq≦0.10 (i) 0.040≦Sq≦0.40 (ii) An antiglare laminate that satisfies the above requirements.

2. The root mean square gradient (Sdq) and root mean square height (Sq) of the hard coat layer are expressed by the following formulas (iii) and (iv), respectively: 0.035≦Sdq≦0.06 (iii) 0.20≦Sq≦0.35 (iv) The antiglare laminate according to claim 1 , which satisfies the above formula:

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

4. 2. The antiglare laminate according to claim 1, wherein the high-hardness resin layer has a thickness of 10 to 250 μm.

5. 2. The antiglare laminate according to claim 1, wherein the total thickness of the substrate 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 or inorganic particles.

7. The polycarbonate resin (a1) is a compound represented by the following general formula (5): 【Chemistry 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, R ６ each independently represent a hydrogen atom, a halogen, or an optionally substituted alkyl group having 1 to 20 carbon atoms or an optionally substituted aryl group having 6 to 12 carbon atoms, and n is an integer of 0 to 4, wherein the substituent is a halogen, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 12 carbon atoms.

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

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

10. A front panel for office automation equipment, portable electronic devices, or televisions, comprising the antiglare laminate according to any one of claims 1 to 7.

11. A method for producing the antiglare laminate according to any one of claims 1 to 7, comprising: 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) and (ii): 0.010≦Sdq≦0.10 (i) 0.040≦Sq≦0.40 (ii) The manufacturing method as described above, comprising the step of satisfying the above.

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