CN114270226A - Anti-glare laminate - Google Patents

Abstract

The present invention provides an anti-glare laminate comprising: a layer containing a resin (A) containing a polycarbonate resin (a1), and a layer provided on a layer containing a resin (A) containing the polycarbonate resin (a1) A layer containing a high hardness resin (B) on at least one side; and a hard coat layer having a concavo-convex shape further provided on the layer containing a high hardness resin (B), the anti-glare laminate satisfies the following conditions ( i) and (ii): (i) the thickness of the layer containing the high hardness resin (B) is 10 to 250 μm, the layer containing the resin (A) containing the polycarbonate resin (a1) and the layer containing the high hardness resin The total thickness of the layers of (B) is 100 to 3,000 μm; (ii) The transmission clarity when light is transmitted through the above-mentioned laminate measured using an optical comb with a width of 2.0 mm is defined as T1, and a width of 2.0 mm is used. T1/T2 is 2.0 or more when the reflection sharpness of the above-mentioned laminate measured at a light incident angle of 45° is set as T2.

Description

Anti-glare laminate

Technical Field

The present invention relates to an antiglare laminate. More specifically, the present invention relates to an antiglare laminate having antiglare properties, high abrasion resistance, and excellent shape stability, which is used as a front panel of a liquid crystal display device for vehicles, a mobile phone terminal, a personal computer, and a tablet PC.

In order to protect the liquid crystal panel and the like, the liquid crystal display device is provided with a front panel. As a material used for a front panel of a conventional liquid crystal display device, a (meth) acrylic resin typified by polymethyl methacrylate (PMMA) can be cited.

In recent years, a sheet made of a polycarbonate resin has been used as a front panel from the viewpoints of high impact resistance, heat resistance, 2-pass processability, light weight, transparency, and the like. In particular, a front panel obtained by hard coating a multilayer sheet obtained by laminating an acrylic resin on the surface layer of a polycarbonate resin sheet has surface hardness and scratch resistance comparable to those of conventional acrylic resins with a hard coating layer, and has excellent impact resistance, heat resistance, processability and transparency of a polycarbonate resin, and thus is widely used as a front panel.

The front panel of the liquid crystal display device having the polycarbonate resin sheet is generally formed by melt extrusion together with an acrylic resin.

In a liquid crystal display device, an optical laminate for antireflection is generally provided on the outermost surface. Such an antireflection optical laminate suppresses reflection of an image or reduces reflectance by light scattering or interference.

As one of the antireflection optical laminates, an antiglare film is known in which an antiglare layer having an uneven shape is formed on the surface of a transparent substrate. The antiglare film can prevent the deterioration of visibility due to reflection of external light and reflection of an image by scattering the external light by the surface roughness. In addition, since the optical laminate is usually provided on the outermost surface of the liquid crystal display device, it is also required to impart hard coatability so as not to be damaged during handling.

In general, a mixture of fine particles and a binder resin or a curable resin is applied to a substrate on a display surface of a liquid crystal display device, an organic Electroluminescence (EL) display device, or the like, and fine irregularities are formed on the surface to prevent specular reflection and reflection of an image. However, when the uneven shape is provided to prevent the reflection of an image, scattering of transmitted light in a straight line increases, and a line of a pixel is blurred, thereby causing character blurring.

Further, when fine particles are added to form surface irregularities, the fine particles on the outermost surface fall off in the scratch resistance test and function as a polishing agent, and therefore, the scratch resistance is significantly lowered as compared with the case where fine particles are not added, which is not preferable.

As described above, as a front panel of a liquid crystal display device for a vehicle, a mobile phone terminal, a personal computer, or a tablet PC, there is no front panel that has excellent impact resistance, heat resistance, anti-glare properties that prevent reflection of an image and simultaneously achieve a performance of suppressing character blurring, has high scratch resistance, and has excellent shape stability.

In patent document 1, fine particles are added to improve the transmission resolution and reduce blurring of characters. The addition of fine particles is not preferable because it can increase pencil hardness and decrease scratch resistance.

Documents of the prior art

Patent document

Patent document 1: japanese patent application laid-open No. 2010-160398

Disclosure of Invention

Technical problem to be solved by the invention

The technical problem to be solved by the present invention is at least one of the problems of the prior art described above. Further, an object of the present invention is to provide an antiglare laminate having both image reflection prevention performance and suppression of character blurring, and having high scratch resistance and excellent shape stability.

Technical solution for solving technical problem

The above-described problems can be solved by the present invention as follows. Namely, the present invention is as follows.

< 1 > an antiglare laminate comprising: a layer comprising a resin (a) containing a polycarbonate resin (a 1); a layer containing a high-hardness resin (B) provided on at least one surface of a layer containing a resin (a) containing a polycarbonate resin (a 1); and a hard coat layer having an uneven shape further provided on the layer containing the high-hardness resin (B), wherein the antiglare laminate satisfies the following conditions (i) and (ii): (i) the thickness of the layer containing the high-hardness resin (B) is 10 to 250 [ mu ] m, and the total thickness of the layer containing the resin (A) containing the polycarbonate resin (a1) and the layer containing the high-hardness resin (B) is 100 to 3,000 [ mu ] m; (ii) when the transmission clarity of light passing through the laminate measured using an optical comb having a width of 2.0mm is T1 and the reflection clarity of the laminate measured using an optical comb having a width of 2.0mm at a light incident angle of 45 DEG is T2, T1/T2 is 2.0 or more.

< 2 > the antiglare laminate of < 1 > wherein the transmission clarity T1 when light is transmitted through the laminate as measured using a 2.0mm wide optical comb is in the range of 30% to T1% to 50%, and the reflection clarity T2 when measured at a light incidence angle of 45 ° using a 2.0mm wide optical comb is in the range of 10% to T2% to 20%.

< 3 > the antiglare laminate of < 1 > or < 2 >, wherein the high-hardness resin (B) contains at least one selected from the following resins (B1) to (B5),

the resin (B1) is a copolymer resin containing a (meth) acrylate structural unit (a) represented by the following general formula (1) and an aliphatic vinyl structural unit (B) represented by the following general formula (2), wherein the total proportion of the (meth) acrylate structural unit (a) and the aliphatic vinyl structural unit (B) is 90 to 100 mol% of the total structural units of the copolymer resin, the proportion of the (meth) acrylate structural unit (a) is 65 to 80 mol% of the total structural units of the copolymer resin,

(wherein R1 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group having 1 to 18 carbon atoms.)

(wherein R3 represents a hydrogen atom or a methyl group, and R4 represents a cyclohexyl group which may have a hydrocarbon group having 1 to 4 carbon atoms.)

The resin (B2) contains 35 to 65 mass% of the resin (B1) and 35 to 65 mass% of a styrene-unsaturated dicarboxylic acid copolymer (C) containing 65 to 90 mass% of a styrene monomer unit (C1) and 10 to 35 mass% of an unsaturated dicarboxylic anhydride monomer unit (C2),

the resin (B3) comprises 55 to 10 mass% of a resin (D) containing a vinyl monomer and 45 to 90 mass% of a styrene-unsaturated dicarboxylic acid copolymer (E) containing 50 to 80 mass% of a styrene monomer unit (E1), 10 to 30 mass% of an unsaturated dicarboxylic acid monomer unit (E2) and 5 to 30 mass% of a vinyl monomer unit (E3),

the resin (B4) is a resin copolymer (G) containing 5 to 20 mass% of a styrene structural unit, 60 to 90 mass% of a (meth) acrylate structural unit and 5 to 20 mass% of an N-substituted maleimide monomer, or a resin which is an alloy of the resin copolymer (G) and the copolymer (E),

the resin (B5) is a copolymer containing a structural unit (H) represented by the following formula (3) and optionally a structural unit (J) represented by the following formula (4).

The antiglare laminate of any one of < 4 > to < 1 > - < 3 >, wherein the hard coat layer having an irregular shape does not contain inorganic particles or organic particles.

The antiglare laminate of any one of < 5 > to < 1 > - < 4 >, wherein the hard coat layer having an uneven shape has at least 1 characteristic selected from antireflection performance, antifouling performance, antistatic performance and weather resistance.

The antiglare laminate of any one of < 6 > to < 1 > < 5 >, wherein a second hard coat layer is provided on a surface opposite to the hard coat layer having irregularities.

< 7 > the antiglare laminate of < 6 >, wherein the second hard coat layer has at least 1 property selected from the group consisting of antireflection performance, antifouling performance, antistatic performance and weather resistance.

The antiglare laminate of any one of < 8 > to < 1 > -to < 7 >, wherein the polycarbonate resin (a1) contains a component derived from a monohydric phenol represented by the following general formula (5).

(in the formula, R₁Represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms, R₂～R₅Each 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(s) such as a halogen or an alkyl group having 1 to 20 carbon atomsOr an aryl group having 6 to 12 carbon atoms. )

< 9 > an in-vehicle display device comprising the antiglare laminate according to any one of claims < 1 > to < 8 >.

< 10 > a front protective plate for touch panel, comprising the antiglare laminate according to any one of < 1 > to < 8 >.

< 11 > a front panel for OA equipment, portable electronic equipment or television, comprising the antiglare laminate according to any one of < 1 > to < 8 >.

< 12 > the method for producing an antiglare laminate according to any one of the above < 1 > -to < 8 >, the method comprising a step of transferring a concave-convex shape to the hard coat layer by pressure-bonding a patterned PET film to the photocurable resin composition on the layer containing the high-hardness resin (B).

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, an antiglare laminate having antiglare properties, high scratch resistance, and excellent shape stability, which is used as a front panel of a liquid crystal display device for vehicles, a mobile phone terminal, a personal computer, or a tablet PC, can be provided.

Drawings

Fig. 1 is a photograph of the laminate obtained in example 1, which was photographed with a white microscope, showing a concave-convex shape capable of preventing reflection and suppressing blurring of characters.

Fig. 2 is a photograph obtained by taking an image of the laminate obtained in comparative example 1 with a white microscope, and shows only the uneven shape having excellent reflection preventing properties.

Fig. 3 is a photograph of the laminate obtained in comparative example 2, which was photographed by a white microscope, showing a concave-convex shape excellent in suppressing only character blurring.

Detailed Description

The present invention will be described in detail below with reference to the following examples of manufacture and examples, but the present invention is not limited to the examples of manufacture and examples, and can be carried out by any method without departing from the scope of the present invention.

The antiglare laminate (hereinafter, sometimes referred to as "resin sheet") of the present invention is provided with a layer containing a high-hardness resin (B) (hereinafter, sometimes referred to as "high-hardness resin layer" or "high-hardness layer") and a hard coat layer having a concavo-convex shape on at least one side of a layer containing a resin (a) containing a polycarbonate resin (al) (hereinafter, sometimes referred to as "base layer"). The substrate layer may be a layer composed of a resin (a) containing a polycarbonate resin (al). The high-hardness layer may be a layer made of a high-hardness resin (B).

The high-hardness resin layer is present between the base material layer and the hard coat layer in the order of lamination, and the outermost surface of the hard coat layer which is the outermost surface layer is provided with a concavo-convex shape. The other surface of the layer containing the resin (a) containing the polycarbonate resin (al) is not particularly specified, and two layers of a high-hardness resin layer and a hard coat layer, or one of them may be provided.

As the high-hardness resin layer, a resin selected from the high-hardness resins (B) is preferably used, and when the high-hardness resin layers are provided on both surfaces of the base layer, it is more preferable to use the same high-hardness resin (B) on both surfaces for the purpose of shape stability.

In one embodiment of the present invention, the hard coat layer has a concavo-convex shape. In the case where the hard coat layers are formed on both sides, the same hard coat layer is preferably provided because the shape stability is better.

In one embodiment of the present invention, the antiglare laminate can be used, for example, in a car navigation system, a Central Information Display (CID), a rear seat entertainment system (RSE), an instrument panel (cluster), and the like, a touch panel protective panel, and a front panel for OA equipment, portable electronic equipment, or television, which are display devices for vehicles. The front panel can be used alone as a front panel of a liquid crystal display device, for example, but may be used as a front panel after being combined with another substrate such as a touch sensor, for example.

Hereinafter, each component member of the antiglare laminate of the present invention will be described.

(resin (A) containing polycarbonate resin (a 1))

The resin (a) containing the polycarbonate resin (a1) used in the present invention is a resin mainly containing the polycarbonate resin (a 1). The content of the polycarbonate resin (a1) in the resin (a) is 75% by mass or more, but since the impact resistance can be improved by increasing the content, it is preferably 90% by mass or more, more preferably 100% by mass.

The polycarbonate resin (al) is not particularly limited as long as it contains a carbonate bond in the main molecular chain, that is, contains a unit of- [ O-R-OCO ] (R is an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and has a linear structure or a branched structure), and a polycarbonate resin containing a structural unit of the following formula (4) is particularly preferably used. By using such a polycarbonate resin, an antiglare laminate having excellent impact resistance can be obtained.

Specifically, as the polycarbonate resin (a1), an aromatic polycarbonate resin (for example, product names: Ipiplon S-2000, Ipiplon S-1000, Ipiplon E-2000, manufactured by Mitsubishi engineering plastics Co., Ltd.) and the like can be used, but not limited thereto.

Further, in recent years, there has been an increasing demand for bending front panels as well, and therefore, it is preferable to use a polycarbonate resin (al) obtained by using a monophenol represented by the following general formula (5) as a chain terminator.

(in the formula, R₁Represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms, R₂～R₅Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 12 carbon atomsThe substituent is halogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 12 carbon atoms. )

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

(in the formula, R₁Represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms. )

More preferably R in the formula (5) or the formula (6)₁Within a specified range of values. Specifically, as R₁The upper limit of the number of carbon atoms of (3) is preferably 36, more preferably 22, and particularly preferably 18. In addition, as R₁The lower limit of the number of carbon atoms of (2) is preferably 8, more preferably 12.

Among the monophenols (chain terminators) represented by the general formula (5) or the general formula (6), it is particularly preferable to use either or both of cetyl paraben and 2-hexyldecyl paraben as the chain terminator.

Using R in the formula (6)₁For example, a monophenol (chain terminator) having an alkyl group having 16 carbon atoms is particularly preferable as the chain terminator to be used for the polycarbonate resin of the present invention because it is excellent in glass transition temperature, melt flowability, moldability, sag resistance, and solvent solubility of the monophenol in the production of the polycarbonate resin.

On the other hand, R in the general formula (5) or the general formula (6)₁When the number of carbon atoms of (b) is excessively increased, the solubility of the monohydric phenol (chain terminator) in the organic solvent tends to be lowered, and the productivity in the production of the polycarbonate resin may be lowered.

For example, provided that R is₁Has 36 or less carbon atoms, and is excellent in productivity and economical efficiency in the production of a polycarbonate resin. Provided that R is₁Has 22 or less carbon atoms, has particularly excellent solubility in organic solvents of monophenols, and can provide a polycarbonate resin having very high productivity and improved economy.

General formula (5) or general formula (6) R in (1)₁When the number of carbon atoms of (2) is too small, the glass transition temperature of the polycarbonate resin may not be sufficiently low, and the thermoformability may be deteriorated.

In the present invention, the weight average molecular weight of the polycarbonate resin (al) affects the impact resistance and molding conditions of the antiglare laminate. That is, when the weight average molecular weight is too small, the impact resistance of the antiglare laminate is lowered, which is not preferable. When the weight average molecular weight is too high, an excessive heat source may be necessary when laminating the layers containing the polycarbonate resin (al), which is not preferable. Further, since a high temperature is required in some molding methods, the polycarbonate resin (al) is exposed to a high temperature, which may adversely affect the thermal stability thereof. The weight average molecular weight of the polycarbonate resin (al) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000. More preferably 25,000 to 65,000. The weight average molecular weight is a weight average molecular weight in terms of standard polystyrene, which is measured by Gel Permeation Chromatography (GPC).

The resin (a) may further contain additives and the like. As the additive, an additive generally used in resin sheets can be used. Examples of the additives include antioxidants, coloring inhibitors, antistatic agents, mold release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, reinforcing materials such as organic fillers and inorganic fillers. The method of mixing the additive and the resin is not particularly limited, and a method of mixing the total amount, a method of dry-blending the master batch, a method of dry-blending the total amount, and the like can be used. 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, based on the total mass of the base material layer.

(high-hardness resin (B))

The high-hardness resin (B) used in the present invention includes at least one selected from the group consisting of a high-hardness resin (B1), a high-hardness resin (B2), a high-hardness resin (B3), a high-hardness resin (B4), and a high-hardness resin (B5).

< high hardness resin (B1) >)

The high-hardness resin (B1) used in the present invention is a copolymer resin containing a (meth) acrylate structural unit (a) represented by the general formula (1) and an aliphatic vinyl structural unit (B) represented by the general formula (2), wherein the total proportion of the methacrylate structural unit (a) and the aliphatic vinyl structural unit (B) is 90 to 100 mol% of the total structural units of the copolymer resin, and the proportion of the methacrylate structural unit (a) is 65 to 80 mol% of the total structural units of the copolymer resin.

(wherein R1 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group having 1 to 18 carbon atoms.)

(wherein R3 represents a hydrogen atom or a methyl group, and R4 represents a cyclohexyl group which may have a hydrocarbon group having 1 to 4 carbon atoms.)

In the present specification, the "hydrocarbon group" may be any of linear, branched and cyclic groups, and may have a substituent.

In the (meth) acrylate structural unit (a) represented by the general formula (1), R2 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 thereof include methyl, ethyl, butyl, lauryl, stearyl, cyclohexyl and isobornyl groups.

Among the (meth) acrylate structural units (a), preferred are (meth) acrylate structural units in which R2 is a methyl group or an ethyl group, and more preferred are methyl methacrylate structural units in which R1 is a methyl group and R2 is a methyl group.

In the aliphatic vinyl structural unit (b) represented by the above general formula (2), R3 is a hydrogen atom or a methyl group, and more preferably a hydrogen atom. R4 is a cyclohexyl group having a cyclohexyl group or a C1-4 hydrocarbon group. Among the above aliphatic vinyl structural units (b), an aliphatic vinyl structural unit in which R3 is a hydrogen atom and R4 is a cyclohexyl group is more preferable.

The high-hardness resin (B1) may contain 1 or 2 or more of the above (meth) acrylate structural units (a), or may contain 1 or 2 or more of the above aliphatic vinyl structural units (B).

The total proportion of the (meth) acrylate structural unit (a) and the aliphatic vinyl structural unit (b) is 90 to 100 mol%, preferably 95 to 100 mol%, and more preferably 98 to 100 mol% with respect to the total of all the structural units of the copolymer resin.

That is, the high-hardness resin (B1) may contain a structural unit other than the (meth) acrylate structural unit (a) and the aliphatic vinyl structural unit (B). The amount thereof is preferably 10 mol% or less, more preferably 5 mol% or less, and particularly preferably 2 mol% or less, based on the total structural units of the resin (B1).

Examples of the structural units other than the (meth) acrylate structural unit (a) and the aliphatic vinyl structural unit (B) include structural units derived from an aromatic vinyl monomer having an unhydrogenated aromatic double bond, which are generated in the process of producing the resin (B1) by polymerizing a (meth) acrylate monomer and an aromatic vinyl monomer and then hydrogenating the aromatic double bond derived from the aromatic vinyl monomer.

The content of the (meth) acrylate structural unit (a) represented by the general formula (1) is preferably 65 to 80 mol%, and more preferably 70 to 80 mol%, based on the total structural units in the high-hardness resin (B1). When the proportion of the (meth) acrylate structural unit (a) is 65 mol% or more based on the total structural units in the resin (B1), a resin layer having excellent adhesion to the base material layer and excellent surface hardness can be obtained. When the amount is 80 mol% or less, the resin sheet is less likely to warp due to water absorption.

The content of the aliphatic vinyl structural unit (B) represented by the general formula (2) is preferably 20 to 35 mol%, more preferably 20 to 30 mol%, based on the total structural units in the high-hardness resin (B1). When the content of the aliphatic vinyl structural unit (b) is 20 mol% or more, warpage under high temperature and high humidity can be prevented, and when the content is 35 mol% or less, peeling at the interface with the base material layer can be prevented.

In the present specification, the "copolymer" may have any structure of a random copolymer, a block copolymer, and an alternating copolymer.

The method for producing the high-hardness resin (B1) is not particularly limited, and is preferably obtained by polymerizing at least one (meth) acrylate monomer and at least one aromatic vinyl monomer, and then hydrogenating the aromatic double bond derived from the aromatic vinyl monomer. And, (meth) acrylic acid means methacrylic acid and/or acrylic acid. Specific examples of the aromatic vinyl monomer used in this case include styrene, α -methylstyrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and derivatives thereof. Of these, styrene is preferred.

In the polymerization of the (meth) acrylate monomer and the aromatic vinyl monomer, a known method can be used, and the polymer can be produced by bulk polymerization, solution polymerization, or the like. The bulk polymerization method is carried out by a method in which a monomer composition containing the above-mentioned monomer and a polymerization initiator is continuously supplied to a complete mixing tank and continuously polymerized at 100 to 180 ℃. The monomer composition may contain a chain transfer agent as necessary.

The polymerization initiator is not particularly limited, and examples thereof include organic peroxides such as t-amyl peroxide-2-ethylhexanoate, t-butyl peroxide-2-ethylhexanoate, benzoyl peroxide, 1-bis (t-hexylperoxy) -3, 3, 5-trimethylcyclohexane, 1-bis (t-hexylperoxy) cyclohexane, 1-bis (t-butylperoxy) cyclohexane, t-hexylpropoxyiisopropyl monocarbonate, t-amyl peroxy-n-octanoate, t-butylisopropyl monocarbonate, and di-t-butyl peroxide, and azo compounds such as 2,2 ' -azobisisobutyronitrile, 2,2 ' -azobis (2-methylbutyronitrile), and 2,2 ' -azobis (2, 4-dimethylvaleronitrile). These can be used alone, or in combination of 2 or more.

The chain transfer agent is used as needed, and for example, α -methylstyrene dimer is cited.

Examples of the solvent used in the solution polymerization method include hydrocarbon solvents such as toluene, xylene, cyclohexane, and methylcyclohexane, ester solvents such as ethyl acetate and methyl isobutyrate, ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as tetrahydrofuran and dioxane, and alcohol solvents such as methanol and isopropanol.

The solvent used in the hydrogenation reaction after the polymerization of the (meth) acrylate monomer and the aromatic vinyl monomer may be the same as or different from the solvent used in the above-mentioned solution polymerization method. 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.

The high-hardness resin (B1) used in the present invention can be obtained by polymerizing the (meth) acrylate monomer and the aromatic vinyl monomer as described above and then hydrogenating the aromatic double bond derived from the aromatic vinyl monomer.

The method of hydrogenation is not particularly limited, and a known method can be used. For example, the reaction can be carried out in a batch or continuous flow process at a hydrogen pressure of 3 to 30MPa and a reaction temperature of 60 to 250 ℃. When the temperature is 60 ℃ or higher, the reaction time is not too long, and when the temperature is 250 ℃ or lower, the occurrence of molecular chain cleavage and hydrogenation of ester sites is reduced.

Examples of the catalyst used for the hydrogenation reaction include solid catalysts in which a metal such as nickel, palladium, platinum, cobalt, ruthenium, or rhodium, or an oxide, salt, or complex of such a metal is supported on a porous carrier such as carbon, alumina, silica alumina, or diatomaceous earth.

The high-hardness resin (B1) is preferably a resin in which 70% or more of the aromatic double bonds derived from the aromatic vinyl monomer are hydrogenated. That is, the proportion of the unhydrogenated portion of the aromatic double bond in the structural unit derived from the aromatic vinyl monomer is preferably 30% or less. When the content exceeds 30%, the transparency of the high-hardness resin (B1) may be lowered. The proportion of the unhydrogenated portion is more preferably in a range of less than 10%, and still more preferably less than 5%.

The weight average molecular weight of the high-hardness resin (B1) is not particularly limited, but is preferably 50,000 to 400,000, more preferably 70,000 to 300,000, from the viewpoint of strength and moldability. The weight average molecular weight is a weight average molecular weight in terms of standard polystyrene measured by Gel Permeation Chromatography (GPC).

The high-hardness resin (B1) may be blended with another resin within a range not impairing the transparency. Examples thereof include methyl methacrylate-styrene copolymer resin, polymethyl methacrylate, polystyrene, polycarbonate, cycloolefin (co) polymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, and various elastomers.

The glass transition temperature of the high-hardness resin (B1) is preferably in the range of 110 to 140 ℃. When the glass transition temperature is 110 ℃ or higher, the laminate provided by the present invention is less likely to be deformed or broken in a hot environment or a moist-hot environment, and is excellent in processability such as continuous heat forming by a mirror roller or a forming roller or batch heat forming by a mirror mold or a forming mold at 140 ℃ or lower. The glass transition temperature in the present invention is a temperature calculated by the midpoint method, which is measured at 10mg of a sample and a temperature increase rate of 10 ℃/min using a differential scanning calorimetry apparatus.

Examples of the high-hardness resin (B1) include Optimas7500 and 6000 (manufactured by mitsubishi gas chemical corporation), but are not limited thereto.

< high hardness resin (B2) >)

The high-hardness resin (B2) used in the present invention is a resin containing 35 to 65 mass% of the high-hardness resin (B1) and 35 to 65 mass% of a styrene-unsaturated dicarboxylic acid copolymer (C) containing 65 to 90 mass% of a styrene monomer unit (C1) and 10 to 35 mass% of an unsaturated dicarboxylic anhydride monomer unit (C2).

The styrene-unsaturated dicarboxylic acid copolymer (C) will be explained below.

< styrene-unsaturated dicarboxylic acid copolymer (C) >)

The styrene-unsaturated dicarboxylic acid copolymer (C) used in the present invention contains a styrene monomer unit (C1) and an unsaturated dicarboxylic anhydride monomer unit (C2).

< styrene monomer Unit (c1) >)

The styrene-based monomer is not particularly limited, and any known styrene-based monomer can be used, and from the viewpoint of availability, styrene, a-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, and the like can be mentioned. Among these, styrene is particularly preferable from the viewpoint of compatibility. These styrene monomers may be mixed in 2 or more.

< unsaturated dicarboxylic anhydride monomer Unit (c2) >)

Examples of the unsaturated dicarboxylic anhydride monomer include anhydrides of maleic acid, itaconic acid, citraconic acid, and aconitic acid, and maleic anhydride is preferable from the viewpoint of compatibility with the vinyl monomer. These unsaturated dicarboxylic anhydride monomers may be mixed in 2 or more.

< composition ratio of styrene-unsaturated dicarboxylic acid copolymer (C) >

The composition ratio of the styrene-unsaturated dicarboxylic acid copolymer (C) is 65 to 90 mass% (preferably 70 to 85 mass%) of the styrene monomer unit (C1), and 10 to 35 mass% (preferably 15 to 30 mass%) of the unsaturated dicarboxylic anhydride monomer unit (C2).

Specific examples of the copolymer (C) include, but are not limited to, XIBOND140 and XIBOND160 produced by POLYSCOPE POLYMERS BV.

< high hardness resin (B3) >)

The high-hardness resin (B3) used in the present invention is a resin comprising 55 to 10 mass% (preferably 50 to 20 mass%) of a resin (D) containing a vinyl monomer and 45 to 90 mass% (preferably 50 to 80 mass%) of a styrene-unsaturated dicarboxylic acid copolymer (E) containing 50 to 80 mass% of a styrene monomer unit (E1), 10 to 30 mass% of an unsaturated dicarboxylic anhydride monomer unit (E2) and 5 to 30 mass% of a vinyl monomer unit (E3).

The resin (D) containing a vinyl monomer and the styrene-unsaturated dicarboxylic acid copolymer (E) will be described in order below.

< resin (D) containing a vinyl monomer >

Examples of the vinyl monomer-containing resin (D) used in the present invention include resins obtained by homopolymerizing vinyl monomers such as acrylonitrile, methacrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate, and methyl methacrylate is particularly preferable as a monomer unit. Further, the copolymer may contain 2 or more kinds of the above monomer units. The weight average molecular weight of the vinyl monomer-containing resin (D) is preferably 10,000 to 500,000, more preferably 50,000 to 300,000.

< styrene-unsaturated dicarboxylic acid copolymer (E) >)

The styrene-unsaturated dicarboxylic acid copolymer (E) used in the present invention contains a styrene monomer unit (E1), an unsaturated dicarboxylic anhydride monomer unit (E2), and a vinyl monomer unit (E3).

< styrene-based monomer Unit (e1) >)

The styrene-based monomer is not particularly limited, and any known styrene-based monomer can be used, and from the viewpoint of availability, styrene, a-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, and the like can be mentioned. Among these, styrene is particularly preferable from the viewpoint of compatibility. These styrene monomers may be mixed in 2 or more.

< unsaturated twoCarboxylic anhydride monomer unit (e2) >

Examples of the unsaturated dicarboxylic anhydride monomer include anhydrides of maleic acid, itaconic acid, citraconic acid, and aconitic acid, and maleic anhydride is preferable from the viewpoint of compatibility with the vinyl monomer. These unsaturated dicarboxylic anhydride monomers may be mixed in 2 or more.

< vinyl monomer Unit (e3) >)

Examples of the vinyl monomer include vinyl monomers such as acrylonitrile, methacrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate. From the viewpoint of compatibility with the vinyl monomer-containing resin (D), Methyl Methacrylate (MMA) is preferred. These vinyl monomers may be mixed in a proportion of 2 or more.

< composition ratio of styrene-unsaturated dicarboxylic acid copolymer (E) >

The composition ratio of the styrene-unsaturated dicarboxylic acid copolymer (E) is 50 to 80 mass% (preferably 50 to 75 mass%) of the styrene monomer unit (E1), 10 to 30 mass% (preferably 10 to 25 mass%) of the unsaturated dicarboxylic anhydride monomer unit (E2), and 5 to 30 mass% (preferably 7 to 27 mass%) of the vinyl monomer unit (E3).

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 50,000 to 200,000, the compatibility with the vinyl monomer-containing resin (D) is good, and the effect of improving heat resistance is excellent. The weight average molecular weights of the resin (D) and the copolymer (E) are weight average molecular weights in terms of standard polystyrene measured by Gel Permeation Chromatography (GPC).

Specific examples of the copolymer (E) include, but are not limited to, RESISFY R100, R200, R310 (manufactured by electrochemical Co., Ltd.), DELPET 980N (manufactured by Asahi Kasei Chemicals Co., Ltd.).

< high hardness resin (B4) >)

The high-hardness resin (B4) used in the present invention is a resin copolymer (G) containing 5 to 20 mass% of a styrene structural unit, 60 to 90 mass% of a (meth) acrylate structural unit, and 5 to 20 mass% of an N-substituted maleimide monomer, or an alloy of the resin copolymer (G) and the copolymer (E).

Examples of the N-substituted maleimide monomer in the resin copolymer (G) include N-arylmaleimides such as N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide and N-tribromophenylmaleimide, and N-phenylmaleimide is preferably N-phenylmaleimide from the viewpoint of compatibility with acrylic resins. These N-substituted maleimide monomers may be mixed in 2 or more. The content of the N-substituted maleimide monomer is 5 to 20 mass%, preferably 5 to 15 mass%, more preferably 5 to 10 mass% with respect to the total amount of the high-hardness resin (B4).

The styrene structural unit is not particularly limited, and any known styrene monomer can be used, and from the viewpoint of availability, styrene, methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, and the like can be mentioned. Among these, styrene is particularly preferable from the viewpoint of compatibility. These styrene monomers may be mixed in 2 or more. The content of the styrene structural unit is 5 to 20 mass%, preferably 5 to 15 mass%, more preferably 5 to 10 mass% with respect to the total mass of the high-hardness resin (B4).

Examples of the (meth) acrylate structural unit 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, and as the monomer unit, methyl methacrylate is particularly preferable. Further, the copolymer may contain 2 or more of the above monomer units.

The content of the (meth) acrylate structural unit is 60 to 90 mass%, preferably 70 to 90 mass%, more preferably 80 to 90 mass% with respect to the total mass of the high-hardness resin (B4).

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

Examples of the resin copolymer (G) include, but are not limited to, DELPET PM120N (manufactured by Asahi Kasei Chemicals Co., Ltd.).

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

< high hardness resin (B5) >)

The high-hardness resin (B5) is a copolymer containing a structural unit (H) represented by the following formula (3) and optionally a structural unit (J) represented by the following formula (4). The high-hardness resin (B5) may or may not contain the structural unit (J), but is preferably contained.

The proportion of the structural unit (H) in the total structural units of the high-hardness resin (B5) is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and particularly preferably 70 to 100 mol%. The proportion of the structural unit (J) in the total structural units of the high-hardness resin (B5) is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, and particularly preferably 0 to 30 mol%.

The total content of the structural unit (H) and the structural unit (J) is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and particularly preferably 98 to 100 mol% with respect to the high-hardness resin (B5).

The high-hardness resin (B5) may contain a structural unit other than the structural unit (H) and the structural unit (J). When other structural units are contained, the amount thereof is preferably 10 mol% or less, more preferably 5 mol% or less, and particularly preferably 2 mol% or less, based on the total structural units of the high-hardness resin (B5).

The method for producing the high-hardness resin (B5) is not particularly limited, and can be produced by the same method as the method for producing the polycarbonate resin (a1) except that bisphenol C is used as a monomer.

Examples of the high-hardness resin (B5) include, but are not limited to, Iupilon KH3410UR, KH3520UR, and KS3410UR (manufactured by mitsubishi engineering plastics corporation).

The weight average molecular weight of the high-hardness resin (B5) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000, and particularly preferably 25,000 to 65,000.

The high-hardness resins (B1) to (B5) may contain additives and the like. As the additive, an additive generally used in resin sheets can be used, and examples of such additives include antioxidants, stainblocker, antistatic agents, mold release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, reinforcing materials such as organic fillers and inorganic fillers, and the like. The method of mixing the additive and the resin is not particularly limited, and a method of mixing the total amount, a method of dry-blending the master batch, a method of dry-blending the total amount, and the like can be used. 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, based on the total mass of the high-hardness resin layer.

The thickness of the high-hardness resin layer affects surface hardness and impact resistance. That is, when the high-hardness resin layer is too thin, the surface hardness becomes low, and when it is too thick, the impact resistance is lowered. 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.

Although another layer may be present between the polycarbonate layer and the high-hardness resin layer, here, a case where the high-hardness resin layer is laminated on the base material layer will be described. The lamination method is not particularly limited, and lamination can be performed similarly even when another layer is present. Examples include: a method of overlapping the substrate layer and the high-hardness resin layer formed separately and heating and pressure-bonding the both; a method of overlapping the substrate layer and the high-hardness resin layer formed separately and bonding the two layers with an adhesive; a method of co-extruding the base material layer and the high-hardness resin layer; and a method of integrating the base material layer on the high-hardness resin layer formed in advance by in-mold molding. Among these, a method of performing coextrusion molding is preferred from the viewpoint of production cost and productivity.

The method of coextrusion molding is not particularly limited. For example, in the feedblock method, a high-hardness resin layer is disposed on one surface of a base material layer by a feedblock, and after being extruded into a sheet shape by a T die, the sheet is cooled while passing through a forming roll to form a desired laminate. In the multi-manifold system, a high-hardness resin layer is disposed on one surface of a base material layer in a multi-manifold die, and the extruded layer is cooled while passing through a forming roll to form a desired laminate.

The total thickness of the base material layer and the high-hardness resin layer is preferably 100 to 3,000 μm, more preferably 500 to 3,000 μm, and particularly preferably 1,000 to 3,000 μm. By setting the total thickness to 100 μm or more, the rigidity of the sheet can be maintained. Further, by setting the total thickness to 3,000 μm or less, it is possible to prevent deterioration of the sensitivity of the touch sensor in the case where a touch panel is provided under a sheet. The ratio of the thickness of the base material layer to the total thickness of the base material layer and the high-hardness resin layer is preferably 75% to 99%, more preferably 80% to 99%, and particularly preferably 85% to 99%. When the amount is within the above range, both hardness and impact resistance can be achieved.

(hard coating)

The antiglare laminate (resin sheet) of the present invention has a hard coat layer. Other layers may be present between the hard coat layer and the high-hardness resin layer, but the hard coat layer is preferably laminated on the high-hardness resin layer. The hard coat layer is preferably an acrylic hard coat layer. In the present specification, "acrylic hard coat layer" means: a coating film having a crosslinked structure is formed by polymerizing a monomer, oligomer or prepolymer containing a (meth) acryloyl group as a polymerizable group. The composition of the acrylic hard coat layer preferably contains 2 to 98% by mass of a (meth) acrylic monomer, 2 to 98% by mass of a (meth) acrylic oligomer, and 0 to 15% by mass of a surface modifier, and more preferably contains 0.001 to 7 parts by mass of a photopolymerization initiator per 100 parts by mass of the total of the (meth) acrylic monomer, the (meth) acrylic oligomer, and the surface modifier.

The hard coat layer preferably contains 5 to 50% by mass of a (meth) acrylic monomer, 50 to 95% by mass of a (meth) acrylic oligomer, and 1 to 10% by mass of a surface modifier, and particularly preferably contains 20 to 40% by mass of a (meth) acrylic monomer, 60 to 80% by mass of a (meth) acrylic oligomer, and 2 to 5% by mass of a surface modifier.

The amount of the photopolymerization initiator is more preferably 0.01 to 5 parts by mass, and particularly preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the total of the (meth) acrylic monomer, the (meth) acrylic oligomer, and the surface modifier.

(1) (meth) acrylic acid-based monomer

The (meth) acrylic monomer may be any monomer having a (meth) acryloyl group as a functional group in the molecule, and may be a 1-functional monomer, a 2-functional monomer, or a 3-or more-functional monomer.

Examples of the 1-functional monomer include (meth) acrylic acid and (meth) acrylate, and specific examples of the 2-functional and/or 3-functional or higher (meth) acrylic monomer 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 diacrylate, neopentyl glycol di (meth) acrylate, 1, 4-butanediol diacrylate, 1, 3-butanediol di (meth) acrylate, dicyclopentyl di (meth) acrylate, polyethylene glycol diacrylate, 1, 4-butanediol oligoacrylate, neopentyl glycol oligoacrylate, and mixtures thereof, 1, 6-hexanediol oligomeric acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane propoxytrimethylene tri (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerol propoxytrimethylene tri (meth) acrylate, trimethylolpropane trimethacrylate, trimethylolpropane ethylene oxide adduct triacrylate, glycerol propylene oxide adduct triacrylate, pentaerythritol tetraacrylate, and the like, but are not limited thereto.

The hard coat layer may contain 1 or 2 or more (meth) acrylic monomers.

(2) (meth) acrylic oligomer

Examples of the (meth) acrylic oligomer include a 2-or more-functional urethane (meth) acrylate oligomer (hereinafter, also referred to as a "multifunctional urethane (meth) acrylate oligomer"), a 2-or more-functional polyester (meth) acrylate oligomer (hereinafter, also referred to as a "multifunctional polyester (meth) acrylate oligomer"), and a 2-or more-functional epoxy (meth) acrylate oligomer (hereinafter, also referred to as a "multifunctional epoxy (meth) acrylate oligomer"). The hard coat layer may contain 1 or 2 or more (meth) acrylic oligomers.

As the polyfunctional urethane (meth) acrylate oligomer, there can be cited a urethanization reaction product of a (meth) acrylate monomer having at least 1 (meth) acryloyloxy group and hydroxyl group in 1 molecule and a polyisocyanate; and urethane-forming reaction products of isocyanate compounds obtained by reacting polyols and polyisocyanates with (meth) acrylate monomers having at least 1 or more (meth) acryloyloxy groups and hydroxyl groups in 1 molecule.

As the (meth) acrylate monomer having at least 1 (meth) acryloyloxy group and hydroxyl group in 1 molecule used for the urethane-forming reaction, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate are cited.

Examples of the polyisocyanate used in the urethane formation reaction include a di-or tri-isocyanate such as hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, xylylene diisocyanate, a diisocyanate obtained by hydrogenating an aromatic isocyanate in these diisocyanates (e.g., a diisocyanate such as hydrogenated toluene diisocyanate or hydrogenated xylylene diisocyanate), triphenylmethane triisocyanate, and dimethylene triphenyltriisocyanate, and a polyisocyanate obtained by polymerizing a diisocyanate.

As the polyol used for the urethane-forming reaction, in addition to general aromatic, aliphatic and alicyclic polyols, polyester polyol, polyether polyol and the like can be used. In general, examples of aliphatic and alicyclic polyols include 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, trimethylolethane, trimethylolpropane, dimethylolheptane, dimethylolpropionic acid, dimethylolbutyric acid, glycerol, hydrogenated bisphenol A, and the like.

Examples of the polyester polyol include those obtained by a dehydration condensation reaction of the above-mentioned polyhydric alcohol 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. The polyether polyol may be, in addition to the polyalkylene glycol, a polyoxymethylene-modified polyol obtained by the reaction of the above polyol or phenol with an alkylene oxide.

In addition, the polyfunctional polyester (meth) acrylate oligomer can be obtained by a dehydration condensation reaction using (meth) acrylic acid, a polycarboxylic acid, and a polyol. Examples of the polycarboxylic acid used in the dehydration condensation reaction include succinic acid, adipic acid, maleic acid, itaconic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may be anhydrides. Examples of the polyhydric alcohol 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, dipentaerythritol, and the like.

The polyfunctional epoxy (meth) acrylate oligomer can be obtained by addition reaction of polyglycidyl ether with (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.

(3) Modifying agent

The modifier used in the present invention is a substance capable of changing the properties of the hard coat layer, such as a leveling agent, an antistatic agent, a surfactant, a water and oil repellent agent, and a UV absorber.

Examples of the leveling agent include polyether-modified polyalkylsiloxane, polyether-modified siloxane, polyalkylsiloxane containing polyester-modified hydroxyl groups, polyether-modified polydimethylsiloxane having alkyl groups, modified polyether, and silicon-modified acrylic acid.

Examples of the antistatic agent include glycerin fatty acid ester monoglyceride, glycerin fatty acid ester organic acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, cationic surfactant, anionic surfactant, and the like.

Examples of the surfactant and water and oil repellent agent include fluorine-containing surfactants and water and oil repellent agents such as oligomers containing a fluorine group/lipophilic group, and oligomers containing a fluorine group/hydrophilic group/lipophilic group/UV reactive group.

Examples of the UV absorber include a hydroxyphenyltriazine system, a benzotriazole system, and a benzophenone system.

The hard coat layer may contain a photopolymerization initiator. In the present specification, the photopolymerization initiator refers to a photo radical generator.

Examples of the monofunctional photopolymerization initiator that can be used in the present invention include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone [ Darocur 2959: manufactured by Merck corporation ]; α -hydroxy- α, α' -dimethylacetophenone [ Darocur 1173: manufactured by Merck corporation ]; acetophenone initiators such as methoxyacetophenone, 2' -dimethoxy-2-phenylacetophenone [ Irgacure-651], and 1-hydroxy-cyclohexyl phenyl ketone; benzoin ether-based initiators such as benzoin ethyl ether and benzoin isopropyl ether; and halogenated ketones, acylphosphine oxides, acylphosphonates, and the like.

The hard coat layer can be formed by, for example, applying a hard coat liquid to a layer (for example, a high-hardness resin layer) located under the hard coat layer and then photo-polymerizing the applied liquid.

The method for applying the hard coat paint of the present invention is not particularly limited, and a known method can be used. Examples thereof include spin coating, dipping, spraying, slide coating, bar coating, roll coating, gravure coating, meniscus coating, flexographic printing, screen printing, brush coating, and the like.

As a lamp used for light irradiation in photopolymerization, a lamp having a light emission distribution at a light wavelength of 420nm or less can be used, and examples thereof include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, a metal halide lamp, and the like. Among these, a high-pressure mercury lamp or a metal halide lamp is preferable because it can efficiently emit light in the initiator active wavelength region without emitting light of a short wavelength which causes the viscoelastic property of the resulting polymer to be lowered by crosslinking or light of a long wavelength which causes the reaction composition to be evaporated by heating in a large amount.

The irradiation intensity of the lamp is a factor that influences the degree of polymerization of the obtained polymer, and can be appropriately controlled according to various properties of the target product. When a general cleavage type initiator having an acetophenone group is blended, the illuminance is preferably 0.1 to 300mW/cm²The range of (1). Particularly preferably, a metal halide lamp is used, and the illuminance is set to 10-40 mW/cm²。

Photopolymerization may be hindered by oxygen in the air or oxygen dissolved in the reactive composition. Therefore, it is desirable that the light irradiation be carried out by a method capable of eliminating reaction inhibition by oxygen. One of such methods is: a method in which the reactive composition is coated with a film made of polyethylene terephthalate or TEFLON, thereby blocking contact with oxygen, and the reactive composition is irradiated with light through the film. In addition, the composition may be irradiated with light through a translucent window in an inert atmosphere in which oxygen is replaced with an inert gas such as nitrogen gas or carbon dioxide gas.

When light irradiation is performed in an inert atmosphere, a certain amount of inert gas is continuously introduced in order to keep the atmospheric oxygen concentration at a low level. By introducing the inert gas, a gas flow is generated on the surface of the reactive composition, and the monomer is vaporized. In order to suppress the level of evaporation of the monomer, the flow velocity of the inert gas is preferably 1m/sec or less, more preferably 0.1m/sec or less, relative to the relative velocity of the laminate coated with the hard coating liquid moving under the inert gas atmosphere. By setting the gas flow velocity in the above range, the evaporation of the monomer due to the gas flow can be substantially suppressed.

In order to improve the adhesion of the hard coat layer, the coated surface may be pretreated. Examples of the treatment include known methods such as a sand blast method, a solvent treatment method, a corona discharge treatment method, a chromic acid treatment method, a flame treatment method, a hot air treatment method, an ozone treatment method, an ultraviolet treatment method, and a primer treatment method using a resin composition.

The irradiation power of UV light (254nm) for the hard coat layer was 20mW/cm²When the metal halide lamp of (3) is irradiated with ultraviolet light, the pencil hardness is preferably 2H or more.

The film thickness of the hard coat layer is preferably 1 μm to 40 μm, more preferably 2 μm to 10 μm. By setting the film thickness to 1 μm or more, sufficient hardness can be obtained. Further, by setting the film thickness to 40 μm or less, the occurrence of cracks during bending can be suppressed. The film thickness of the hard coat layer can be measured by observing the cross section with a microscope or the like and actually measuring the interface to the surface of the coating film.

In one embodiment of the present invention, the hard coat layer having the uneven shape may have at least 1 characteristic of antireflection performance, antifouling performance, antistatic performance, and weather resistance. The method for applying the treatment such as the antireflection treatment, the antifouling treatment, the antistatic treatment, and the weather resistance treatment to the hard coat layer is not particularly limited, and a known method can be used. Examples thereof include a method of applying a reflection reducing coating material, a method of depositing a dielectric thin film, and a method of applying an antistatic coating material.

As a method for forming the irregularities on the hard coat layer, for example, molding using a mold can be cited. The molding using a mold can be produced by a method of forming a mold having a shape complementary to the uneven surface and curing the transparent base material coated with the hard coating agent with ultraviolet rays while the mold is in close contact with the transparent base material.

As a method for evaluating the blurring of characters, transmission image clarity (transmission clarity) according to JIS K7374 can be cited. The width of the optical comb is 0.125mm, 0.25mm, 0.5mm, 1.0mm, 2.0mm, and the variation of the value is large when the width of the optical comb is narrow, and the variation of the value is small when the width of the optical comb is wide, so that the width of the optical comb is preferably 2.0 mm.

The larger the value of the transmission resolution, the more suppressed the blurring of characters is, and the smaller the value, the more serious the blurring of characters is. In the present invention, the transmission clarity can be measured by the method described in the examples below.

As a method for evaluating reflection of an image, a reflected image clarity (reflection clarity) measured at a light incident angle of 45 ° in accordance with JIS K7374 can be cited. The width of the optical comb is 0.125mm, 0.25mm, 0.5mm, 1.0mm, 2.0mm, and the variation of the value is large when the width of the optical comb is narrow, and the variation of the value is small when the width of the optical comb is wide, so that the width of the optical comb is preferably 2.0 mm.

The larger the value of the reflection resolution measured at a light incidence angle of 45 °, the more likely reflection of the image occurs, and the smaller the value, the less likely reflection of the image occurs. In the present invention, the reflection resolution can be measured by the method described in the following examples.

In the present invention, in order to achieve both of character blurring and image reflection performance, when the transmission resolution when light is transmitted is T1 measured with an optical comb having a width of 2.0mm and the reflection resolution when light is reflected at a light incident angle of 45 ° measured with an optical comb having a width of 2.0mm is T2, T1/T2 is preferably 2.0 or more, more preferably 3.0 or more, and particularly preferably 3.0 to 4.0. The reflection sharpness can be measured when the back reflection is suppressed by attaching a black tape to the back surface of the uneven surface.

The transmission definition T1 when light is transmitted as measured using a 2.0mm wide optical comb preferably satisfies 30% ≦ T1 ≦ 50%, more preferably satisfies 40% ≦ T1 ≦ 50%, and the reflection definition T2 as measured using a 2.0mm wide optical comb at a light incidence angle of 45 ° preferably satisfies 10% ≦ T2 ≦ 20%, more preferably satisfies 10% ≦ T2 ≦ 15%.

In the present invention, the hard coat layer having a concavo-convex shape preferably does not contain inorganic particles or organic particles. The concave-convex shape in the present invention is provided by transfer. As described above, the hard coat layer does not contain inorganic particles or organic particles, whereby scratch resistance can be improved. In the present invention, the hard coat layer may have a second hard coat layer on a side opposite to the hard coat layer having the concavities and convexities. In a preferred embodiment of the present invention, the second hard coat layer has at least 1 characteristic selected from the group consisting of antireflection performance, antifouling performance, antistatic performance and weather resistance.

Another embodiment of the present invention provides the method for producing an antiglare laminate, including the step of transferring the uneven shape to the hard coat layer by pressure-bonding a patterned PET film to a photocurable resin composition on the layer containing the high-hardness resin (B). As the patterned PET film, for example, PTH, PTHA, or PTHZ of embler manufactured by UNITIKA, PF11, PF23 of low flash point AG film manufactured by cellophane, or the like can be used.

Examples

The following examples of the present invention are shown, but the present invention is not limited by the examples.

< transmission clarity (T1) >

The measurement was performed by using a Suga Test Instruments co., ltd. "ICM 1T", based on JIS K7374, in such a manner that the flow direction of the antiglare laminate was parallel to the direction of the optical comb teeth of the optical comb. In the optical comb, the transmitted resolution was defined as the resolution transmitted from the light source using an optical comb having a width of 2.0 mm.

< clarity of reflection (T2) >

The measurement was performed by using a Suga Test Instruments co., ltd. "ICM 1T", based on JIS K7374, in such a manner that the flow direction of the antiglare laminate was parallel to the direction of the optical comb teeth of the optical comb. In the optical comb, a reflection image clarity measured at a light incident angle of 45 ° was taken as a reflection clarity using an optical comb having a width of 2.0 mm. The measurement was performed by attaching a black tape (model 117BLA black plastic tape manufactured by 3M JAPAN corporation) to the back surface of the uneven surface to suppress back surface reflection.

Hardness of SW

For the anti-glare laminate, STEEL WOOL #0000 manufactured by NIHON STEEL WOOL co., ltd. was used, and the thickness was visually observed at 100g/cm²The degree of damage after 15 load cycles was evaluated in 10 stages. Respectively labeled as level 1 to level 10.

Level 1: no damage (same degree as inorganic glass).

10 level: there was a majority of damage (to the same extent as polycarbonate).

< shape stability >

The test piece was cut into pieces of 100mm by 60 mm. The cut test piece was mounted on a 2-point support type holder, and after the state adjustment was performed for 24 hours or more in an environmental test machine set to a temperature of 23% and a relative humidity of 50%, the warpage was measured (before processing). Thereafter, the test piece was mounted on a holder, and put into an environmental tester set at a temperature of 85 ℃ and a relative humidity of 85%, and held in this state for 120 hours. The resultant was moved together with the holder to an environmental tester set at a temperature of 23% and a relative humidity of 50%, and the resultant was held for 4 hours, and then the warpage was measured again (after the treatment). The warpage was measured using a 3-dimensional shape measuring machine (KS-1000, manufactured by KEYENCE) equipped with an electric stage, and the test piece taken out was horizontally set with the convex portion facing upward, scanned at 1 mm intervals, and the convex portion at the center was measured as the warpage. The absolute value of the difference in the amount of warpage before and after the treatment, i.e., | (the amount of warpage after the treatment) - (the amount of warpage before the treatment) | was evaluated as the shape stability.

Example 1

< laminate (X-1) >)

A synthetic resin laminate was obtained by molding using a multilayer extrusion apparatus having a single screw extruder having an axial diameter of 35mm, a single screw extruder having an axial diameter of 65mm, a feed block connected to all the extruders, and a T-die connected to the feed block. Optimas7500, manufactured by Mitsubishi gas chemical corporation, as a high hardness resin (B1) was continuously introduced into a single-screw extruder having an axial diameter of 35mm, and the mixture was extruded under conditions of a cylinder temperature of 240 ℃ and a discharge rate of 2.6 kg/h. Further, a polycarbonate resin (product name: Ipiplon S-1000, manufactured by Mitsubishi engineering plastics Co., Ltd.) was continuously introduced into a single-screw extruder having an axial diameter of 65mm, and the mixture was extruded at a cylinder temperature of 280 ℃ and a discharge rate of 50.0 kg/h. The feedblock connected to all the extruders was equipped with 2 kinds of 2-layer distribution pins, and the high hardness resin (B1) and the polycarbonate resin were introduced at a temperature of 270 ℃ to laminate them. The resin was extruded from a T die connected to the tip thereof at a temperature of 270 ℃ into a sheet form, and the sheet was cooled while transferring the mirror surface using 3 mirror surface finishing rolls set at 120 ℃, 130 ℃ and 190 ℃ from the upstream side to obtain a laminate (X-1) of a high-hardness resin (B1) layer and a polycarbonate resin layer. The thickness of the laminate (X-1) was 1.0mm, and the thickness of the high-hardness resin (B1) layer was 60 μm in the vicinity of the center.

The Optimas7500, manufactured by mitsubishi gas chemical corporation, used as the high-hardness resin (B1), is a copolymer resin containing a (meth) acrylate structural unit (a) represented by the general formula (1) and an aliphatic vinyl structural unit (B) represented by the general formula (2), and the copolymer resin is such that the total proportion of the (meth) acrylate structural unit (a) and the aliphatic vinyl structural unit (B) is 99 mol% of the total structural units of the copolymer resin, and the proportion of the (meth) acrylate structural unit (a) is 75 mol% of the total structural units of the copolymer resin.

< Photocurable resin composition (Y-1) >)

The photocurable resin composition (Y-1) was obtained by adding 3 parts by mass of a photoinitiator to 100 parts by mass of a mixture of 60% by mass of U6HA, 35% by mass of #260, and 5% by mass of a fluorine-based leveling agent.

U6 HA: a 6-functional urethane acrylate oligomer (manufactured by shinkanmura chemical industries, Ltd.);

# 260: 1, 9-nonanediol diacrylate (manufactured by Osaka organic chemical industries, Ltd.);

a fluorine-based leveling agent;

photoinitiator: i-184 (manufactured by BASF corporation [ compound name: 1-hydroxy-cyclohexylphenylketone ]).

< patterned PET film (Z-1) >)

As a PET film for transferring an uneven shape, C-50G-100-1 manufactured by Mitsukuai industry was used.

A photocurable resin composition (Y-1) was applied to the high-hardness resin (B1) layer of the laminate (X-1) by a bar coater so that the cured coating film thickness was 5 to 10 μm, and the patterned surface of the patterned PET film (Z-1) was covered with the coating liquid so as to be in contact therewith and pressure-bonded thereto. Thereafter, a metal halide lamp (20mW/cm) was irradiated from a light source at a distance of 12cm for 30 seconds to cure the film, and the patterned PET film was peeled off to obtain an antiglare laminate having a hard coat layer having irregularities on the high-hardness resin (B1) layer.

Example 2

An antiglare laminate was obtained in the same manner as in example 1, except that C-50G-100-2 (Z-2) manufactured by Islands industries was used as the patterned PET film.

Example 3

An antiglare laminate was obtained in the same manner as in example 1, except that C-50G-100-3 (Z-3) manufactured by Islands industries was used as the patterned PET film.

Example 4

Production of < high hardness resin (B2) >

40 mass% of the high hardness resin (B1) used in example 1 and 60 mass% of XIBOND140 made by POLYSCOPE POLYMERS BV as the styrene-unsaturated dicarboxylic acid copolymer (C) were fed into a blender and mixed for 30 minutes, and then melt-kneaded at a cylinder temperature of 230 ℃ using an extruder (made by Toshiba machine, TEM-26 SS, L/D40) having a screw diameter of 26mm, extruded into a strand, and pelletized using a pelletizer to obtain a high hardness resin (B2). The granulation can be stably performed.

The XIBOND140 produced by POLYSCOPE POLYMERS BV used as the styrene-unsaturated dicarboxylic acid copolymer (C) is a resin containing 85 mass% of a styrene monomer unit (C1) and 15 mass% of an unsaturated dicarboxylic anhydride monomer unit (C2).

< laminate (X-2) >)

A synthetic resin laminate was obtained by molding using a multilayer extrusion apparatus equipped with a single-screw extruder having an axial diameter of 35mm, a single-screw extruder having an axial diameter of 65mm, a feed block connected to all the extruders, and a T-die connected to the feed block. A high-hardness resin (B2) was continuously introduced into a single-screw extruder having an axial diameter of 35mm, and the mixture was extruded under conditions of a cylinder temperature of 240 ℃ and a discharge rate of 2.6 kg/h. Further, a polycarbonate resin (product name: Ipiplon S-1000, manufactured by Mitsubishi engineering plastics Co., Ltd.) was continuously introduced into a single-screw extruder having an axial diameter of 65mm, and the mixture was extruded at a cylinder temperature of 280 ℃ and a discharge rate of 50.0 kg/hr. The feedblock connected to all extruders was equipped with 2 kinds of 2-layer distribution pins, and the high hardness resin (B2) and polycarbonate resin were introduced at a temperature of 270 ℃ to laminate them. The resin was extruded from a T die connected to the tip thereof at a temperature of 270 ℃ into a sheet form, and the sheet was cooled while transferring the mirror surface using 3 mirror surface finishing rolls set at 120 ℃, 130 ℃ and 190 ℃ from the upstream side, to obtain a laminate (X-2) of a high-hardness resin (B2) layer and a polycarbonate resin layer. The thickness of the laminate (X-2) was 1.0mm, and the thickness of the high-hardness resin (B2) layer was 60 μm in the vicinity of the center.

A photocurable resin composition (Y-1) was applied to the high-hardness resin (B2) layer of the laminate (X-2) by a bar coater so that the cured coating film thickness was 5 to 10 μm, and the patterned surface of the patterned PET film (Z-1) was covered with the coating liquid so as to be in contact therewith and pressure-bonded thereto. Thereafter, the resultant was irradiated with a metal halide lamp (20mW/cm) for 30 seconds at a light source distance of 12cm to cure the film, and the patterned PET film was peeled off to obtain an antiglare laminate having a hard coat layer having irregularities on the high-hardness resin (B2) layer.

Example 5

Production of < high hardness resin (B3) >

75% by mass of RESISFY R100 (manufactured by DENKA) as a styrene-unsaturated dicarboxylic acid copolymer (E) and 25% by mass of a methyl methacrylate resin Parapet HR-L (manufactured by Coli, weight average molecular weight: 90,000) as a vinyl monomer-containing resin (D) were charged into a blender and mixed for 30 minutes, and then melt-kneaded at a cylinder temperature of 230 ℃ using an extruder (manufactured by Toshiba machine, TEM-26 SS, L/D. approx.40) having a screw diameter of 26mm, extruded into a strand, and pelletized by a pelletizer to obtain a high-hardness resin (B3). The granulation can be stably performed.

Among them, RESISFY R100 (manufactured by DENKA) used as the styrene-unsaturated dicarboxylic acid copolymer (E) is a copolymer containing 21 mass% of a methyl methacrylate structural unit, 64 mass% of a styrene structural unit, and 15 mass% of a maleic anhydride structural unit.

< laminate (X-3) >)

A synthetic resin laminate was obtained by molding using a multilayer extrusion apparatus equipped with a single-screw extruder having an axial diameter of 35mm, a single-screw extruder having an axial diameter of 65mm, a feed block connected to all the extruders, and a T-die connected to the feed block. A high-hardness resin (B3) was continuously introduced into a single-screw extruder having an axial diameter of 35mm, and the mixture was extruded under conditions of a cylinder temperature of 240 ℃ and a discharge rate of 2.6 kg/h. Further, a polycarbonate resin (product name: Ipiplon S-1000, manufactured by Mitsubishi engineering plastics Co., Ltd.) was continuously introduced into a single-screw extruder having an axial diameter of 65mm, and the mixture was extruded at a cylinder temperature of 280 ℃ and a discharge rate of 50.0 kg/hr. The feedblock connected to all the extruders was equipped with 2 kinds of 2-layer distribution pins, and the high hardness resin (B3) and the polycarbonate resin were introduced at 270 ℃ to laminate them. The resin was extruded from a T die connected to the tip thereof at a temperature of 270 ℃ into a sheet form, and the sheet was cooled while transferring the mirror surface using 3 mirror surface finishing rolls set at 120 ℃, 130 ℃ and 190 ℃ from the upstream side, to obtain a laminate (X-3) of a high-hardness resin (B3) layer and a polycarbonate resin layer. The thickness of the resulting laminate (X-3) was 1.0mm, and the thickness of the layer of the high-hardness resin (B3) was 60 μm in the vicinity of the center.

A photocurable resin composition (Y-1) was applied to the high-hardness resin (B3) layer of the laminate (X-3) by a bar coater so that the cured coating film thickness was 5 to 10 μm, and the patterned surface of the patterned PET film (Z-1) was covered with the coating liquid so as to be in contact therewith and pressure-bonded thereto. Thereafter, a metal halide lamp (20mW/cm) was irradiated from a light source at a distance of 12cm for 30 seconds to cure the film, and the patterned PET film was peeled off to obtain an antiglare laminate having a hard coat layer having irregularities on the high-hardness resin (B3) layer.

Example 6

Production of < high hardness resin (B4) >

75% by mass of the styrene-unsaturated dicarboxylic acid copolymer (E) used in example 5 and 25% by mass of DELPET PM-120N (manufactured by Asahi Kasei Chemicals) as the resin copolymer (G) were charged into a blender and mixed for 30 minutes, and then melt-kneaded at a cylinder temperature of 230 ℃ using an extruder (manufactured by Toshiba machine, TEM-26 SS, L/D. approximately.40) having a screw diameter of 26mm, extruded into a strand, and pelletized using a pelletizer to obtain a high-hardness resin (B4), wherein DELPET PM-120N is a copolymer containing 7% by mass of styrene structural units, 86% by mass of methyl methacrylate structural units, and 7% by mass of N-phenylmaleimide structural units. The granulation can be stably performed.

< laminate (X-4) >)

A synthetic resin laminate was obtained by molding using a multilayer extrusion apparatus equipped with a single-screw extruder having an axial diameter of 35mm, a single-screw extruder having an axial diameter of 65mm, a feed block connected to all the extruders, and a T-die connected to the feed block. A high-hardness resin (B4) was continuously introduced into a single-screw extruder having an axial diameter of 35mm, and the mixture was extruded under conditions of a cylinder temperature of 240 ℃ and a discharge rate of 2.6 kg/h. Further, a polycarbonate resin (product name: Ipiplon S-1000, manufactured by Mitsubishi engineering plastics Co., Ltd.) was continuously introduced into a single-screw extruder having an axial diameter of 65mm, and the mixture was extruded at a cylinder temperature of 280 ℃ and a discharge rate of 50.0 kg/hr. The feedblock connected to all the extruders was equipped with 2 kinds of 2-layer distribution pins, and the high hardness resin (B4) and the polycarbonate resin were introduced at a temperature of 270 ℃ to laminate them. The resin was extruded from a T die connected to the tip thereof at a temperature of 270 ℃ into a sheet form, and the sheet was cooled while transferring the mirror surface using 3 mirror surface finishing rolls set at 120 ℃, 130 ℃ and 190 ℃ from the upstream side, to obtain a laminate (X-4) of a high-hardness resin (B4) layer and a polycarbonate resin layer. The thickness of the laminate (X-4) was 1.0mm, and the thickness of the high-hardness resin (B4) layer was 60 μm in the vicinity of the center.

The photocurable resin composition (Y-1) was applied to the high-hardness resin (B4) layer of the laminate (X-4) by a bar coater so that the cured coating film thickness was 5 to 10 μm, and the patterned surface of the patterned PET film (Z-1) was covered with the coating liquid so as to be in contact therewith and pressure-bonded thereto. Thereafter, the resultant was irradiated with a metal halide lamp (20mW/cm) for 30 seconds at a light source distance of 12cm to cure the film, and the patterned PET film was peeled off to obtain an antiglare laminate having a hard coat layer having irregularities on the high-hardness resin (B4) layer.

Example 7

< laminate (X-5) >)

A synthetic resin laminate was obtained by molding using a multilayer extrusion apparatus equipped with a single-screw extruder having an axial diameter of 35mm, a single-screw extruder having an axial diameter of 65mm, a feed block connected to all the extruders, and a T-die connected to the feed block. Ilpilon KH3410UR (manufactured by Mitsubishi engineering plastics Co., Ltd.) as a high-hardness resin (B5) was continuously introduced into a single-screw extruder having an axial diameter of 35mm, and the mixture was extruded under conditions of a cylinder temperature of 270 ℃ and a discharge rate of 2.6 kg/h. Further, a polycarbonate resin (product name: Ipiplon S-1000, manufactured by Mitsubishi engineering plastics Co., Ltd.) was continuously introduced into a single-screw extruder having an axial diameter of 65mm, and the mixture was extruded at a cylinder temperature of 280 ℃ and a discharge rate of 50.0 kg/hr. The feedblock connected to all the extruders was equipped with 2 kinds of 2-layer distribution pins, and the high hardness resin (B5) and the polycarbonate resin were introduced at 270 ℃ to laminate them. The resin was extruded from a T die connected to the tip thereof at a temperature of 270 ℃ into a sheet form, and the sheet was cooled while transferring the mirror surface using 3 mirror surface finishing rolls set at 120 ℃, 130 ℃ and 190 ℃ from the upstream side, to obtain a laminate (X-5) of a high-hardness resin (B5) layer and a polycarbonate resin layer. The thickness of the laminate (X-5) was 1.0mm, and the thickness of the high-hardness resin (B5) layer was 60 μm in the vicinity of the center.

A photocurable resin composition (Y-1) was applied to the high-hardness resin (B5) layer of the laminate (X-5) by a bar coater so that the cured coating film thickness was 5 to 10 μm, and the patterned surface of the patterned PET film (Z-1) was covered with the coating liquid so as to be in contact therewith and pressure-bonded thereto. Thereafter, a metal halide lamp (20mW/cm) was irradiated from a light source at a distance of 12cm for 30 seconds to cure the film, and the patterned PET film was peeled off to obtain an antiglare laminate having a hard coat layer having irregularities on the high-hardness resin (B5) layer.

Comparative example 1

An antiglare laminate was obtained in the same manner as in example 1, except that PS-27 (Z-4) made of cellophane was used as the patterned PET film.

Comparative example 2

50 parts by mass of an acrylic ultraviolet-curable resin (100% solid content, product name: LIGHT ACRYLATE DPE-6A Kyoeisha Co., Ltd.), 0.5 part by mass of silica fine particles (octylsilane-treated fumed silica, average primary particle diameter 12nm, NIPPON AEROSIL CO., LTD. manufactured), 1 part by mass of an acrylic silane-treated silica (average particle diameter 1.9 μm, product name: SE-6050-SYB ADMATECHS Co., Ltd.) and 3 parts by mass of a photoinitiator (product name: Omnirad184IGM Resins) were mixed with 50 parts by mass of MEK and stirred to prepare coating solution (i). Thereafter, coating liquid (i) was applied onto a PET (polyethylene terephthalate) film so that the dry film thickness became 2.5 μm, dried at 80 ℃ for 2 minutes, and then cured by irradiating ultraviolet rays at a linear velocity of 1.5 m/min on a conveyor belt equipped with a high-pressure mercury lamp having a light source distance of 12cm and a power of 80W/cm, to produce a patterned PET film (Z-5), and an antiglare laminate was obtained in the same manner as in example 1 except for the above.

Comparative example 3

50 parts by mass of an acrylic ultraviolet-curable resin (100% solid content, product: LIGHT ACRYLATE DPE-6A Kyoeisha Co., Ltd.), 1.5 parts by mass of silica fine particles (octylsilane-treated fumed silica, average primary particle diameter 1.9 μm, product name: SE 6050-SYB ADMATECHS Co., Ltd.) and 3 parts by mass of a photoinitiator (product name Irgacure184, product of Toyotsu Chemiplas Co., Ltd.) were mixed with 50 parts by mass of MEK and stirred to prepare a coating solution (Y-2). The coating liquid (Y-2) was applied to the laminate (X-1) described in example 1 so that the dry film thickness became 2.5 μm, dried at 80 ℃ for 2 minutes, and then cured by irradiation with a 30-second metal halide lamp (20mW/cm) while purging with nitrogen gas, to obtain an antiglare laminate.

Comparative example 4

A hard coat layer was formed in the same manner as in example 1 except that a laminate (X-6) obtained by using a methyl methacrylate resin, Parapet HR-L (manufactured by Coli, weight average molecular weight: 90,000) in place of the high-hardness resin (B1) was used, to obtain an antiglare laminate.

The anti-glare laminates obtained in examples 1 to 7 and comparative examples 1 to 4 were evaluated for transmission clarity, 45 ° reflection clarity, SW hardness, and shape stability. The results are shown in the following table.

[ Table 1]

As described above, according to the present invention, it is possible to provide an antiglare laminate having both image reflection prevention performance and glare resistance against character blurring, high abrasion resistance, and excellent shape stability.

Claims (12)

1. An anti-glare laminate, comprising: a layer comprising a resin (A) containing a polycarbonate resin (a1); a layer containing a high hardness resin (B) provided on at least one side of a layer containing the resin (A) containing the polycarbonate resin (a1); and a hard coat layer having a concavo-convex shape further provided on the layer containing the high hardness resin (B), The anti-glare laminate satisfies the following conditions (i) and (ii): (i) The thickness of the layer containing the high hardness resin (B) is 10 to 250 μm, the layer containing the resin (A) containing the polycarbonate resin (a1) and the layer containing the high hardness resin (B) The total thickness of the layers is 100 to 3,000 μm; (ii) The transmission clarity when light is transmitted through the laminate measured using a 2.0 mm wide optical comb is defined as T1, and the 2.0 mm wide optical comb measured at a light incident angle of 45° When the reflection clarity of the laminate is set to T2, T1/T2 is 2.0 or more. 2. The anti-glare laminate according to claim 1, wherein: The transmission clarity T1 measured by using a 2.0mm width optical comb through the laminated body satisfies 30%≤T1≤50%, measured using a 2.0mm width optical comb at a light incident angle of 45° The reflection clarity T2 satisfies 10%≤T2≤20%. 3. The anti-glare laminate according to claim 1 or 2, characterized in that: The high hardness resin (B) contains at least one selected from the following resins (B1) to (B5), The resin (B1) contains a (meth)acrylate structural unit (a) represented by the following general formula (1) and an aliphatic vinyl structural unit (b) represented by the following general formula (2). A copolymer resin, wherein the total ratio of the (meth)acrylate structural unit (a) and the aliphatic vinyl structural unit (b) is 90 to 100 mol % of all the structural units of the copolymer resin, so The proportion of the (meth)acrylate structural unit (a) is 65-80 mol% of the total structural unit of the copolymer resin,

In formula (1), R1 is a hydrogen atom or a methyl group, R2 is an alkyl group having 1 to 18 carbon atoms,

In formula (2), R3 is a hydrogen atom or a methyl group, and R4 is a cyclohexyl group which may have a hydrocarbon group having 1 to 4 carbon atoms; The resin (B2) is a resin containing 35 to 65 mass % of the resin (B1) and 35 to 65 mass % of the styrene-unsaturated dicarboxylic acid-based copolymer (C), wherein the styrene-unsaturated The saturated dicarboxylic acid copolymer (C) contains 65-90 mass % of styrene-based monomer units (c1) and 10-35 mass % of unsaturated dicarboxylic acid anhydride monomer units (c2); The resin (B3) is a resin containing 55 to 10% by mass of a vinyl-based monomer-containing resin (D) and 45 to 90% by mass of a styrene-unsaturated dicarboxylic acid-based copolymer (E), wherein the The styrene-unsaturated dicarboxylic acid-based copolymer (E) contains 50 to 80 mass % of styrene-based monomer units (e1), 10 to 30 mass % of unsaturated dicarboxylic acid monomer units (e2), and vinyl groups The monomer unit (e3) is 5 to 30% by mass; The resin (B4) is a resin containing 5 to 20 mass % of styrene structural units, 60 to 90 mass % of (meth)acrylate structural units, and 5 to 20 mass % of N-substituted maleimide monomers Copolymers (G), or resins which are alloys of resinous copolymers (G) and said copolymers (E); The resin (B5) is a copolymer containing a structural unit (H) represented by the following formula (3) and an optional structural unit (J) represented by the following formula (4),

4. The anti-glare laminate according to any one of claims 1 to 3, wherein: The hard coat layer having the concavo-convex shape does not contain inorganic particles or organic particles. 5. The anti-glare laminate according to any one of claims 1 to 4, wherein: The hard coat layer having a concavo-convex shape has at least one characteristic selected from the group consisting of antireflection performance, antifouling performance, antistatic performance and weather resistance. 6. The anti-glare laminate according to any one of claims 1 to 5, wherein: It has a 2nd hard-coat layer on the surface opposite to the said hard-coat layer which has unevenness|corrugation. 7. The anti-glare laminate according to claim 6, wherein: The second hard coat layer has at least one characteristic selected from the group consisting of antireflection performance, antifouling performance, antistatic performance and weather resistance. 8. The anti-glare laminate according to any one of claims 1 to 7, wherein: The polycarbonate resin (a1) contains a component derived from a monohydric phenol represented by the following general formula (5),

In formula (5), R ₁ represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms, and R ₂ to R ₅ each independently represent a hydrogen atom, a halogen, or a carbon which may have a substituent An alkyl group having 1 to 20 atoms or an aryl group having 6 to 12 carbon atoms, 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. 9. A vehicle-mounted display device, characterized in that: The anti-glare laminate according to any one of claims 1 to 8 is contained. 10. A touch panel front protection board, characterized in that: The anti-glare laminate according to any one of claims 1 to 8 is contained. 11 . A front panel for OA equipment, portable electronic equipment, or television, comprising the anti-glare laminate according to claim 1 . 12 . A method for producing an anti-glare laminate for producing the anti-glare laminate according to claim 1 , wherein: 12 . It includes the step of transferring the concavo-convex shape to the hard coat layer by press-bonding a patterned PET film on the photocurable resin composition on the layer containing the high hardness resin (B).

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