阅读说明：本技术 防眩性叠层体 (Anti-glare laminate ) 是由 小泽归心 于 2020-03-19 设计创作，主要内容包括：本发明提供具有优异的耐冲击性、耐热性和防眩性能,并且抑制闪耀的发生,具有高的耐擦伤性,形状稳定性也优异的防眩性叠层体。更详细而言,提供如下的防眩性叠层体,其包括：包含含有聚碳酸酯树脂(a1)的树脂(A)的层；设置于包含含有聚碳酸酯树脂(a1)的树脂(A)的层的至少1个面的、包含高硬度树脂(B)的层；和设置于包含高硬度树脂(B)的层上的、具有凹凸形状的硬涂层,该防眩性叠层体满足下述条件(i)和(ii)：(i)上述包含高硬度树脂(B)的层的厚度为10～250μm,上述包含含有聚碳酸酯树脂(a1)的树脂(A)的层与包含上述高硬度树脂(B)的层的合计厚度为100～3,000μm；(ii)上述叠层体的由JIS K 7136规定的雾度为15％以上,使用2.0mm宽度的光梳以45°的光入射角测得的反射清晰度为30％以下,将该叠层体设置在265ppi的光源上用柯尼卡美能达制Prometoric Y29测得的亮度标准偏差/评价范围的平均亮度为2.0以下。(The invention provides an anti-dazzle laminate which has excellent impact resistance, heat resistance and anti-dazzle performance, inhibits the generation of sparkle, has high scratch resistance and has excellent shape stability. More specifically, an antiglare laminate comprising: a layer comprising a resin (a) containing a polycarbonate resin (a 1); a layer comprising a high-hardness resin (B) provided on at least 1 surface of the layer comprising the resin (a) comprising the polycarbonate resin (a 1); and a hard coat layer having an uneven shape provided on the layer containing the high-hardness resin (B), the antiglare laminate satisfying 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) the laminate has a haze of 15% or more as defined in JIS K7136, a reflection resolution of 30% or less as measured at a light incidence angle of 45 ℃ using a 2.0mm wide comb, and an average luminance of 2.0 or less as measured by a luminance standard deviation/evaluation range as measured by Prometoric Y29 manufactured by Konika Menten on a 265ppi light source.)

1. An antiglare laminate comprising:

a layer comprising a resin (a) containing a polycarbonate resin (a 1);

a layer comprising a high-hardness resin (B) provided on at least 1 surface of the layer comprising the resin (a) comprising the polycarbonate resin (a 1); and

a hard coat layer having a concavo-convex shape provided on the layer containing the high-hardness resin (B),

the antiglare laminate satisfies the following conditions (i) and (ii):

(i) the layer comprising the high-hardness resin (B) has a thickness of 10 to 250 [ mu ] m, and the total thickness of the layer comprising the resin (A) containing the polycarbonate resin (a1) and the layer comprising the high-hardness resin (B) is 100 to 3,000 [ mu ] m;

(ii) the laminate has a haze of 15% or more as defined in JIS K7136, a reflection resolution of 30% or less as measured at a light incidence angle of 45 DEG using a 2.0mm wide optical comb, and an average luminance of 2.0 or less as measured by a luminance standard deviation/evaluation range as measured by Prometoric Y29 manufactured by Konika Menten on a 265ppi light source.

2. The antiglare laminate of claim 1, wherein:

the high-hardness resin (B) includes any one of the following resins (B1) to (B4),

the resin (B1) is a copolymer resin comprising 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,

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

in the formula (2), R3 is a hydrogen atom or a methyl group, R4 is a cyclohexyl group which may have a hydrocarbon group having 1 to 4 carbon atoms;

the resin (B2) is a resin comprising 55 to 10 mass% of a resin (C) containing a vinyl monomer and 45 to 90 mass% of a styrene-unsaturated dicarboxylic acid copolymer (D) comprising 50 to 80 mass% of a styrene monomer unit (D1), 10 to 30 mass% of an unsaturated dicarboxylic acid monomer unit (D2) and 5 to 30 mass% of a vinyl monomer unit (D3),

the resin (B3) is a resin copolymer (G) comprising 5 to 20 mass% of a styrene structural unit, 70 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 resin copolymer (D),

the resin (B4) is a copolymer comprising a structural unit (H) represented by the following general formula (3) and optionally comprising a structural unit (J) represented by the following general formula (4),

3. the antiglare laminate of claim 1 or 2, wherein:

the ratio of the angle of 5 DEG or less in the inclination angle distribution of the above-described uneven shape measured by using a white interference microscope VS-1000 manufactured by Hitachi high and New technology is 65-80%.

4. The antiglare laminate according to any one of claims 1 to 3, wherein:

the hard coat layer having a concavo-convex shape does not contain inorganic particles or organic particles.

5. The antiglare laminate according to any one of claims 1 to 4, wherein:

the hard coat layer having a concavo-convex shape has at least 1 characteristic of antireflection performance, antifouling performance, antistatic performance and weather resistance.

6. The antiglare laminate according to any one of claims 1 to 5, wherein:

and a second hard coat layer on the surface opposite to the hard coat layer having the irregularities.

7. The antiglare laminate according to any one of claims 1 to 6, wherein:

the second hard coat layer has at least 1 characteristic among antireflection performance, antifouling performance, antistatic performance and weather resistance.

8. The antiglare 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 the formula (5), 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, 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. An in-vehicle display device, comprising:

the antiglare laminate according to any one of claims 1 to 8.

10. A touch panel front protection plate, comprising:

the antiglare laminate according to any one of claims 1 to 8.

11. A front panel for OA equipment, portable electronic equipment or television, comprising: the antiglare laminate according to any one of claims 1 to 8.

12. A method for producing an antiglare laminate according to any one of claims 1 to 8, the method comprising:

and a step of pressure-bonding a patterned PET film onto the photocurable resin composition on the layer containing the high-hardness resin (B), thereby transferring the uneven shape to the hard coat layer.

Technical Field

The present invention relates to an antiglare laminate. More specifically, the present invention relates to an antiglare laminate which has excellent impact resistance, heat resistance and antiglare property, can suppress the occurrence of glare (glare), has high scratch resistance and excellent shape stability, and can be used as a front panel in a liquid crystal display device for vehicle use, a mobile phone terminal, a personal computer, and a tablet personal computer.

Background

The liquid crystal display device is provided with a front panel for the purpose of protecting the liquid crystal panel and the like. 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 containing a polycarbonate resin has been used as a front panel from the viewpoint of having high impact resistance, heat resistance, secondary processability, light weight, transparency, and the like. In particular, a front panel obtained by laminating an acrylic resin on a surface layer of a polycarbonate resin sheet and applying a hard coat layer to a multilayer sheet has surface hardness and scratch resistance comparable to those of conventional acrylic resins with a hard coat layer, and also 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 is a laminate in which reflection of an image is suppressed or reflectance is reduced by scattering or interference of light.

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 anti-glare film can scatter external light by the uneven shape of the surface, and prevent the reduction of visibility caused by reflection of external light or reflection of images. 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 scratched during handling.

In order to prevent reflection of an external scene on a display surface of a liquid crystal display device, an organic Electroluminescence (EL) display device, or the like, in general, a mixture of fine particles and a binder resin or a curable resin is applied to a substrate to form fine irregularities on the surface, thereby preventing regular reflection and exhibiting antiglare properties. However, in a high-definition display device having a small pixel size, image quality such as image glare and character blurring is degraded in a conventional surface irregularity size. That is, in the case of a high-definition display device, the size of the surface irregularities in the related art is similar in order of magnitude to the pixel size of high-definition display, and glare is generated by the lens effect due to the surface irregularities. With the conventional particle size, scattering near the straight-ahead transmitted light increases, the outline of the pixel becomes unclear, and blurring of characters occurs. The intensity distribution of the transmitted scattered light depends on the size of the added fine particles, and when the size of the added fine particles is small, scattering around the straight-ahead transmitted light is reduced, and flare is reduced.

In order to solve these problems, attempts have been made to control the surface roughness by reducing the size of the added fine particles or by using fine particles having a concentrated particle size distribution. However, in these methods, it is necessary to control the position of the center of gravity of the fine particles in order to prevent glare and character blurring. Further, since the uneven shape of the surface is small, it is difficult to achieve sufficient antiglare properties at the same time, and there is a disadvantage in terms of cost.

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

Jp 2001-215307 a (patent document 1) discloses an anti-glare layer in which transparent fine particles having an average particle diameter of 15 μm or less are contained in a film having a thickness of 2 times or more the average particle diameter, and in which the transparent fine particles are present on the side contacting the air in the film to form a fine uneven structure on the surface. However, in the anti-glare layer, the intensity distribution of the transmitted scattered light is controlled by the particle size, and thus glare on the display surface cannot be effectively prevented. In addition, since the particles are added, the abrasion resistance is lowered due to the falling-off of the particles.

As described above, there has not been a front panel for a liquid crystal display device for vehicle mounting, a mobile phone terminal, a personal computer, or a tablet personal computer, which has excellent impact resistance, heat resistance, and antiglare property, can suppress the occurrence of glare, has high abrasion resistance, and has excellent shape stability.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2001-215307

Disclosure of Invention

Technical problem to be solved by the invention

The invention provides an anti-glare laminate which has excellent impact resistance, heat resistance and anti-glare performance, can inhibit the generation of sparkle, has high scratch resistance and has 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 comprising a high-hardness resin (B) provided on at least 1 surface of the layer comprising the resin (a) comprising the polycarbonate resin (a 1); and

a hard coat layer having a concavo-convex shape 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 [ 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) the laminate has a haze of 15% or more as defined in JIS K7136, a reflection resolution of 30% or less as measured at a light incidence angle of 45 ℃ using a 2.0mm wide comb, and an average luminance of 2.0 or less as measured by a luminance standard deviation/evaluation range as measured by Prometoric Y29 manufactured by Konika Menten on a 265ppi light source.

< 2 > the antiglare laminate according to the above < 1 >, wherein the high-hardness resin (B) comprises any one of the following resins (B1) to (B4),

the resin (B1) is a copolymer resin comprising 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) is a resin comprising 55 to 10 mass% of a resin (C) containing a vinyl monomer and 45 to 90 mass% of a styrene-unsaturated dicarboxylic acid copolymer (D) comprising 50 to 80 mass% of a styrene monomer unit (D1), 10 to 30 mass% of an unsaturated dicarboxylic acid monomer unit (D2) and 5 to 30 mass% of a vinyl monomer unit (D3),

the resin (B3) is a resin copolymer (G) comprising 5 to 20 mass% of a styrene structural unit, 70 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 resin copolymer (D),

the above resin (B4) is a copolymer comprising a structural unit (H) represented by the following general formula (3) and optionally comprising a structural unit represented by the following general formula (4),

< 3 > the anti-glare laminate according to the above < 1 > or < 2 >, wherein the ratio of the angle of 5 ° or less in the inclination angle distribution of the above-mentioned uneven shape measured using a white interference microscope VS-1000 manufactured by hitachi high tech is 65 to 80%.

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

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

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

< 7 > the anti-glare laminate according to any one of the above < 1 > to < 6 >, wherein the second hard coat layer has at least 1 characteristic selected from the group consisting of an anti-reflection performance, an anti-fouling performance, an anti-static performance and a weather resistance.

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

< 10 > a front protective plate for a 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 > a method for producing an antiglare laminate, the method comprising: and (c) a step of transferring the uneven 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).

Detailed Description

The present invention will be described in detail below by way of examples of production examples and examples, but the present invention is not limited to the examples of production and examples, and can be modified in any manner without departing from the scope of the present invention.

The antiglare laminate (hereinafter, sometimes referred to as "resin sheet") of the present invention has a layer (hereinafter, sometimes referred to as "high-hardness resin layer" or "high-hardness layer") comprising a high-hardness resin composition (B) and a hard coat layer having irregularities, on at least 1 surface of a layer (hereinafter, sometimes referred to as "base layer") comprising a resin (a) containing a polycarbonate resin (al). The substrate layer may be a layer formed of a resin (a) containing a polycarbonate resin (al). The high-hardness layer may be a layer formed of the high-hardness resin composition (B).

In the order of lamination, the high-hardness layer is present between the base material layer and the hard coat layer, and gives a concave-convex shape to the outermost surface of the hard coat layer which is the outermost surface layer. The other surface of the layer containing the resin (a) containing the polycarbonate resin (al) is not particularly specified, and both or either of the high-hardness resin layer and the hard coat layer may be provided.

In the case where the high-hardness resin layer is provided on both surfaces of the base layer, it is more preferable to use the same high-hardness resin composition (B) on both surfaces in view 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 improved.

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

Hereinafter, each constituent material 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 weight or more, but since the impact resistance is improved by increasing the content, it is preferably 90% by weight or more, more preferably 100% by weight.

The polycarbonate resin (al) is not particularly limited as long as it contains a carbonate bond in the molecular main chain, that is, contains a unit of- [ O-R-OCO ] (R is a group having a linear structure or a branched structure and containing an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group), and a polycarbonate resin containing a structural unit of the following formula (3) is particularly preferably used.

By using such a polycarbonate resin, a resin laminate having excellent impact resistance can be obtained.

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

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

(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, 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. )

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. )

R in the general formula (5) or the general formula (6)₁More preferably within a specific numerical range. 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 (c) is preferably 8, more preferably 12.

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

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

On the other hand, if in the formula (5) or in the formula (6)R₁If the number of carbon atoms of (2) is too large, the solubility of the monohydric phenol (end terminator) in the organic solvent may be lowered, and the productivity in the production of the polycarbonate resin may be lowered.

As an example, if R₁When the number of carbon atoms of (2) is 36 or less, the productivity is high and the economical efficiency is good in the production of a polycarbonate resin. If R is₁When the number of carbon atoms of (2) is 22 or less, the monophenol, particularly, the organic solvent, has excellent solubility, and the productivity and the economy can be particularly improved in the production of a polycarbonate resin.

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

In the present invention, the weight average molecular weight of the polycarbonate resin (al) affects the impact resistance and molding conditions of the synthetic resin laminate. That is, when the weight average molecular weight is too small, the impact resistance of the synthetic resin laminate is undesirably lowered. When the weight average molecular weight is too high, an excessive heat source may be necessary when laminating the layer containing the polycarbonate resin (al), which is not preferable. In addition, since a high temperature is required in the molding method, the polycarbonate resin (al) is exposed to a high temperature, and the thermal stability thereof may be adversely affected. 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, as measured by Gel Permeation Chromatography (GPC), as described in examples below.

The resin (a) may further contain additives and the like. As the additive, an additive generally used in a resin sheet can be used. Examples of the additives include antioxidants, stainblocker agents, 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 whole amount, a method of dry-blending the base particles, a method of dry-blending the whole amount, and the like can be used. The amount of the additive is preferably 0 to 10 mass%, more preferably 0 to 7 mass%, and particularly preferably 0 to 5 mass% with respect to the total mass of the base material layer.

The thickness of the resin (A) is preferably 0.3 to 10mm, more preferably 0.3 to 5mm, and particularly preferably 0.3 to 3.5 mm.

(high-hardness resin composition (B))

The high-hardness resin composition (B) used in the present invention is 1 selected from the group consisting of the resin composition (B1), the resin composition (B2), the resin composition (B3) and the resin composition (B4).

< resin composition (B1) >)

The resin composition (B1) used in the present invention is a copolymer resin comprising 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 a linear, branched, and cyclic group, 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.

As the aliphatic vinyl structural unit (b) represented by the above general formula (2), for example, R3 is a hydrogen atom or a methyl group, and more preferably a hydrogen atom. Preferably, R4 is a structural unit of a cyclohexyl group or a cyclohexyl group having a hydrocarbon group having 1 to 4 carbon atoms. Among the above aliphatic vinyl structural units (b), more preferred is an aliphatic vinyl structural unit wherein R3 is a hydrogen atom and R4 is a cyclohexyl group.

The resin composition (B1) may contain 1 or 2 or more of the above (meth) acrylate structural units (a), and 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 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 whole 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 containing an aromatic double bond that is not hydrogenated, 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 resin (B1). When the proportion of the (meth) acrylate structural unit (a) to the total structural units in the resin (B1) is 65 mol% or more, a resin layer having excellent adhesion to the base material layer and surface hardness can be obtained. When the amount is 80 mol% or less, warpage due to water absorption of the resin sheet is less likely to occur.

The content of the aliphatic vinyl structural unit (B) represented by the general formula (2) is preferably 20 to 35 mol%, and more preferably 20 to 30 mol%, based on the total structural units in the resin (B1). If 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 if it is 35 mol% or less, peeling at the interface with the substrate can be prevented.

In addition, in the present specification, the "copolymer" may have any structure of random, block and alternating copolymers.

The method for producing the resin composition (B1) is not particularly limited, and a method in which at least 1 (meth) acrylate monomer and at least 1 aromatic vinyl monomer are polymerized, and then the aromatic double bond derived from the aromatic vinyl monomer is hydrogenated to obtain the resin composition (B1) is preferred. Wherein, (meth) acrylic acid represents 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. Preferred among these is styrene.

The polymerization of the (meth) acrylate monomer and the aromatic vinyl monomer can be carried out by a known method, and can be produced by, for example, bulk polymerization, solution polymerization, or the like. The bulk polymerization method is carried out by a method of continuously supplying a monomer composition comprising the monomer and a polymerization initiator to a complete mixing tank and continuously polymerizing 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 tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, 1-bis (tert-hexylperoxy) -3, 3, 5-trimethylcyclohexane, 1-bis (tert-hexylperoxy) cyclohexane, 1-bis (tert-butylperoxy) cyclohexane, tert-hexylpropoxyiisopropyl monocarbonate, tert-amyl peroxy-n-octanoate, tert-butylperoxyisopropyl monocarbonate, organic peroxides such as di-tert-butyl peroxide, azo compounds such as 2,2 ' -azobisisobutyronitrile, 2 ' -azobis (2-methylbutyronitrile), 2 ' -azobis (2, 4-dimethylvaleronitrile), and the like. These may 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 for 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 polymerization solvent described above. 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.

As described above, the resin composition (B1) used in the present invention can be obtained by polymerizing the (meth) acrylate monomer and the aromatic vinyl monomer 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 method under the conditions of a hydrogen pressure of 3 to 30MPa and a reaction temperature of 60 to 250 ℃. By setting the temperature to 60 ℃ or higher, the reaction time is not excessively consumed, and by setting the temperature to 250 ℃ or lower, the occurrence of molecular chain cleavage and hydrogenation of ester sites is less likely.

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

The resin composition (B1) preferably has 70% or more of the aromatic double bonds derived from the aromatic vinyl monomer 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. If the content exceeds 30%, the transparency of the resin composition (B1) may be lowered. The proportion of the unhydrogenated portion is more preferably in a range of less than 10%, and still more preferably in a range of less than 5%.

The weight average molecular weight of the resin composition (B1) is not particularly limited, but is preferably 50,000 to 400,000, and 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), as described in examples below.

Other resins may be blended in the resin composition (B1) within a range not to impair the transparency. Examples thereof include methyl methacrylate-styrene copolymer resins, polymethyl methacrylate, polystyrene, polycarbonate, cycloolefin (co) polymer resins, acrylonitrile-styrene copolymer resins, acrylonitrile-butadiene-styrene copolymer resins, and various elastomers.

The glass transition temperature of the resin composition (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 heat environment, and when the glass transition temperature is 140 ℃ or lower, the laminate 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. The glass transition temperature in the present invention is a temperature at which a sample 10mg and a temperature rise rate of 10 ℃/min are measured using a differential scanning calorimetry measuring apparatus, and calculated by a midpoint method.

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

< resin composition (B2) >)

The resin composition (B2) used in the present invention is a resin composition comprising 55 to 10 mass% (preferably 50 to 20 mass%) of a resin (C) containing a vinyl monomer and 45 to 90 mass%, preferably 50 to 80 mass% of a styrene-unsaturated dicarboxylic acid copolymer (D), wherein the styrene-unsaturated dicarboxylic acid copolymer (D) comprises 50 to 80 mass% of a styrene monomer unit (D1), 10 to 30 mass% of an unsaturated dicarboxylic anhydride monomer unit (D2), and 5 to 30 mass% of a vinyl monomer unit (D3).

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

< resin (C) containing a vinyl monomer >

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

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

The styrene-unsaturated dicarboxylic acid copolymer (D) used in the present invention comprises a styrene-based monomer unit (D1), an unsaturated dicarboxylic anhydride monomer unit (D2), and a vinyl-based monomer unit (D3).

< styrene-based monomer Unit (d1) >)

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 (d2) >)

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 (d3) >)

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 (C), 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 (D) >

The composition ratio of the styrene-unsaturated dicarboxylic acid copolymer (D) is 50 to 80 mass% (preferably 50 to 75 mass%) of the styrene monomer unit (D1), 10 to 30 mass% (preferably 10 to 25 mass%) of the unsaturated dicarboxylic anhydride monomer unit (D2), and 5 to 30 mass% (preferably 7 to 27 mass%) of the vinyl monomer unit (D3).

The weight average molecular weight of the styrene-unsaturated dicarboxylic acid copolymer (D) 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 (C) is good, and the effect of improving heat resistance is excellent. The weight average molecular weights of the resin (C) and the copolymer (D) are weight average molecular weights in terms of standard polystyrene measured by Gel Permeation Chromatography (GPC) as described in examples described later.

Specific examples of the resin copolymer (D) include Rejisufai (レジスファイ) R100, R200, R310 (manufactured by the electric chemical industry Co., Ltd.), Delpet 980N (manufactured by Asahi Chemicals Co., Ltd.).

< resin composition (B3) >)

The resin composition (B3) used in the present invention is a resin copolymer (G) comprising 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 resin copolymer (D).

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 used from the viewpoint of compatibility with an acrylic resin. These N-substituted maleimide monomers may be mixed in 2 or more. The content of the N-substituted maleimide structural unit is 5 to 20% by mass, preferably 5 to 15% by mass, and preferably 5 to 10% by mass, based on the total amount of the resin composition (B3).

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% by mass, preferably 5 to 15% by mass, and more preferably 5 to 10% by mass, based on the total mass of the resin (B3).

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 particularly, methyl methacrylate is preferable as the monomer unit. Further, a copolymer containing 2 or more of the monomer units may be used.

The content of the (meth) acrylate structural unit is 60 to 90% by mass, preferably 70 to 90% by mass, and more preferably 80 to 90% by mass, based on the total mass of the resin composition (B3).

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.

< resin composition (B4) >)

The resin composition (B4) is a copolymer containing a structural unit (H) represented by the following general formula (3) and optionally containing a structural unit (J) represented by the following general formula (4). The resin composition (B4) may or may not include the structural unit (J), and preferably includes the structural unit (J).

The proportion of the structural unit (H) in the total structural units of the resin composition (B4) 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 resin composition (B4) 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 resin composition (B4).

The resin composition (B4) 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 resin composition (B4).

Examples of the other structural unit include a structural unit represented by the following general formula (4).

The method for producing the resin composition (B4) 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 resin composition (B4) include, but are not limited to, Iupilon KH3410UR, KH3520UR, and KS3410UR (manufactured by mitsubishi engineering plastics corporation).

The weight average molecular weight of the resin composition (B4) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000, and particularly preferably 25,000 to 65,000.

The resin compositions (B1) to (B4) may contain additives and the like. As the additive, an additive generally used in a resin sheet 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. The method of mixing the additive and the resin is not particularly limited, and a method of mixing the whole amount, a method of dry-blending the base particles, a method of dry-blending the whole amount, and the like can be used. The amount of the additive is preferably 0 to 10 mass%, more preferably 0 to 7 mass%, and particularly preferably 0 to 5 mass% with respect to the total mass of the base material layer.

The thickness of the high-hardness resin layer affects the surface hardness and impact resistance. That is, if the high-hardness resin layer is too thin, the surface hardness becomes low, and if it is too thick, the impact resistance becomes low. 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 other layers 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 method of laminating the layers is not particularly limited, and the layers may be similarly laminated even when other layers are 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 substrate layer by in-mold molding on the high-hardness resin layer formed in advance. Among these, the coextrusion molding method 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 in 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 mold, and the resulting material is extruded into a sheet form, and then cooled while passing through a forming roll to form a desired laminate.

The total thickness of the substrate layer and the high-hardness resin layer is preferably 0.5 to 3.5mm, more preferably 0.5 to 3.0mm, and particularly preferably 1.2 to 3.0 mm. By setting the total thickness to 0.5mm or more, the rigidity of the sheet can be maintained. Further, by setting the thickness to 3.5mm or less, it is possible to prevent deterioration of the sensitivity of the touch sensor when the touch panel is set under the 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%. By setting the above range, both hardness and impact resistance can be achieved.

(hard coating)

The anti-glare 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, and 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, the "acrylic hard coat layer" refers to a coating film formed by polymerizing a monomer or oligomer or prepolymer containing a (meth) acryloyl group as a polymerizable group to form a crosslinked structure. The composition of the acrylic hard coat layer preferably contains 2 to 98 mass% of a (meth) acrylic monomer, 2 to 98 mass% of a (meth) acrylic oligomer, and 0 to 15 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 more preferably contains 5 to 50 mass% of a (meth) acrylic monomer, 50 to 95 mass% of a (meth) acrylic oligomer, and 1 to 10 mass% of a surface modifier, and particularly preferably contains 20 to 40 mass% of a (meth) acrylic monomer, 60 to 80 mass% of a (meth) acrylic oligomer, and 2 to 5 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, glyceryl 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 include 1 or more than 2 (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 include 1 or more than 2 (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 with polyisocyanates and (meth) acrylate monomers having at least 1 or more (meth) acryloyloxy groups and hydroxyl groups in 1 molecule.

Examples of the (meth) acrylate monomer having at least 1 (meth) acryloyloxy group and hydroxyl group in 1 molecule used in the urethane-forming reaction include 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, and dipentaerythritol penta (meth) acrylate.

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

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

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 a polyoxyalkylene-modified polyol obtained by reacting the above polyol or phenol with an alkylene oxide, in addition to the polyalkylene glycol.

In addition, the polyfunctional polyester (meth) acrylate oligomer is obtained by a dehydration condensation reaction using (meth) acrylic acid, a polycarboxylic acid, and a polyol. Examples of 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 is obtained by addition reaction of a 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 leveling agent, an antistatic agent, a surfactant, a water and oil repellent agent, a UV absorber, or the like capable of changing the properties of the hard coat layer.

Examples of the leveling agent include polyether-modified polyalkylsiloxane, polyether-modified siloxane, polyalkylsiloxane containing a polyester-modified hydroxyl group, polyether-modified polydimethylsiloxane having an alkyl group, 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 fluorine groups and lipophilic groups and oligomers containing fluorine groups, hydrophilic groups, lipophilic groups and UV reactive groups.

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: merck Co. ]; α -hydroxy- α, α' -dimethylacetophenone [ DAROCUR 1173: merck Co. ]; 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; others, halogenated ketones, acyl phosphine oxides, acyl phosphonates, 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 subjecting the layer to photopolymerization.

The method for applying the hard coat paint in the present invention is not particularly limited, and a known method can be used. Examples of the coating method include spin coating, dip coating, spray coating, slide coating, bar coating, roll coating, gravure coating, meniscus coating, flexographic printing, screen printing, beating coating (brush coating method), and brush coating.

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 them, a high-pressure mercury lamp or a metal halide lamp is preferable because it efficiently emits light in the active wavelength region of the initiator, and does not emit a large amount of light of a short wavelength at which the viscoelastic property of the resulting polymer is reduced by crosslinking and light of a long wavelength at which the reaction composition is evaporated by heating.

The irradiation intensity of the lamp is a factor affecting the degree of polymerization of the resulting polymer, and is appropriately controlled for each property 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。

The photopolymerization reaction is inhibited by oxygen in the air or oxygen dissolved in the reactive composition. Therefore, it is desirable to perform light irradiation by a method capable of eliminating reaction inhibition by oxygen. One of such methods is: a method in which the reactive composition is covered with a film made of polyethylene terephthalate or teflon, contact with oxygen is blocked, and light is irradiated to the reactive composition through the film. In addition, the composition may be irradiated with light through a light-transmissive window in an inert atmosphere in which oxygen is replaced with an inert gas such as nitrogen or carbon dioxide.

In the case of performing light irradiation 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, in terms of the relative velocity with respect to 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 by the gas flow can be substantially suppressed.

For the purpose of improving 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 hard coat layer had an output of 20mW/cm under irradiation with UV light (254nm)²In the case of irradiating the metal halide lamp with ultraviolet rays, 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. When the film thickness is 1 μm or more, sufficient hardness can be obtained. Further, the film thickness of 40 μm or less can suppress the occurrence of cracks during bending. 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 distance from the interface to the surface of the coating film.

In one embodiment of the present invention, the hard coat layer having the concavo-convex shape may have at least 1 characteristic of antireflection performance, antifouling performance, antistatic performance and weather resistance. The hard coat layer is not particularly limited in treatment methods such as antireflection treatment, antifouling treatment, antistatic treatment, and weather resistance treatment, and known methods can be used. For example, a method of applying a reflection reducing coating material, a method of depositing a dielectric thin film, a method of applying an antistatic coating material, and the like can be cited.

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 substrate coated with the hard coating layer with ultraviolet rays in close contact therewith.

In order to suppress reflection of an image, the uneven shape of the present invention preferably has a haze of 15% or more as defined in JIS K7136 and a reflection resolution of 30% or less as measured at a light incident angle of 45 ° using a 2.0mm wide optical comb. The light incident surface in the measurement of haze was opposite to the surface having irregularities. The reflection clarity can be measured by sticking a black tape on the back surface of the uneven surface to suppress back surface reflection.

In addition, in the inclination angle distribution of the uneven shape measured by using a white microscope VS-1000 manufactured by hitachi high and new technology co., ltd, the proportion of angles of 5 ° or less is large, and the regular reflection light increases and the reflection of the image is likely to occur, so the proportion of angles of 5 ° or less of the inclination angle distribution is preferably 65 to 80%.

In the present invention, the hard coat layer having the concavo-convex shape does not contain inorganic particles or organic particles. The concave-convex shape of the present invention is provided by transfer. In this way, the hard coat layer does not contain inorganic particles or organic particles, and the scratch resistance can be improved.

Another embodiment of the present invention provides a method for producing the antiglare laminate, comprising: and a step of transferring the uneven shape to the hard coat layer by pressure-bonding the patterned PET film with a photocurable resin composition on the layer containing the high-hardness resin (B). As the PET film with a pattern, for example, PTH, PTHA, and PTHZ, manufactured by Unitika, Emblet, PF11, PF23, manufactured by Daicel, and the like, can be used.

Examples

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

< haze >

The haze was calculated by the method specified in JIS K7136 using "HR-100" manufactured by village color Co., Ltd.

< reflection definition (imaging) >

The measurement was performed by using an ICM 1T manufactured by Shiga tester, JIS K7374, and by arranging the optical laminate so that the traveling direction of the optical laminate was parallel to the comb tooth direction of the optical comb. The optical comb used a 2.0mm optical comb, and the reflected image clarity measured at a light incident angle of 45 ° was taken as the reflection clarity. The measurement was carried out by attaching a black tape (model 117BLA of black vinyl tape manufactured by 3M japan) to the back surface of the uneven surface to suppress back surface reflection.

< sparkle >

For glare, an antiglare laminate was placed on 265ppi iPad6 showing green (R: 29, G: 205, B: 0) in such a manner that the uneven shape was upward, and an image was taken using PrometricY29 manufactured by konica minolta, and then 60mm × 60mm was selected from the image. The selected image was divided into 9 parts using the Random Mura Sequence of the analysis software "True Test", and the degree of glare was calculated as "(display) luminance standard deviation/average luminance of evaluation range" in each of the areas divided into 9 parts. The average of the blaze degrees calculated for each of the 9 regions is preferably 2.0 or less when used as a front panel. The distance between the lens and the antiglare laminate was 500 mm.

A method of calculating the flare degree: average luminance of standard deviation of (display) luminance/evaluation range

Sparkle degree: good quality of 2.0 or less

Sparkle degree: blaze greater than 2.0

< Angle of inclination >

White interference microscope VS-1000 manufactured by Hitachi high and new technology is used, and calculation is carried out according to the measured inclination angle distribution.

Hardness of SW

The visual observation was carried out using a steel wool # 0000 at 100g/cm²The case of the flaw when the load was reciprocated 15 times was evaluated in 10 stages. Are described as RANK1 to RANK 10. RANK 1: inorganic glass (non-marred) RANK 10: polycarbonate (mass scar)

< shape stability >

The test piece was cut into pieces of 100mm by 60 mm. The cut test piece was placed on a 2-point support type holder, and put into an environmental testing machine set at a temperature of 23% and a relative humidity of 50% for 24 hours or more, and after conditioning, the warpage was measured (before processing). Then, the test piece was set on a holder, and the test piece was 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. Subsequently, the stent was transferred to an environmental tester set to 23% of temperature and 50% of relative humidity, and the state was maintained for 4 hours, and then warpage (after treatment) was measured again. The warpage was measured by using a three-dimensional shape measuring machine (KS-1000, manufactured by KEYENCE) having an electric stage, horizontally setting the taken-out test piece in a convex state, scanning the test piece at 1 mm intervals, and measuring the bulge at the center as the warpage. The absolute value of the difference between the amounts of warpage before and after the treatment, i.e., | (amount of warpage after the treatment) - (amount of warpage before the treatment) | was evaluated as the shape stability.

Example 1

< laminate (X-1) >

The synthetic resin laminate was molded 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, made by Mitsubishi gas chemical, as a high hardness resin (B1) was continuously introduced into a single screw extruder having an axial diameter of 35mm, and extruded under conditions of a cylinder temperature of 240 ℃ and a discharge speed 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 had 2 kinds of 2-layer distribution pins, and the high hardness resin and the polycarbonate resin were introduced at a temperature of 270 ℃ and laminated. The sheet was extruded through a T die connected to the tip thereof at a temperature of 270 ℃ and cooled while transferring the mirror surface with 3 mirror-finished rolls set at a temperature of 120 ℃, 130 ℃ and 190 ℃ from the upstream side, to obtain a resin laminate (X-1) comprising a high-hardness resin layer and a polycarbonate resin layer. The thickness of the laminate was 1.0mm, and the thickness of the high-hardness resin (B1) layer was 60 μm in the vicinity of the center.

< photocurable resin composition (Y) >)

U6 HA: 60% by weight of a 6-functional urethane acrylate oligomer (available from Nomura chemical Co., Ltd.),

# 260: 35% by weight of 1, 9-nonanediol diacrylate (manufactured by Osaka organic chemical Co., Ltd.),

A mixture of 5 wt% of the fluorine-based leveling agent was used as 100 parts by weight

Photoinitiator: 3 parts by weight of I-184 (product name: 1-hydroxy-cyclohexylphenylketone, manufactured by BASF corporation) was added to obtain a photocurable resin composition (Y).

< patterned PET film (Z-1) >)

As a PET film for transferring an uneven shape, PS 27-1 manufactured by Daicel was used.

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

Example 2

An antiglare laminate was obtained in the same manner as in example 1, except that PS 27-2 (Z-2) manufactured by Daicel was used for the PET film with a pattern.

Example 3

An antiglare laminate was obtained in the same manner as in example 1, except that PS 27-3 (Z-3) manufactured by Daicel was used for the PET film with a pattern.

Example 4

Production of < high hardness resin (B2) >

A resin composition (B2) was obtained in the same manner as in production example 5, except that R-100 was 75% by mass as the styrene-unsaturated dicarboxylic acid copolymer (D) and the methyl methacrylate resin Parapet HR-L was 25% by mass as the vinyl monomer-containing resin (C). The pellets can be stably produced.

< laminate (X-2) >)

The synthetic resin laminate was molded 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. 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 E-2000, 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 had 2 kinds of 2-layer distribution pins, and the high hardness resin and the polycarbonate resin were introduced at a temperature of 270 ℃ and laminated. The sheet-like laminate was extruded through a T die connected to the tip thereof at a temperature of 270 ℃ and cooled while transferring the mirror surface with 3 mirror-finished rolls set at temperatures of 120 ℃, 130 ℃ and 190 ℃ from the upstream side, to obtain an antiglare laminate of a high-hardness resin layer and a polycarbonate resin layer. The thickness of the laminate was 1.0mm, and the thickness of the high-hardness resin (B2) layer was 60 μm in the vicinity of the center.

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

Example 5

An antiglare laminate was obtained in the same manner as in example 4, except that PS 27-2 (Z-2) manufactured by Daicel was used for the PET film with a pattern.

Example 6

An antiglare laminate was obtained in the same manner as in example 4, except that PS 27-3 (Z-3) manufactured by Daicel was used for the PET film with a pattern.

Example 7

Production of < high hardness resin (B3) >

A resin copolymer (D) was prepared by adding 75% by mass of a copolymer (Rejisufai R100 (manufactured by Denka)) comprising 21% by mass of a methyl methacrylate structural unit, 64% by mass of a styrene structural unit and 15% by mass of a maleic anhydride structural unit, adding 25% by mass of a copolymer Delpet PM-120N (manufactured by Asahi Chemicals) comprising 7% by mass of a styrene structural unit, 86% by mass of a methyl methacrylate structural unit and 7% by mass of an N-phenylmaleimide structural unit, mixing the mixture with a mixer for 30 minutes, and then melt-kneading the mixture at a cylinder temperature of 230 ℃ using an extruder (manufactured by Toshiba machine, TEM-26 SS, L/D. apprxeq.40) having a screw diameter of 26mm, extruding the mixture in a strand form, and pelletizing the mixture with a pelletizer to obtain a resin composition (B3). The granulation is carried out stably.

< laminate (X-3) >)

The synthetic resin laminate was molded 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. 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 E-2000, 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 had 2 kinds of 2-layer distribution pins, and the high hardness resin and the polycarbonate resin were introduced at a temperature of 270 ℃ and laminated. The resin laminate was extruded in a sheet form using a T die connected to the tip thereof at a temperature of 270 ℃ and cooled while transferring the mirror surface with 3 mirror-finished rolls set at temperatures of 120 ℃, 130 ℃ and 190 ℃ from the upstream side, to obtain a resin laminate of a high-hardness resin layer and a polycarbonate resin layer. The thickness of the laminate was 1.0mm, and the thickness of the high-hardness resin (B3) layer was 60 μm in the vicinity of the center.

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

Example 8

An antiglare laminate was obtained in the same manner as in example 7, except that PS 27-2 (Z-2) manufactured by Daicel was used for the PET film with a pattern.

Example 9

An antiglare laminate was obtained in the same manner as in example 7, except that PS 27-3 (Z-3) manufactured by Daicel was used for the PET film with a pattern.

Example 10

Production of < high hardness resin (B4) >

A copolymer (Rejisufai R100 (manufactured by Denka)) of 21 mass% of a methyl methacrylate structural unit, 64 mass% of a styrene structural unit, and 15 mass% of a maleic anhydride structural unit (Delpet PM 120N; manufactured by Asahi Chemicals) and a copolymer (Delpet PM 120N; manufactured by Asahi Kasei) of 25 mass% of a styrene structural unit, 86 mass% of a methyl methacrylate structural unit, and 7 mass% of an N-phenylmaleimide structural unit (manufactured by Toshiba machinery) were introduced into an extruder (TEM-26 SS, L/D. apprxeq.40; manufactured by Toshiba machinery) having a screw diameter of 26mm, and melt-kneaded at 240 ℃ to obtain a high-hardness resin (B4).

< laminate (X-4) >)

The synthetic resin laminate was molded 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. KH3410UR made of Mitsubishi engineering plastic as a high-hardness resin (B4) was continuously introduced into a single-screw extruder having a shaft diameter of 35mm, and the mixture was extruded at a cylinder temperature of 240 ℃ and a discharge speed of 2.6 kg/hr. 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 had 2 kinds of 2-layer distribution pins, and the high hardness resin and the polycarbonate resin were introduced at a temperature of 270 ℃ and laminated. The resin laminate was extruded in a sheet form using a T die connected to the tip thereof at a temperature of 270 ℃ and cooled while transferring the mirror surface with 3 mirror-finished rolls set at temperatures of 120 ℃, 130 ℃ and 190 ℃ from the upstream side, to obtain a resin laminate of a high-hardness resin layer and a polycarbonate resin layer. The thickness of the laminate 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) is applied to the high-hardness resin layer of the laminate (X-4) by a bar coater so that the cured coating film thickness is 5 to 10 μm, and the laminate is covered and pressed so that the pattern surface of the patterned PET film (Z-1) comes into contact with the coating liquid. Then, a metal halide lamp (20mW/cm) was irradiated at a light source distance of 12cm for 30 seconds to cure the resin, and the patterned PET film was peeled off to obtain an antiglare laminate having a hard coat layer with irregularities on the high-hardness resin layer (B3).

Example 11

An antiglare laminate was obtained in the same manner as in example 10, except that PS 27-2 (Z-2) manufactured by Daicel was used for the PET film with a pattern.

Example 12

An antiglare laminate was obtained in the same manner as in example 10, except that PS 27-3 (Z-3) manufactured by Daicel was used for the PET film with a pattern.

Comparative example 1

An anti-glare laminate was obtained in the same manner as in example 1, except that PTH-50 (Z-4) manufactured by UNITIKA TRADING was used as the PET film having a pattern.

Comparative example 2

An antiglare laminate was obtained in the same manner as in example 1, except that the PET film with a pattern was changed to C-50G-100 (Z-5) manufactured by Ishikaki industries.

Comparative example 3

An antiglare laminate was obtained in the same manner as in example 1, except that the PET film with a pattern was changed to C-50G-30 (Z-6) manufactured by Ishikaki industries.

Comparative example 4

50 parts by mass of an acrylic ultraviolet-curable resin (100% solid content, product name: LIGHT ACRYLATE DPE-6A Kyoeisha chemical Co., Ltd.), 0.5 part by mass of silica fine particles (octylsilane-treated fumed silica, average primary particle diameter 12nm, product name: Japan Aerosil Co., Ltd.), 1 part by mass of acrylic silane-treated silica (average particle diameter 1.9 μm, product name: SE-6050-SYB Admatox Co., Ltd.), and 3 parts by mass of a photoinitiator (product name: Omnirad184IGM Resins) were mixed and stirred with MEK50 parts by mass to prepare a coating liquid (i). Then, an antiglare laminate was obtained in the same manner as in example 1 except that the coating liquid (i) was applied onto a PET (polyethylene terephthalate) film so that the dry film thickness was 2.5 μm, dried at 80 ℃ for 2 minutes, and then cured by irradiating ultraviolet light at a light source distance of 12cm using a conveyor belt equipped with a high-pressure mercury lamp with an output of 80W/cm at a linear speed of 1.5 m/min, and the thus-obtained patterned PET film (Z-7) was used.

Comparative example 5

A laminate was produced in the same manner as in example 1 except that a laminate (X-5) obtained using a methyl methacrylate resin Parapet HR-L (manufactured by Kuraray, weight average molecular weight: 90,000) in place of the high-hardness resin composition (B1) was used, and a hard coat layer was formed to obtain an antiglare laminate.

Comparative example 6

50 parts by mass of an acrylic ultraviolet-curable resin (100% solid content, product of LIGHT ACRYLATE DPE-6A Kyoeisha chemical Co., Ltd.), silica fine particles (octylsilane-treated gas phase method, average primary particle diameter 1.9 μm, product name: SE 6050-SYB Admatox Co., Ltd.), and 3 parts by mass of a photoinitiator (product name: Irgacure184, product of Toyotsu Chemiplas) were mixed and stirred with MEK 50% by mass to prepare a coating liquid. Then, the laminate (X-5) described in comparative example 5 was coated to a dry film thickness of 2.5 μm, dried at 80 ℃ for 2 minutes, and then cured by irradiating a metal halide lamp (20mW/cm) for 30 seconds while purging with nitrogen, to obtain an antiglare laminate.

The antiglare laminates obtained in examples 1 to 12 and comparative examples 1 to 6 were evaluated for haze, reflection clarity (image quality), glare, proportion of an inclination angle of 5 ° or less, SW hardness, and form stability. The results are shown in the following table.

[ Table 1]

As described above, according to the present invention, an antiglare laminate having excellent impact resistance, heat resistance, and antiglare properties, in which occurrence of glare can be suppressed, high scratch resistance, and excellent shape stability can be obtained.