JP2024040722A - Anti-glare laminate and its manufacturing method - Google Patents

Abstract

[Problem] To provide an anti-glare laminate having anti-glare performance that combines image reflection prevention performance and suppression of character blurring, high scratch resistance, and excellent shape stability, and a method for producing the same. [Solution] The above problem can be solved by an anti-glare laminate having a substrate layer containing at least a polycarbonate resin (a1), a high-hardness resin layer containing a high-hardness resin (B), and a hard coat layer arranged in this order, in which the developed interface area ratio (Sdr), arithmetic mean height (Sa), and autocorrelation length (Sal) of the hard coat layer satisfy the following formulas (i) to (iii): 0≦Sdr≦0.6 (i) 0≦Sa≦0.16 (ii) 0≦Sal≦15.0 (iii). [Selected Figure] None

Description

The present invention relates to an anti-glare laminate and a method for manufacturing the same. More specifically, the present invention provides front panels for vehicle-mounted liquid crystal display devices, mobile phone terminals, personal computers, and tablet PCs that have anti-glare performance, high scratch resistance, and excellent shape stability. The present invention relates to an anti-glare laminate used as an anti-glare laminate and a method for producing the same.

A liquid crystal display device is provided with a front plate for the purpose of protecting the liquid crystal panel and the like. Materials used for the front panel of conventional liquid crystal display devices include (meth)acrylic resins represented by polymethyl methacrylate (PMMA).

In addition, in recent years, sheets made of polycarbonate resin have been used as front plates because they have high impact resistance, heat resistance, secondary processability, light weight, and transparency. In particular, the front panel, which is made by applying a hard coat to a multilayer sheet in which acrylic resin is laminated on the surface layer of a polycarbonate resin sheet, has a surface hardness and scratch resistance comparable to that of conventional hard-coated acrylic resin, but is made of polycarbonate resin. It is widely used as a front plate because of its excellent impact resistance, heat resistance, workability, and transparency.

The front panel of a liquid crystal display device including the above-mentioned polycarbonate resin sheet is generally formed by a melt extrusion method 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 image reflection and reduces reflectance by scattering and interference of light.

As one type of antireflection optical laminate, an antiglare film is known in which an antiglare layer having an uneven shape is formed on the surface of a transparent base material. This anti-glare film can scatter external light due to the uneven shape of its surface, thereby preventing a decrease in visibility due to reflection of external light or image reflection. Further, since this optical laminate is usually installed on the outermost surface of a liquid crystal display device, it is also required to be provided with hard coating properties to prevent scratches during handling.

For display surfaces such as liquid crystal display devices and organic electroluminescence (EL) display devices, a mixture of fine particles and a binder resin or a curable resin is usually applied to a base material to form fine irregularities on the surface. Prevents specular reflection and prevents image glare. However, if a concave-convex shape is provided to prevent image reflection, the scattering of straight-progressing transmitted light increases, making the outline of the pixel vague and causing character blurring.

Additionally, if fine particles are added to create surface irregularities, the fine particles on the outermost surface will fall off during the scratch resistance test and act as an abrasive, resulting in a marked drop in scratch resistance compared to when no fine particles are added. Undesirable.

As mentioned above, the front panels of in-vehicle liquid crystal display devices, mobile phone terminals, personal computers, and tablet PCs have excellent impact resistance, heat resistance, and the ability to prevent image reflection while suppressing text blurring. There has not been a front plate that has excellent anti-glare properties, high scratch resistance, and excellent shape stability. In Patent Document 1, fine particles are added to improve the clarity of transmission and reduce blurring of characters. Addition of fine particles improves pencil hardness, but it is not preferable because it reduces scratch resistance.

JP2010-160398

An object of the present invention is to solve at least one of the above-mentioned conventional problems. Furthermore, the present invention provides an anti-glare laminate that has anti-glare performance that combines image reflection prevention performance and text blur suppression, high scratch resistance, and excellent shape stability, and its production. The task is to provide a method.

（式中、Ｒ^５は、炭素数８～３６のアルキル基、または炭素数８～３６のアルケニル基を表し、Ｒ^６はそれぞれ独立して、水素原子、ハロゲン、または置換基を有してもよい炭素数１～２０のアルキル基若しくは炭素数６～１２のアリール基を表し、ｎは０～４の整数であり、ここで、前記置換基は、ハロゲン、炭素数１～２０のアルキル基、または炭素数６～１２のアリール基である。）で表される１価フェノール由来の成分を含む、上記＜１＞～＜６＞のいずれかに記載の防眩性積層体。
＜８＞ 上記＜１＞～＜７＞のいずれかに記載の防眩性積層体を含む、車載用表示装置。
＜９＞ 上記＜１＞～＜７＞のいずれかに記載の防眩性積層体を含む、タッチパネル前面保護板。
＜１０＞ 上記＜１＞～＜７＞のいずれかに記載の防眩性積層体を含む、ＯＡ機器用、携帯電子機器用、またはテレビ用の前面板。
＜１１＞ 上記＜１＞～＜７＞のいずれかに記載の防眩性積層体の製造方法であって、
ハードコート層の表面に、柄目付きＰＥＴフィルムを圧着して凹凸形状を転写し、転写後のハードコート層が、下記式（i）～（iii）：
０≦Ｓｄｒ≦０．６ （i）
０≦Ｓａ≦０．１６ （ii）
０≦Ｓａｌ≦１５．０ （iii）
を満たすようにする工程を含む、前記製造方法。 The above problems can be solved by the following invention. That is, the present invention is as follows.
<1> An antiglare laminate in which a base layer containing at least a polycarbonate resin (a1), a high hardness resin layer containing a high hardness resin (B), and a hard coat layer are arranged in this order, The developed interface area ratio (Sdr), arithmetic mean height (Sa), and autocorrelation length (Sal) of the hard coat layer are expressed by the following formulas (i) to (iii):
0≦Sdr≦0.6 (i)
0≦Sa≦0.16 (ii)
0≦Sal≦15.0 (iii)
An anti-glare laminate that satisfies the following requirements.
<2> The developed interface area ratio (Sdr), arithmetic mean height (Sa), and autocorrelation length (Sal) of the hard coat layer are expressed by the following formulas (iv) to (vi):
0≦Sdr≦0.3 (iv)
0.03≦Sa≦0.13 (v)
3.0≦Sal≦8.0 (vi)
The antiglare laminate according to <1> above, which satisfies the following.
<3> The anti-glare laminate according to <1> or <2> above has a change in warpage of 350 μm or less after being kept in an environment with a temperature of 85° C. and a relative humidity of 85% for 120 hours. Anti-glare laminate.
<4> The antiglare laminate according to any one of <1> to <3> above, wherein the high hardness resin layer has a thickness of 10 to 250 μm.
<5> The antiglare laminate according to any one of <1> to <4> above, wherein the total thickness of the base layer and the high-hardness resin layer is 100 to 3,000 μm.
<6> The antiglare laminate according to any one of <1> to <5> above, wherein the hard coat layer does not contain organic particles or inorganic particles.
<7> The polycarbonate resin (a1) has the following general formula (5):

(In the formula, R ⁵ represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms, and each R ⁶ may independently have a hydrogen atom, a halogen, or a substituent. represents a good alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, n is an integer of 0 to 4, where the substituent is a halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.) The antiglare laminate according to any one of <1> to <6> above.
<8> An in-vehicle display device comprising the antiglare laminate according to any one of <1> to <7> above.
<9> A touch panel front protection plate comprising the antiglare laminate according to any one of <1> to <7> above.
<10> A front plate for office automation equipment, portable electronic equipment, or television, comprising the antiglare laminate according to any one of <1> to <7> above.
<11> A method for producing an antiglare laminate according to any one of <1> to <7> above, comprising:
A patterned PET film is pressed onto the surface of the hard coat layer to transfer the uneven shape, and the hard coat layer after the transfer has the following formulas (i) to (iii):
0≦Sdr≦0.6 (i)
0≦Sa≦0.16 (ii)
0≦Sal≦15.0 (iii)
The manufacturing method includes the step of satisfying the following.

According to the present invention, an anti-glare laminate that has anti-glare performance that combines image reflection prevention performance and text blur suppression, high scratch resistance, and excellent shape stability, and the production thereof method can be provided.

Hereinafter, the present invention will be explained in detail by illustrating manufacturing examples, examples, etc., but the present invention is not limited to the illustrated manufacturing examples, examples, etc., and within a range that does not significantly deviate from the content of the present invention. If so, you can change it to any method you like.

In the antiglare laminate of the present invention, a base layer containing at least a polycarbonate resin (a1), a high hardness resin layer containing a high hardness resin, and a hard coat layer are arranged in this order.

The order of lamination of the anti-glare laminate is preferably base layer - high hardness resin layer - hard coat layer. The other surface of the base material layer is not particularly specified. In one embodiment, a high hardness resin layer can be provided on the other side of the base layer. In this case, the antiglare laminate has a structure of a high hardness resin layer, a base material layer, a high hardness resin layer, and a hard coat layer. In one embodiment, a high hardness resin layer and a hard coat layer can be provided on the other surface of the base layer. In this case, the anti-glare laminate has a structure of hard coat layer-high hardness resin layer-substrate layer-high hardness resin layer-hard coat layer.

When high-hardness tree layers are provided on both sides of the base material layer, it is more desirable to use the same high-hardness tree layers on both sides for shape stability. Further, when providing hard coat layers on both sides of the base material, it is more desirable to provide similar hard coat layers on both sides because shape stability is improved. Note that the base material layer and the high-hardness resin layer, and the high-hardness resin layer and the hard coat layer may be laminated directly, or may be laminated via another layer, but they are not laminated directly. It is preferable.

In one embodiment, the anti-glare laminate is used, for example, as an in-vehicle display device such as a car navigation, a center information display (CID), a rear seat entertainment (RSE), a cluster, etc., a touch panel full protection plate, and an OA device, a mobile electronic device, etc. It can be used for equipment, TV front panels, etc. Further, for example, the front plate can be used alone as a front plate of a liquid crystal display device, but it may also be used in combination as a front plate, for example by laminating it with another substrate such as a touch sensor.

Each component of the anti-glare laminate according to the present invention will be explained below.

<Base material layer>
The base material layer contains polycarbonate resin (a1). The base material layer may further contain additives and the like.

[Polycarbonate resin (a1)]
The polycarbonate resin (al) has a carbonate ester bond in the main chain of the molecule, that is, a -[O-R-OCO]- unit (R is an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group). and may have a linear or branched structure), but is not particularly limited to polycarbonate resins containing the structural unit of the following formula (4). It is preferable to use By using such a polycarbonate resin, a resin laminate with excellent impact resistance can be obtained.

Specifically, as the polycarbonate resin (a1), aromatic polycarbonate resins (for example, manufactured by Mitsubishi Engineering Plastics, trade names: Iupilon S-2000, Iupilon S-1000, Iupilon E-2000), etc. can be used. However, it is not limited to this.

In addition, in recent years, there has been an increasing demand for bending the front panel, so it is preferable to use monohydric phenol represented by the following general formula (5) as the terminal capping agent for the polycarbonate resin (al). .

In the formula, R ⁵ represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms, and R ⁶ each independently represents a hydrogen atom, a halogen, or a carbon number that may have a substituent. represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, n is an integer of 0 to 4, and the substituent is a halogen, an alkyl group having 1 to 20 carbon atoms, or a carbon It is an aryl group of number 6 to 12. In addition, in this specification, an "alkyl group" and an "alkenyl group" may be linear or branched, and may have a substituent.

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

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

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

If the upper limit of the number of carbon atoms in R ⁵ in general formula (5) or general formula (6) is appropriate, the solubility of monohydric phenol (terminal capping agent) in organic solvents tends to increase, and when producing polycarbonate resin. This is preferable because it increases productivity.

As an example, if the number of carbon atoms in R ⁵ is 36 or less, productivity is high and economic efficiency is also good in producing polycarbonate resin. When the number of carbon atoms in R ⁵ is 22 or less, the monohydric phenol has particularly excellent solubility in organic solvents, and the productivity can be extremely high in producing polycarbonate resin, and the economic efficiency can also be improved.

If the lower limit of the number of carbon atoms in R ⁵ in general formula (5) or general formula (6) is appropriate, the glass transition point of the polycarbonate resin will not be too high, and it will have suitable thermoformability. preferable.

For example, when monohydric phenol (terminal stopper), which is an alkyl group having 16 carbon atoms, is used as R ⁵ in general formula (6), glass transition temperature, melt fluidity, moldability, drawdown resistance, polycarbonate resin Monohydric phenol has excellent solvent solubility during production, and is particularly preferred as a terminal capping agent for use in the polycarbonate resin in the present invention.

Among monohydric phenols (terminal capping agents) represented by general formula (5) or general formula (6), either or both of para-hydroxybenzoic acid hexadecyl ester and para-hydroxybenzoic acid 2-hexyldecyl ester is terminal-terminated. Particular preference is given to using it as an agent.

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

The number of polycarbonate resins (a1) contained in the base material layer may be one or two or more.

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

[Additive]
The base material layer may further contain an additive.

As additives, those commonly used in antiglare laminates can be used. Examples of additives include antioxidants, anti-coloring agents, antistatic agents, mold release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, organic fillers, and inorganic fillers. Examples include reinforcing materials such as

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 layer. .

The method of mixing the additive and the resin is not particularly limited, and methods such as a method of compounding the entire amount, a method of dry blending a masterbatch, a method of dry blending the entire amount, etc. can be used.

[Structure of base material layer]
The thickness of the base material layer is preferably 0.3 to 10 mm, more preferably 0.3 to 5 mm, and particularly preferably 0.3 to 3.5 mm.

<High hardness resin layer>
The high hardness resin layer contains high hardness resin. In addition, the high hardness resin layer may further contain additives and the like as necessary. By providing the high hardness resin layer between the base material layer and the hard coat layer, it is possible to obtain an antiglare laminate with high shape stability. Further, the high hardness resin layer may have a function of increasing the hardness of the anti-glare laminate. In addition, in this specification, a high-hardness resin is a resin with higher hardness than the polycarbonate resin used as a base material, and has a pencil hardness of HB or more, preferably HB to 3H, more preferably H to 3H, and even more preferably It means a 2H to 3H resin. Note that the pencil hardness of the high hardness resin layer is the result of evaluation by a pencil scratch hardness test based on JIS K 5600-5-4:1999. Specifically, a pencil is pressed against the surface of the high-hardness resin layer at an angle of 45 degrees under a load of 750 g with gradually increasing hardness, and the hardness of the hardest pencil that does not produce any scratch marks is evaluated as the pencil hardness.

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

(Resin (B1))
The resin (B1) contains a (meth)acrylic acid ester structural unit (a) represented by the following general formula (1) and an aliphatic vinyl structural unit (b) represented by the following general formula (2). It is a copolymer resin. At this time, the resin (B1) (copolymer resin) may further include other structural units. The total proportion of the (meth)acrylic acid ester structural unit (a) and the aliphatic vinyl structural unit (b) is 90 to 100 mol% of the total structural units of the copolymer resin, preferably 95 to 100 mol%. It is 100 mol%, more preferably 98 to 100 mol%. Further, the proportion of the (meth)acrylic acid ester structural unit (a) is 65 to 80 mol% of the total structural units of the copolymer resin. Note that in this specification, (meth)acrylic refers to methacryl and/or acrylic.

In the formula, R ¹ is a hydrogen atom or a methyl group, preferably a methyl group.

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

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

The resin (B1) may contain only one type of (meth)acrylic acid ester structural unit (a) represented by the general formula (1), or may contain two or more types.

In the formula, R ³ is a hydrogen atom or a methyl group, preferably a hydrogen atom.

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

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

The aliphatic vinyl structural unit (b) represented by the general formula (2) may contain only one type or two or more types in the resin (B1).

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

Only one type of other structural units may be contained in the resin (B1), or two or more types may be contained in the resin (B1).

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

Further, the content of the aliphatic vinyl structural unit (b) represented by the general formula (2) is preferably 20 to 35 mol% based on the total structural units of the resin (B1) (copolymer resin). , more preferably 20 to 30 mol%. It is preferable that the content of the aliphatic vinyl structural unit (b) is 20 mol % or more because warpage can be prevented under high temperature and high humidity conditions. On the other hand, it is preferable that the content of the aliphatic vinyl structural unit (b) is 35 mol % or less because peeling at the interface with the base layer can be prevented.

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

In addition, in this specification, a "copolymer" may have any structure of a random copolymer, a block copolymer, and an alternating copolymer.

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

The glass transition temperature of the resin (B1) is preferably 110 to 140°C, more preferably 110 to 135°C, particularly preferably 110 to 130°C. It is preferable that the glass transition point is 110° C. or higher because the resin sheet is less likely to be deformed or cracked in a heat environment or a moist heat environment. On the other hand, a temperature of 140° C. or lower is preferable because it provides excellent workability when molded by continuous heat forming using mirror-finished rolls or shaping rolls, or batch-type heat forming using mirror-finished molds or shaping molds. Note that the glass transition temperature in the present invention is a temperature measured using a differential scanning calorimeter using a sample of 10 mg at a heating rate of 10° C./min and calculated by the midpoint method.

Specific examples of the resin (B1) include Optimus 7500 and 6000 (manufactured by Mitsubishi Gas Chemical). In addition, the resin (B1) mentioned above may be used alone or in combination of two or more types.

The method for producing the resin (B1) is not particularly limited, but after polymerizing at least one type of (meth)acrylic acid ester monomer and at least one type of aromatic vinyl monomer, the aromatic vinyl monomer derived from the aromatic vinyl monomer is Those obtained by hydrogenating heavy bonds are preferred.

Examples of the aromatic vinyl monomer include, but are not limited to, styrene, α-methylstyrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and derivatives thereof. Among these, the aromatic vinyl monomer is preferably styrene.

Known methods can be used to polymerize the (meth)acrylic acid ester monomer and the aromatic vinyl monomer. For example, it can be manufactured by a bulk polymerization method, a solution polymerization method, or the like.

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

The polymerization initiator is not particularly limited, but includes t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, 1,1-di(t- hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, t-hexylpropoxyisopropyl monocarbonate, t-amyl Organic peroxides such as peroxy normal octoate, t-butylperoxyisopropyl monocarbonate, di-t-butyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methyl butyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and other azo compounds. These can be used alone or in combination of two or more.

The chain transfer agent includes, but is not particularly limited to, α-methylstyrene dimer.

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

The solvent used in the hydrogenation reaction after polymerizing the (meth)acrylic acid ester monomer and the aromatic vinyl monomer may be the same as or different from the polymerization solvent described above. For example, 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. Examples include solvents.

After polymerizing a (meth)acrylic acid ester monomer and an aromatic vinyl monomer as described above, resin (B1) is obtained by hydrogenating the aromatic double bond derived from the aromatic vinyl monomer.

The hydrogenation method is not particularly limited, and known methods can be used. For example, it can be carried out in a batch system or a continuous flow system at a hydrogen pressure of 3 to 30 MPa and a reaction temperature of 60 to 250°C. It is preferable that the reaction temperature is 60° C. or higher because the reaction time does not take too long. On the other hand, it is preferable that the reaction temperature is 250° C. or lower because side reactions such as molecular chain scission and hydrogenation of ester moieties do not occur or hardly occur.

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

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

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

(Resin (B2))
The resin (B2) contains 35 to 65% by mass of the resin (B1), preferably 40 to 60% by mass, and 35 to 65% by mass of the styrene-unsaturated dicarboxylic acid copolymer (C), preferably 40 to 60% by mass. Contains 60% by mass. Further, the styrene-unsaturated dicarboxylic acid copolymer (C) contains 65 to 90% by mass of the styrene structural unit (c1) and 10 to 35% by mass of the unsaturated dicarboxylic anhydride structural unit (c2). include. That is, resin (B2) is a resin composition containing two or more types of resin.

Resin (B1)
The resin (B1) may be any of the above-mentioned resins. In this case, the resin (B1) may be used alone or in combination of two or more kinds.

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

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

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

・Unsaturated dicarboxylic anhydride structural unit (c2)
Examples of the unsaturated dicarboxylic anhydride monomer include, but are not particularly limited to, acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid. Among these, maleic anhydride is preferred from the viewpoint of compatibility with the styrenic monomer. These unsaturated dicarboxylic anhydride monomers may be used alone or in combination of two or more.

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

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

(Resin (B3))
The resin (B3) contains 55 to 10% by mass of the resin (D) containing a vinyl monomer and 45 to 90% by mass of the styrene-unsaturated dicarboxylic acid copolymer (E). The styrene-unsaturated dicarboxylic acid copolymer (E) contains 50 to 80% by mass of styrene structural units (e1), 10 to 30% by mass of unsaturated dicarboxylic acid structural units (e2), and vinyl-based Contains 5 to 30% by mass of structural unit (e3). That is, resin (B3) is a resin composition containing two or more types of resin.

・Resin containing vinyl monomer (D)
Examples of the resin (D) containing a vinyl monomer include, but are not limited to, acrylonitrile, methacrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and methacrylic acid. , methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate. Among these, the resin (D) containing a vinyl monomer preferably contains methyl methacrylate as a structural unit. The resin (D) containing a vinyl monomer may be a polymer using one type of the above-mentioned structural units, or a copolymer using a combination of two or more types.

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

The resin (D) containing the vinyl monomer described above may be used alone or in combination of two or more types.

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

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

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

・Unsaturated dicarboxylic anhydride structural unit (e2)
Examples of the unsaturated dicarboxylic anhydride monomer include, but are not particularly limited to, acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid. Among these, maleic anhydride is preferred from the viewpoint of compatibility with vinyl monomers. These unsaturated dicarboxylic anhydride monomers may be used alone or in combination of two or more.

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

・Vinyl structural unit (e3)
Examples of vinyl monomers include, but are not limited to, acrylonitrile, methacrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, Examples include vinyl monomers such as ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate. Among these, methyl methacrylate (MMA) is preferred from the viewpoint of compatibility with the resin (D) containing a vinyl monomer. These vinyl monomers may be used alone or in combination of two or more.

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

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. It is preferable that the weight average molecular weight is within the above range because it has good compatibility with the resin (D) containing a vinyl monomer and is excellent in improving heat resistance.

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

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

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

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

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

・(Meth)acrylic acid ester structural unit The (meth)acrylic acid ester monomer is not particularly limited, and includes acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacryl acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and the like. Among these, methyl methacrylate is preferred. These (meth)acrylic acid ester monomers may be used alone or in combination of two or more.

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

・N-substituted maleimide structural unit N-substituted maleimide monomers include, but are not particularly limited to, N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, and N-hydroxyphenylmaleimide. , N-arylmaleimides such as N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, and N-tribromophenylmaleimide. Among these, N-phenylmaleimide is preferred from the viewpoint of compatibility with the (meth)acrylic acid structural unit. Note that these N-substituted maleimide monomers may be used alone or in combination of two or more.

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

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

Specific examples of the resin copolymer (G) include Delpet PM120N (manufactured by Asahi Kasei Chemical Co., Ltd.), but are not limited thereto.

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

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

At this time, it is preferable that the resin copolymer (G) and the styrene-unsaturated dicarboxylic acid copolymer (E) be an alloy of materials having high glass transition temperatures.

Methods for producing the alloy include, but are not particularly limited to, a method of melting and kneading at a cylinder temperature of 240° C. using a twin-screw extruder with a screw diameter of 26 mm, extruding it into a strand shape, and pelletizing it with a pelletizer.

(Resin (B5))
The resin (B5) contains a structural unit (H) represented by the following formula (3). It is preferable that the resin (B5) is a copolymer further containing a structural unit (J) represented by the following formula (4). Furthermore, the copolymer may further contain other structural units.

The content of the structural unit (H) represented by formula (3) is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, based on the total structural units of the resin (B5). The amount is more preferably 70 to 100 mol%.

The content of the structural unit (J) represented by formula (4) is preferably 0 to 50 mol%, and preferably 0 to 40 mol%, based on the total structural units of the resin (B5). More preferably, it is 0 to 30 mol%.

The content of other structural units is preferably 10 mol% or less, more preferably 5 mol% or less, and preferably 2 mol% or less, based on the total structural units of the resin (B5). Particularly preferred.

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%, based on the total structural units of the resin (B5). It is preferably 98 to 100 mol%, and more preferably 98 to 100 mol%.

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

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

The method for producing the resin (B5) is not particularly limited, but it can be produced in the same manner as the method for producing the polycarbonate resin (a1) described above, except for using bisphenol C as a monomer.

(Resin (B6))
The resin (B6) contains 35 to 65% by mass of the resin (D) containing a vinyl monomer and 35 to 65% by mass of the styrene-unsaturated dicarboxylic acid copolymer (C). Further, the styrene-unsaturated dicarboxylic acid copolymer (C) contains 65 to 90% by mass of the styrene structural unit (c1) and 10 to 35% by mass of the unsaturated dicarboxylic anhydride structural unit (c2). include. That is, resin (B6) is a resin composition containing two or more types of resin.

・Resin containing vinyl monomer (D)
As the resin (D) containing a vinyl monomer, the same resin as described in the above-mentioned resin (B3) is used. The resin (D) containing the vinyl monomer may be used alone or in combination of two or more types.

・Styrene-unsaturated dicarboxylic acid copolymer (C)
As the styrene-unsaturated dicarboxylic acid copolymer (C), those similar to those described in the above resin (B2) can be used. The styrene-unsaturated dicarboxylic acid copolymer (C) may be used alone or in combination of two or more.

By including at least one selected from the group consisting of the above resins (B1) to (B6) as the high hardness resin, an antiglare laminate having better shape stability under high temperature and high humidity can be obtained. It is preferable because it can absorb moisture.

[Additive]
The high hardness resin layer may contain additives.

The additive is not particularly limited, and those commonly used in antiglare laminates can be used. Specific examples include antioxidants, anti-coloring agents, anti-static agents, mold release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, organic fillers and inorganic fillers. Examples include reinforcing materials.

The amount of the additive is preferably 0 to 10% by mass, more preferably 0 to 7% by mass, particularly 0 to 5% by mass, based on the total mass of the high hardness resin layer. preferable.

The method of mixing the additive and the resin is not particularly limited, and methods such as a method of compounding the entire amount, a method of dry blending a masterbatch, a method of dry blending the entire amount, etc. can be used.

[Configuration of high hardness resin layer]
The thickness of the high hardness resin layer is preferably 10 to 250 μm, more preferably 30 to 200 μm, particularly preferably 60 to 150 μm. It is preferable that the thickness of the high hardness resin layer is 10 μm or more because the surface hardness becomes high. On the other hand, it is preferable that the thickness of the high hardness resin layer is 250 μm or less because impact resistance becomes high.

[Lamination of high hardness resin layer to base material layer]
As described above, an additional layer may exist between the base material layer and the high hardness resin layer, but here, a case will be described in which the high hardness resin layer is laminated on the base material layer.

The total thickness of the base material layer and the high hardness resin layer is preferably 100 to 3,500 μm, more preferably 100 to 3,000 μm, even more preferably 500 to 3,000 μm, particularly preferably 1,200 to 3,000 μm. It is preferable that the total thickness is 100 μm or more because the rigidity of the sheet can be maintained. On the other hand, it is preferable that the total thickness is 3500 μm or less because it can prevent the sensitivity of the touch sensor from deteriorating when a touch panel is installed 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%, particularly preferably 85 to 99%. be. By setting it within the above range, both hardness and impact resistance can be achieved.

The method of laminating the high hardness resin layer on the base material layer is not particularly limited, and the method of overlapping the separately formed base material layer and the high hardness resin layer and bonding them together under heat; A method of overlapping a material layer and a high-hardness resin layer and bonding them together with an adhesive; A method of co-extrusion molding the base material layer and a high-hardness resin layer; Examples include a method of integrally forming the base material layer by in-mold molding. Among these, coextrusion is preferred from the viewpoint of manufacturing cost and productivity.

The coextrusion method is not particularly limited. For example, in the feedblock method, a high-hardness resin layer is placed on one side of the base material layer using a feedblock, extruded into a sheet using a T-die, and then cooled while passing through forming rolls to form the desired laminate. do. In addition, in the multi-manifold method, a high-hardness resin layer is placed on one side of the base material layer in a multi-manifold die, extruded into a sheet, and then cooled while passing through forming rolls to form the desired laminate. .

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

Preferably, the hard coat layer does not contain organic particles or inorganic particles. By not containing organic particles and inorganic particles, scratch resistance can be improved. Note that, as will be described later, by performing antiglare treatment on the hard coat layer by transfer using a mold, a hard coat layer having an uneven shape without containing organic particles and inorganic particles can be formed.

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

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

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

In addition, when a photopolymerization initiator is included, the content of the photopolymerization initiator is based on 100 parts by mass of the total of the (meth)acrylic monomer, (meth)acrylic oligomer, and surface modifier. The amount is preferably 0.001 to 7 parts by weight, more preferably 0.01 to 5 parts by weight, and even more preferably 0.1 to 3 parts by weight. Note that in this specification, a photopolymerization initiator refers to a photoradical generator.

[(meth)acrylic monomer]
As the (meth)acrylic monomer, any one having a (meth)acryloyl group as a functional group in the molecule can be used. Specifically, a monofunctional monomer, a bifunctional monomer, or a trifunctional or higher functional monomer can be mentioned.

Examples of monofunctional monomers include (meth)acrylic acid and (meth)acrylic acid ester.

Further, as specific examples of bifunctional and/or trifunctional or more functional (meth)acrylic monomers, 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-butylene glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, polyethylene glycol diacrylate, 1,4-butanediol oligoacrylate, neopentyl glycol oligoacrylate , 1,6-hexanediol oligoacrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxytri(meth)acrylate, trimethylolpropanepropoxytri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerylpropoxytriacrylate Examples include (meth)acrylate, trimethylolpropane trimethacrylate, trimethylolpropane ethylene oxide adduct triacrylate, glycerin propylene oxide adduct triacrylate, and pentaerythritol tetraacrylate.

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

[(meth)acrylic oligomer]
Examples of (meth)acrylic oligomers include polyfunctional urethane (meth)acrylate oligomers having two or more functionalities (hereinafter also referred to as "polyfunctional urethane (meth)acrylate oligomers"), and polyfunctional polyester (meth)acrylate oligomers having two or more functionalities. (hereinafter also referred to as "polyfunctional polyester (meth)acrylate oligomer"), bifunctional or higher polyfunctional epoxy (meth)acrylate oligomer (hereinafter also referred to as "polyfunctional epoxy (meth)acrylate oligomer"), and the like.

The polyfunctional urethane (meth)acrylate oligomer is a urethane reaction product of a (meth)acrylate monomer having at least one (meth)acryloyloxy group and a hydroxyl group in one molecule and a polyisocyanate; Examples include urethane reaction products of isocyanate compounds obtained by reacting with isocyanates and (meth)acrylate monomers having at least one (meth)acryloyloxy group and hydroxyl group in one molecule.

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

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

As polyols used in the urethanization reaction, aromatic, aliphatic, and alicyclic polyols, as well as polyester polyols, polyether polyols, and the like are generally used.

Aliphatic and cycloaliphatic polyols typically include 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, trimethylolethane, trimethylolpropane, dimethylolheptane, Examples include methylolpropionic acid, dimethylolbutyric acid, glycerin, hydrogenated bisphenol A, and the like.

Examples of polyester polyols include those obtained by a dehydration condensation reaction between the above-mentioned polyols and polycarboxylic acids. Specific examples of polycarboxylic acids include succinic acid, adipic acid, maleic acid, trimellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may be anhydrides.

In addition to polyalkylene glycols, examples of polyether polyols include polyoxyalkylene-modified polyols obtained by reacting the above-mentioned polyols or phenols with alkylene oxide.

The polyfunctional polyester (meth)acrylate oligomer is obtained by a dehydration condensation reaction using (meth)acrylic acid, polycarboxylic acid, and 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. Polyols used in the dehydration condensation reaction include 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimethylolheptane, dimethylolpropionic acid, dimethylol Examples include butyrionic acid, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and the like.

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

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

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

Examples of the leveling agent include polyether-modified polyalkylsiloxane, polyether-modified siloxane, polyester-modified hydroxyl group-containing polyalkylsiloxane, polyether-modified polydimethylsiloxane having an alkyl group, modified polyether, silicone-modified acrylic, and the like. .

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 the water/oil repellent include fluorine-containing interfaces such as oligomers containing fluorine-containing groups and lipophilic groups, and oligomers containing fluorine-containing groups, hydrophilic groups, lipophilic groups, and UV-reactive groups. Includes active agents and water and oil repellents.

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

Examples of the organic particles include acrylic particles and silicon particles.

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

[Photopolymerization initiator]
Examples of the photopolymerization initiator include monofunctional photopolymerization initiators. Specifically, 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone [Darocur 2959: Merck & Co., Ltd.]; α-hydroxy-α,α'-dimethylacetophenone [Darocur 1173: Merck & Co., Ltd.] Acetophenone-based initiators such as methoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone [Irgacure-651], and 1-hydroxy-cyclohexylphenyl ketone; Benzoin ether-based initiators such as benzoin ethyl ether and benzoin isopropyl ether Other examples include halogenated ketones, acylphosphinoxides, and acyl phosphonates. These photopolymerization initiators may be used alone or in combination of two or more.

[UV absorber]
Examples of UV absorbers include hydroxyphenyltriazine, benzotriazole, and bengophenone. The UV absorbers may be used alone or in combination of two or more.

[Configuration of hard coat layer]
The thickness of the hard coat layer is preferably 1 to 40 μm, more preferably 2 to 10 μm. It is preferable that the thickness of the hard coat layer is 1 μm or more because sufficient hardness can be obtained. On the other hand, it is preferable that the thickness of the hard coat layer is 40 μm or less because it is possible to suppress the occurrence of cracks during bending. The thickness of the hard coat layer can be measured by observing the cross section with a microscope or the like and actually measuring from the coating film interface to the surface.

The pencil hardness of the surface of the hard coat layer is preferably HB or higher, more preferably H or higher, even more preferably 2H or higher, and particularly preferably 2H to 3H. The pencil hardness of the hard coat layer is the result of evaluation using a pencil scratch hardness test based on JIS K 5600-5-4:1999. Specifically, a pencil was pressed against the surface of the hard coat layer at an angle of 45 degrees under a load of 750 g with gradually increasing hardness, and the hardness of the hardest pencil that did not produce any scratches was evaluated as the pencil hardness.

Since the hard coat layer has an uneven shape, it is possible to obtain an anti-glare laminate having excellent anti-glare properties and a good feel to the touch. Specifically, the hard coat layer has a developed interface area ratio (Sdr), an arithmetic mean height (Sa), and an autocorrelation length (Sal) that satisfy the following formulas (i) to (iii). In addition, in this specification, the developed interface area ratio (Sdr), arithmetic mean height (Sa), and autocorrelation length (Sal) are based on ISO 25178-2:2012, as described in the examples described later. Measured in accordance with

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

Regarding the formula (i), the developed interface area ratio (Sdr) is an index of anti-glare property and is correlated with haze. When Sdr exceeds 0.6, light scattering becomes excessive, resulting in whitening and poor texture. Formula (i) more preferably satisfies 0≦Sdr≦0.5, further preferably satisfies 0≦Sdr≦0.4, and particularly preferably satisfies 0≦Sdr≦0.3.

Regarding the formula (ii), the arithmetic mean height (Sa) is an index of anti-glare properties and is correlated with image clarity. When Sa exceeds 0.16, light scattering becomes excessive, resulting in whitening and poor texture. Formula (ii) more preferably satisfies 0.01≦Sa≦0.15, further preferably satisfies 0.02≦Sa≦0.14, and preferably satisfies 0.03≦Sa≦0.13. Particularly preferred.

Regarding the formula (iii), the autocorrelation length (Sal) is an index of anti-glare property and is correlated with glare. In a high-definition display device with a small pixel size, the conventional surface unevenness size causes deterioration of image quality such as screen glare and blurred characters. That is, in the case of a high-definition display device, the conventional surface unevenness size is close in order to the pixel size of high-definition display, and glare occurs due to the lens effect due to the surface unevenness. With conventional fine particle sizes, scattering in the vicinity of straight transmitted light increases, making pixel outlines vague and blurring characters. Furthermore, the intensity distribution of the transmitted scattered light depends on the size of the added particles; smaller particles reduce the scattering around the straight transmitted light and reduce glare, but larger particles reduce the scattering around the straight transmitted light. Increases and glare occurs. When Sal exceeds 15.0, scattering in the vicinity of straight transmitted light increases and glare increases. Formula (iii) more preferably satisfies 1.0≦Sal≦12.0, further preferably satisfies 2.0≦Sal≦10.0, and preferably satisfies 3.0≦Sal≦8.0. Particularly preferred.

<Haze>
The haze in the hard coat layer of the anti-glare laminate of the present invention is preferably 30% or less, more preferably 25% or less, even more preferably 22% or less, and still more preferably 21%. is particularly preferred. Note that in this specification, haze is a value measured in accordance with JIS K 7136:2000 using model HR-100 (manufactured by Murakami Color Research Institute).

<Glare>
The glare in the hard coat layer of the anti-glare laminate of the present invention is preferably 8% or less, more preferably 7% or less, even more preferably 6% or less, and even more preferably 5% or less. It is particularly preferable. In this specification, the uneven shape of the anti-glare laminate was installed upward on a 265 ppi iPad 6 (registered trademark) displaying green (R: 0, G: 205, B: 0), and Prometric Y29 manufactured by Konica Minolta was used. After capturing the image, extract a 60 mm x 60 mm area from the captured screen, divide the extracted image into 9 using the Random Mura sequence of the analysis software "True Test", and set the "(display) brightness standard" in each of the 9 divided areas. The value of glare can be calculated by "deviation/average brightness of evaluation range". It is preferable that the average of the glare values calculated for each of the nine regions is 2.0 or less when used as a front plate. The distance between the lens and the antiglare laminate was 500 mm.
・Glare value calculation method: (Display) Brightness standard deviation/Average brightness of evaluation range

<Image clarity>
An example of a method for evaluating image reflection is the image clarity (image clarity) of reflection measured at a light incident angle of 60° based on JIS K7374. The optical comb widths are 0.125mm, 0.25mm, 0.5mm, 1.0mm, and 2.0mm.The narrower the optical comb width, the larger the variation in the value, and the wider the optical comb width, the smaller the variation in the value. Therefore, the optical comb width is preferably 2.0 mm.
The reflection sharpness measured at a light incident angle of 60° indicates that the larger the value, the more likely the image will be reflected, and the smaller the value, the less likely the image will be reflected. In addition, in the present invention, the reflection sharpness can be measured by the method described in the Examples described later.

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

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

The method of applying the hard coat liquid (polymerizable composition, reaction composition) is not particularly limited, and known methods can be used. Examples include spin coat method, dip method, spray method, slide coat method, bar coat method, roll coat method, gravure coat method, meniscus coat method, flexographic printing method, screen printing method, beat coat method, and separation method. .

As the lamp used for light irradiation in photopolymerization, one having a light emission distribution at a light wavelength of 420 nm or less is used. Examples include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, and the like. Among these, high-pressure mercury lamps or metal halide lamps efficiently emit light in the active wavelength region of the photopolymerization initiator, and emit short-wavelength light that reduces the viscoelastic properties of the resulting polymer due to crosslinking, and This is preferable because it does not emit a lot of long-wavelength light that heats and evaporates light.

The irradiation intensity of the lamp is a factor that influences the degree of polymerization of the obtained polymer, and is appropriately controlled depending on the performance of the target product. When a conventional cleavage type photopolymerization initiator having an acetophenone group is blended, the illumination intensity is preferably in the range of 0.1 to 300 mW/cm ² . In particular, it is preferable to use a metal halide lamp and set the illumination intensity to 10 to 40 mW/cm ² .

The photopolymerization reaction is inhibited by oxygen in the air or oxygen dissolved in the reactive composition. Therefore, it is desirable that the light irradiation be performed using a method that can eliminate the reaction inhibition caused by oxygen. One such method is to cover the reactive composition with a film made of polyethylene terephthalate or Teflon (registered trademark) to cut off contact with oxygen, and then irradiate the reactive composition with light through the film. Alternatively, the reactive composition may be irradiated with light through a light-transmitting window in an inert atmosphere in which oxygen 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 always introduced in order to maintain the atmospheric oxygen concentration at a low level. The introduction of this inert gas generates an air current on the surface of the reactive composition, causing monomer evaporation. In order to suppress the level of monomer evaporation, the air flow velocity of the inert gas is preferably 1 m/sec or less relative to the laminate coated with the hard coat liquid moving in the inert gas atmosphere, More preferably, it is 0.1 m/sec or less. By setting the airflow velocity within the above range, monomer evaporation due to the airflow can be substantially suppressed.

In order to improve the adhesion of the hard coat layer, the coated surface may be pretreated. Examples of treatments include known methods such as sandblasting, solvent treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone treatment, ultraviolet treatment, and primer treatment with a resin composition. Can be mentioned.

The method of forming irregularities on the hard coat layer (antiglare treatment) is not particularly limited, but a method using a mold is preferred. For example, first, a high hardness resin layer, a coating film obtained by applying a reactive composition, and a mold are laminated in this order. Next, a method of photopolymerizing the reactive composition and demolding the mold is included. The photopolymer (hard coat layer) of the reactive composition has a shape that reflects the rough surface of the mold on its contact surface with the mold. That is, the antiglare treatment of the hard coat layer is performed by transfer using a mold.

The mold is not particularly limited as long as it transmits UV light, and glass, transparent resin, etc. can be used. In one embodiment, the mold is a mold in which a transparent film and a transparent resin having a rough surface are laminated. Examples of the transparent film include PET film. Examples of the transparent resin having a rough surface include acrylic resin and the like. At this time, the rough surface of the transparent resin is not particularly limited, and may be formed by adding particles (organic particles, inorganic particles, etc.) into the transparent resin, or may be formed by etching the transparent resin. Alternatively, it may be formed by printing and curing a transparent resin. Although the shape of the rough surface is not particularly limited, it is preferably patterned from the viewpoint of use in applications such as liquid crystal panels. By controlling the type of mold used (material, surface haze, thickness, shape, etc.), the amount of particles added, etc., the surface (irregular shape) of the hard coat layer can be controlled. This makes it possible to form a hard coat layer that satisfies the above formulas (i) to (iii). Preferably, a hard coat layer satisfying the above formulas (iv) to (vi) can also be formed.

Among the methods for forming the hard coat layer described above, it is preferable to pressure-bond a patterned PET film and transfer the uneven shape. That is, according to one embodiment of the present invention, a method for manufacturing an anti-glare laminate is provided. At this time, the manufacturing method includes a step of press-bonding a patterned PET film to the surface of the hard coat layer to transfer the uneven shape. Note that, as the patterned PET film, for example, PTH, PTHA, and PTHZ of Emblem manufactured by Unitika, PF11 and PF23 of low glare AG film manufactured by Daicel, etc. can be used.
An example of a method for producing a patterned PET film preferably used in the method for producing an anti-glare laminate of the present invention is to apply a coating liquid to a PET (polyethylene terephthalate) film with a dry film thickness of 2.0 to 4.0 μm. After drying for 1 to 3 minutes at 70 to 90°C, UV rays were applied at a line speed of 1.0 to 3.0 m/min using a conveyor equipped with a high-pressure mercury lamp with a light source distance of 12 cm and an output of 80 W/cm. A patterned PET film can be produced by irradiating and curing it.
The coating liquid preferably contains an organic solvent such as methyl ethyl ketone (MEK), an acrylic ultraviolet curable resin, fine silica particles, and a photoinitiator. The contents of these components include 70 to 80 parts by mass of an organic solvent such as methyl ethyl ketone (MEK), 19 to 29 parts by mass of an acrylic ultraviolet curable resin, and 0 silica particles (average particle size 3.5 to 5.0 μm). .2 to 1.0 parts by weight, and preferably 2.0 to 4.0 parts by weight of the photoinitiator. This makes it possible to form a hard coat layer that satisfies the above formulas (i) to (iii).

<Physical properties of anti-glare laminate>
In one embodiment, the antiglare laminate preferably has high shape stability. Specifically, the amount of change in warpage after being held in an environment with a temperature of 85°C and a relative humidity of 85% for 120 hours is preferably 350 μm or less, more preferably 250 μm or less, and 175 μm or less. is more preferable, and particularly preferably 75 μm or less. It is preferable that the amount of change in warpage is 350 μm or less because it can be suitably used even in a high temperature and high humidity environment. Note that high shape stability can be obtained by using a high hardness resin layer. By interposing the high-hardness resin layer between the base material layer and the hard coat layer, the shape of the anti-glare laminate is stabilized even in a high-temperature, high-humidity environment. In addition, the materials of the base material layer and the hard coat layer, the difference in glass transition temperature (Tg) between the base material layer and the high hardness resin layer, the difference in hardness, and the glass transition temperature (Tg) between the high hardness resin layer and the hard coat layer. Shape stability can also be controlled by appropriately changing the difference, hardness difference, etc.

<Application>
The anti-glare laminate of the present invention is excellent in anti-glare properties and feels good to the touch, and is therefore used as a protective plate for a liquid crystal surface, a front plate, etc., as described above. In one embodiment, an in-vehicle display device including an anti-glare laminate is provided. In another embodiment, a touch panel front protection plate including an anti-glare laminate is provided. Furthermore, in another embodiment, a front plate for office automation equipment, portable electronic equipment, or television is provided.

Examples of the present invention are shown below, but the present invention is not limited to the embodiments.

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

[Developed interface area ratio (Sdr)]
Observation conditions Objective lens: 20x Acquisition mode: Accuracy priority Measurement area: 645μm x 645μm
Analysis conditions Correction: Remove spike noise, remove slope

[Arithmetic mean height (Sa)]
Observation conditions Objective lens: 20x Acquisition mode: Accuracy priority Measurement area: 645μm x 645μm
Analysis conditions Correction: Remove spike noise, remove slope

[Autocorrelation length (Sal)]
Observation conditions Objective lens: 100x Acquisition mode: Accuracy priority Measurement area: 129μm x 129μm
Analysis conditions Correction: Remove spike noise, remove slope

<Haze>
Haze was calculated by the method specified in JIS K 7136:2000 using "HR-100" manufactured by Murakami Color Research Institute.

<Reflection clarity (image clarity)>
Measurement was carried out using "ICM 1T" manufactured by Suga Test Instruments Co., Ltd., installed in accordance with JIS K7374 so that the flow direction of the anti-glare laminate and the direction of the comb teeth of the optical comb were parallel. Among the optical combs, a 2.0 mm optical comb was used, and the image clarity of reflection measured at a light incident angle of 60° was defined as the reflection clarity. Measurements were carried out by pasting black tape (black vinyl tape model number 117BLA, manufactured by 3M Japan Co., Ltd.) on the back side of the uneven surface to suppress back reflection.

<Glare>
The uneven shape of the anti-glare laminate was placed facing upward on a 265ppi iPad 6 (registered trademark) with green display (R: 0, G: 205, B: 0), and after taking an image with Konica Minolta's Prometric Y29, the shooting screen Extract a 60mm x 60mm image from ” was used to calculate the glare value. It is preferable that the average of the glare values calculated for each of the nine regions is 2.0 or less when used as a front plate. The distance between the lens and the antiglare laminate was 500 mm.
・Glare value calculation method: (Display) Brightness standard deviation/Average brightness of evaluation range

<SW hardness>
Using steel wool #0000 manufactured by Nippon Steel Wool, the uneven hard coat layer of the anti-glare laminate was subjected to 15 reciprocations with a load of 100 g/ ^cm2 , and the degree of damage was evaluated on a 10-point scale by visual observation. did. It is described as RANK1 to RANK10. Note that the measurement was performed twice, and if different results were obtained, that range was taken as the measurement result.

RANK1: No scratches (equivalent to inorganic glass)
RANK 2: 1 to 5 scratches RANK 3: 6 to 10 scratches RANK 4: 11 to 15 scratches RANK 5: 16 to 20 scratches RANK 6: 21 to 25 scratches RANK 7: 26 to 30 scratches RANK 8: 31 to 40 scratches RANK 9 : 41 or more scratches (same as polymethacrylic acid)
RANK10: 41 or more scratches (same as polycarbonate)

<Shape stability>
A test piece (antiglare laminate) was cut into a size of 100 mm x 60 mm. The cut test piece was set in a two-point support type holder and placed in an environmental testing machine set at a temperature of 23% and a relative humidity of 50% for over 24 hours to adjust the condition, and then warpage was measured (before treatment). Next, the test piece was set in a holder and put into an environmental testing machine set at a temperature of 85° C. and a relative humidity of 85%, and kept in that state for 120 hours. Further, the holder was moved together with the holder into an environmental testing machine set at a temperature of 23% and a relative humidity of 50%, and the warp was measured again after being held in that state for 4 hours (after treatment). To measure the warpage, use a three-dimensional shape measuring machine (KS-1000 manufactured by KEYENCE) equipped with an electric stage.The sample taken out is placed horizontally in a convex state, and scanned at 1 mm intervals to measure the central part. The bulge was measured as the warp. The absolute value of the difference in the amount of warpage before and after treatment, i.e.
| (Amount of warpage after treatment) - (Amount of warpage before treatment) |
was evaluated as shape stability.

[Example 1]
<Laminated body>
Synthetic resin is produced using a multilayer extrusion device that includes a single-screw extruder with a shaft diameter of 35 mm, a single-screw extruder with a shaft diameter of 65 mm, a feed block connected to all the extruders, and a T-die connected to the feed block. A laminate was molded. Optimas 7500 manufactured by Mitsubishi Gas Chemical was continuously introduced as a high-hardness resin (B1) into a single-screw extruder with a shaft diameter of 35 mm, and extrusion was performed at a cylinder temperature of 240° C. and a discharge rate of 2.6 kg/h. In addition, polycarbonate resin (manufactured by Mitsubishi Engineering Plastics, trade name: Iupilon S-1000) was continuously introduced into a single-screw extruder with a shaft diameter of 65 mm, and extruded at a cylinder temperature of 280°C and a discharge rate of 50.0 kg/h. Ta. A feed block connected to all the extruders was equipped with distribution pins of two types and two layers, and the temperature was set to 270° C., and high hardness resin (B1) and polycarbonate resin were introduced and laminated. It is extruded into a sheet using a T-die connected to the end at a temperature of 270°C, and cooled while transferring the mirror surface using three mirror-finishing rolls at temperatures of 120°C, 130°C, and 190°C from the upstream side. A laminate of a layer (B1) (high hardness resin layer) and a polycarbonate resin layer (base material layer) was obtained. The thickness of the obtained laminate was 1.0 mm, and the thickness of the high hardness resin (B1) layer was 60 μm near the center.

In addition, Optimas 7500 manufactured by Mitsubishi Gas Chemical used as the high hardness resin (B1) contains the (meth)acrylic acid ester structural unit (a) represented by the above general formula (1) and the above general formula (2). It is a copolymer resin containing an aliphatic vinyl structural unit (b). At this time, the total proportion of the (meth)acrylic acid ester structural unit (a) and the aliphatic vinyl structural unit (b) is 99 mol% of the total structural units of the copolymer resin, and the (meth)acrylic The proportion of the acid ester structural unit (a) is 75 mol% of the total structural units of the copolymer resin.

<Photocurable resin composition (Y-1)>
U6HA (6-functional urethane acrylate oligomer, manufactured by Shin Nakamura Chemical Co., Ltd.) 60% by mass, #260 (1,9-nonanediol diacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 35% by mass, and fluorine-based leveling A photocurable resin composition was prepared by adding 3 parts by mass of photoinitiator I-184 (manufactured by BASF Corporation [compound name: 1-hydroxy-cyclohexyl phenyl ketone]) to 100 parts by mass of a mixture containing 5% by mass of the agent. Product (Y-1) was obtained.

<Patterned PET film (Z-1)>
Coating liquid (i) was prepared by mixing and stirring 22.7 parts by mass of acrylic ultraviolet-curable resin (solid content 100%, product name: Light Acrylate DPE-6A; manufactured by Kyoeisha Chemical Co., Ltd.), 0.3 parts by mass of silica fine particles (NP-30, average particle size 4 μm, manufactured by AGC Si-Tech Co., Ltd.), and 3 parts by mass of photoinitiator (product name Omnirad 184; manufactured by IGM Resins) with external addition, relative to 77 parts by mass of MEK. Next, coating liquid (i) was applied to a PET (polyethylene terephthalate) film so as to have a dry film thickness of 2.5 μm, and after drying at 80° C. for 2 minutes, the film was irradiated with ultraviolet light at a line speed of 1.5 m/min on a conveyor equipped with a high-pressure mercury lamp with a light source distance of 12 cm and an output of 80 W/cm to cure the film, thereby preparing a patterned PET film (Z-1).

The photocurable resin composition (Y-1) is cured on the high hardness resin (B1) layer of the laminate of the high hardness resin (B1) layer (high hardness resin layer) and the polycarbonate resin layer (base material layer). The coating was applied using a bar coater so that the subsequent coating thickness was 5 to 10 μm, and the patterned PET film (Z-1) was covered and pressure-bonded so that the pattern surface came into contact with the coating solution. After that, the light source distance was 12 cm, the metal halide lamp (20 mW/cm) was irradiated for 30 seconds to cure the patterned PET film, and the anti-glare layer with a rough hard coat layer was formed on the high hardness resin layer (B1). A laminate was obtained.

[Example 2]
An antiglare laminate was produced in the same manner as in Example 1, except that the following high hardness resin (B3) was used instead of the high hardness resin (B1).

High hardness resin (B3) was prepared as follows. That is, 75% by mass of Regisphy R100 (manufactured by Denki Kagaku Kogyo) was used as the styrene-unsaturated dicarboxylic acid copolymer (E) and Parapet HR-, which is a methyl methacrylate resin, was used as the resin containing a vinyl monomer (D). 25% by mass of L (manufactured by Kuraray) was added and mixed for 30 minutes using a blender. Next, using an extruder with a screw diameter of 26 mm (manufactured by Toshiba Machine, TEM-26SS, L/D≒40), the mixture was melted and kneaded at a cylinder temperature of 230°C, extruded into a strand, and pelletized with a pelletizer. A high hardness resin (B3) was obtained. Pelletization was performed stably.

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

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

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

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

The coating liquid (ii) contains 77 parts by mass of MEK, 22.6 parts by mass of acrylic ultraviolet curable resin (solid content 100%, trade name: Light Acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.), and silica fine particles (NP- 30, average particle diameter 4 μm, manufactured by AGC SITEC Co., Ltd.) and 3 parts by mass of a photoinitiator (trade name Omnirad 184; manufactured by IGM Resins) were mixed externally and stirred.

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

<Patterned PET film (Z-3)>
A patterned PET film (Z-3) was produced using the following coating solution (iii) instead of coating solution (i).

The coating liquid (iii) contains 77 parts by mass of MEK, 22.8 parts by mass of acrylic ultraviolet curable resin (solid content 100%, trade name: Light Acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.), and silica fine particles (NP- 30, average particle diameter 4 μm, manufactured by AGC SITEC Co., Ltd.) and 3 parts by mass of a photoinitiator (trade name Omnirad 184; manufactured by IGM Resins) were mixed and stirred.

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

<Patterned PET film (Z-4)>
A patterned PET film (Z-4) was produced using the following coating solution (iv) instead of coating solution (i).

The coating liquid (iv) contains 71.5 parts by mass of MEK, 27.7 parts by mass of acrylic ultraviolet curable resin (solid content 100%, trade name: Light Acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.), silica fine particles ( 0.8 parts by mass of NP-30 (average particle size 4 μm, manufactured by AGC SITEC) and 3 parts by mass of a photoinitiator (trade name Omnirad 184; manufactured by IGM Resins) were mixed and stirred.

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

<Patterned PET film (Z-5)>
A patterned PET film (Z-5) was produced using the following coating solution (v) instead of coating solution (i).

The coating liquid (v) contains 80 parts by mass of MEK, 19.4 parts by mass of acrylic ultraviolet curable resin (solid content 100%, trade name: Light Acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.), and silica fine particles (NP- 30, average particle diameter 4 μm, manufactured by AGC SITEC Co., Ltd.) and 3 parts by mass of a photoinitiator (trade name Omnirad 184; manufactured by IGM Resins) were mixed and stirred.

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

<Patterned PET film (Z-6)>
A patterned PET film (Z-6) was prepared using the following coating liquid (vi) instead of coating liquid (i) so that the dry film thickness was 4.0 μm.

The coating liquid (vi) contains 80 parts by mass of MEK, 19.4 parts by mass of acrylic ultraviolet curable resin (solid content 100%, trade name: Light Acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.), and silica fine particles (NP- 30, average particle diameter 4 μm, manufactured by AGC SITEC Co., Ltd.) and 3 parts by mass of a photoinitiator (trade name Omnirad 184; manufactured by IGM Resins) were mixed and stirred.

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

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

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

The coating liquid (vii) contains 71.5 parts by mass of MEK, 27.0 parts by mass of acrylic ultraviolet curable resin (solid content 100%, trade name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.), silica fine particles ( 1.5 parts by mass of NP-30 (average particle size 4 μm, manufactured by AGC SITEC) and 3 parts by mass of a photoinitiator (trade name Omnirad 184; manufactured by IGM Resins) were mixed and stirred.

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

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

The coating liquid (viii) contains 90.0 parts by mass of MEK, 9.5 parts by mass of acrylic ultraviolet curable resin (solid content 100%, trade name: Light Acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.), silica fine particles ( 0.5 parts by mass of NP-30 (average particle size 4 μm, manufactured by AGC SITEC) and 3 parts by mass of a photoinitiator (trade name Omnirad 184; manufactured by IGM Resins) were mixed and stirred.

[Comparative example 3]
Prevention was carried out in the same manner as in Example 1, except that Nakajima Kogyo's C-50 G-100 (Z-9) was used as the patterned PET film instead of the patterned PET film (Z-1). A glare laminate was produced.

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

That is, to 50 parts by mass of MEK, 50 parts by mass of acrylic ultraviolet curable resin (100% solids product: Light Acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.), silica fine particles (octylsilane-treated fumed silica, average primary particle size 1) .9 μm, trade name: SE6050-SYB, manufactured by Admatex Co., Ltd.), and 3 parts by mass of a photoinitiator (trade name, Irgacure 184, manufactured by Toyotsu Chemiplus Co., Ltd.) are mixed and stirred to form a photocurable composition. Product (Y-2) was produced.

The photocurable composition (Y-2) was coated on the high hardness resin layer using a bar coater so that the coating film thickness after curing was 2.5 μm, and dried at 80° C. for 2 minutes. An anti-glare laminate was obtained by curing by irradiating with a metal halide lamp (20 mW/cm) for 30 seconds at a light source distance of 12 cm while purging with nitrogen.

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

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

As is clear from the results in Table 2, Examples 1 to 9 have excellent anti-glare properties because Sdr, Sa, and Sal satisfy formulas (i) to (iii). Furthermore, it was confirmed that Examples 1 to 8 using high hardness resins (B1), (B3), or (B6) were also excellent in shape stability.

On the other hand, Comparative Examples 1 and 2 had insufficient antiglare properties because Sdr and Sa did not satisfy formulas (i) and (ii). It was confirmed that the anti-glare properties were also insufficient in terms of haze and image clarity.

Comparative Example 3 had insufficient anti-glare properties because Sa and Sal did not satisfy formulas (ii) and (iii). It was confirmed that the anti-glare properties were insufficient from the viewpoints of image clarity and glare.

Furthermore, Comparative Example 4 had insufficient anti-glare properties because Sdr did not satisfy formula (i). It was also confirmed that the anti-glare properties were insufficient from the viewpoint of glare. It was confirmed that since the hard coat layer contained silica particles, the glare increased and the SW hardness was insufficient.

Claims (11)

An anti-glare laminate in which a base material layer containing at least a polycarbonate resin (a1), a high hardness resin layer containing a high hardness resin (B), and a hard coat layer are arranged in this order, wherein the hard coat layer The developed interface area ratio (Sdr), arithmetic mean height (Sa), and autocorrelation length (Sal) are expressed by the following formulas (i) to (iii):
0≦Sdr≦0.6 (i)
0≦Sa≦0.16 (ii)
0≦Sal≦15.0 (iii)
An anti-glare laminate that satisfies the following requirements. The developed interface area ratio (Sdr), arithmetic mean height (Sa), and autocorrelation length (Sal) of the hard coat layer are expressed by the following formulas (iv) to (vi):
0≦Sdr≦0.3 (iv)
0.03≦Sa≦0.13 (v)
3.0≦Sal≦8.0 (vi)
The antiglare laminate according to claim 1, which satisfies the following. The anti-glare laminate according to claim 1 or 2, wherein the anti-glare laminate has a change in warpage of 350 μm or less after being kept in an environment of 85° C. and 85% relative humidity for 120 hours. The antiglare laminate according to any one of claims 1 to 3, wherein the high hardness resin layer has a thickness of 10 to 250 μm. The antiglare laminate according to any one of claims 1 to 4, wherein the total thickness of the base layer and the high hardness resin layer is 100 to 3,000 μm. The antiglare laminate according to any one of claims 1 to 5, wherein the hard coat layer does not contain organic particles or inorganic particles. The polycarbonate resin (a1) has the following general formula (5):

(In the formula, R ⁵ represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms, and each R ⁶ may independently have a hydrogen atom, a halogen, or a substituent. represents a good alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, n is an integer of 0 to 4, where the substituent is a halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. An on-vehicle display device comprising the anti-glare laminate according to any one of claims 1 to 7. A touch panel front protection plate comprising the anti-glare laminate according to any one of claims 1 to 7. A front plate for office automation equipment, portable electronic equipment, or television, comprising the anti-glare laminate according to any one of claims 1 to 7. A method for producing an anti-glare laminate according to any one of claims 1 to 7, comprising:
A patterned PET film is pressed onto the surface of the hard coat layer to transfer the uneven shape, and the hard coat layer after the transfer has the following formulas (i) to (iii):
0≦Sdr≦0.6 (i)
0≦Sa≦0.16 (ii)
0≦Sal≦15.0 (iii)
The manufacturing method includes the step of satisfying the following.