WO2021193215A1

WO2021193215A1 - Anti-glare laminate body

Info

Publication number: WO2021193215A1
Application number: PCT/JP2021/010482
Authority: WO
Inventors: 帰心小澤
Original assignee: 三菱瓦斯化学株式会社; Ｍｇｃフィルシート株式会社
Priority date: 2020-03-26
Filing date: 2021-03-16
Publication date: 2021-09-30
Also published as: TW202144173A; JPWO2021193215A1; CN114929479A

Abstract

Provided is an anti-glare laminate body having excellent anti-glare properties and excellent feeling of touch.　An anti-glare laminate body comprising at least a base material layer comprising a polycarbonate resin (a1), a high-hardness resin layer comprising a high-hardness resin, and a hard coat layer which are arranged in this order, in which the arithmetic average roughness (Ra), the maximum profile peak height (Rp), the maximum profile valley depth (Rv) and the skewness (Rsk) of the hard coat layer satisfy formulae (1) to (3), and the dynamical friction factor (μk) of the hard coat layer satisfies formula (4) as measured using a touch contact probe as a contact probe at a load of 50 g, a scanning speed of 10 mm/sec. and a scanning distance of 90 mm.

Description

Anti-glare laminate

The present invention relates to an antiglare laminate. More specifically, the present invention has antiglare properties used as an in-vehicle display device, a touch panel front protective plate for a mobile phone terminal, a personal computer, a tablet PC, a front plate for an OA device, a portable electronic device, a front plate for a television, and the like. Regarding the laminate.

The liquid crystal display device is provided with a protective plate or a front plate for the purpose of protecting the liquid crystal panel and the like. A (meth) acrylic resin typified by polymethyl methacrylate (PMMA) is used for the protective plate or front plate of a conventional liquid crystal display device.

Such a protective plate or front plate may be subjected to antiglare treatment that can suppress the reflection of an image or reduce the reflectance by scattering or interference of light. In addition, since the protective plate or the front plate is operated by a finger, it is also important that the protective plate or the front plate is excellent in touch when touched by a hand.

For example, Patent Document 1 describes an invention relating to a touch panel having an uneven surface on the operator side. At this time, the coefficient of static friction and the arithmetic mean roughness (Ra _2.5 ) of the unevenness satisfy predetermined conditions. As a result, Patent Document 1 describes that it has outdoor antiglare properties and is excellent in touch panel operability. More specifically, Patent Document 1 describes a coating film obtained by applying a concavo-convex layer coating solution containing an acrylic monomer, organic particles, and inorganic particles on a triacetyl cellulose (TAC) film. A laminate or the like in which an uneven layer is formed by irradiating with ultraviolet rays is described.

Further, it is desired that the shape stability is excellent in a high temperature and high humidity environment, such as when it is used as a front plate used in a temperature and humidity environment exceeding 40 ° C. such as in an automobile interior. For example, it is preferable that the amount of change in warpage before and after exposure to the environment at a temperature of 85 ° C. and a humidity of 85% is small.

By the way, in recent years, polycarbonate resin has been widely used as a protective plate or a front plate because it has high impact resistance, heat resistance, secondary workability, light weight and transparency.

International Publication No. 2017/188186

An object of the present invention is to provide an antiglare laminate having excellent antiglare properties and touch comfort when a polycarbonate resin is used.

The present inventor has conducted diligent studies in order to solve the above problems. As a result, it has been found that the above problems can be solved by forming a predetermined laminated structure including a base material layer containing a polycarbonate resin, a high hardness resin layer, and a hard coat layer, and controlling the surface of the hard coat layer. , The present invention has been completed. That is, the present invention is as follows.

<1> An antiglare laminate in which a base material layer containing at least a polycarbonate resin (a1), a high hardness resin layer containing a high hardness resin, and a hard coat layer are arranged in this order.
The arithmetic mean roughness (Ra), maximum peak height (Rp), maximum valley depth (Rv), and skewness (Rsk) of the hard coat layer are the following equations (1) to (3):

The filling,
Using a tactile contact as the contact of the hard coat layer, the dynamic friction coefficient (μk) measured at a load of 50 g, a scanning speed of 10 mm / sec, and a scanning distance of 90 mm is the following equation (4):

Anti-glare laminate that meets the requirements.
_{<2> The reflectance (SCI 550} ) including the specularly reflected light and the reflectance (SCE ₅₅₀ ) excluding the specularly reflected light of the hard coat layer at a wavelength of 550 nm are calculated by the following equation (5):

The antiglare laminate according to <1> above.

<3> The prevention according to <1> or <2>, wherein the amount of change in warpage of the antiglare laminate after being held at a temperature of 85 ° C. and a relative humidity of 85% for 120 hours is 350 μm or less. Dazzling laminate.
<4> The antiglare laminate according to any one of <1> to <3>, 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>, wherein the total thickness of the base material layer and the high hardness resin layer is 100 to 3,000 μm.
<6> High hardness resin (B)
The following general formula (1):

(In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² is an alkyl group having 1 to 18 carbon atoms.)
The (meth) acrylic acid ester structural unit (a) represented by and the following general formula (2):

(In the formula, R ³ is a hydrogen atom or a methyl group, and R ⁴ is a cyclohexyl group which may have a hydrocarbon machine having 1 to 4 carbon atoms.)
It is a copolymer resin containing the aliphatic vinyl structural unit (b) represented by, and the total ratio of the (meth) acrylic acid ester structural unit (a) and the aliphatic vinyl structural unit (b) is the same. The resin (B1) is 90 to 100 mol% of all the constituent units of the polymerized resin, and the ratio of the (meth) acrylic acid ester constituent unit (a) is 65 to 80 mol% of all the constituent units of the copolymerized resin. ),
The resin (B1) is 35 to 65% by mass, the styrene-unsaturated dicarboxylic acid copolymer (C) is 35 to 65% by mass, and the styrene-unsaturated dicarboxylic acid copolymer (C) is styrene-based. The resin (B2), which contains the structural unit (c1) in an amount of 65 to 90% by mass and the unsaturated dicarboxylic acid anhydride structural unit (c2) in an amount of 10 to 35% by mass.
The resin (D) containing a vinyl monomer is contained in an amount of 55 to 10% by mass, and the styrene-unsaturated dicarboxylic acid-based copolymer (E) is contained in an amount of 45 to 90% by mass. The coalescence (E) is 50 to 80% by mass of the styrene-based constituent unit (e1), 10 to 30% by mass of the unsaturated dicarboxylic acid constituent unit (e2), and 5 to 30% by mass of the vinyl-based constituent unit (e3). Including, resin (B3),
A resin copolymer (G) containing 5 to 20% by mass of a styrene constituent unit, 70 to 90% by mass of a (meth) acrylic acid ester constituent unit, and 5 to 20% by mass of an N-substituted maleimide constituent unit, or a resin. A resin (B4), which is an alloy of the polymer (G) and a styrene-unsaturated dicarboxylic acid-based copolymer (E).
The following general formula (3):

35 to 65% by mass of the resin (B5) containing the structural unit (H) represented by, and the resin (D) containing a vinyl-based monomer, and the styrene-unsaturated dicarboxylic acid-based copolymer (C). 35 to 65% by mass, and the styrene-unsaturated dicarboxylic acid copolymer (C) contains 65 to 90% by mass of the styrene-based structural unit (c1) and 10 of the unsaturated dicarboxylic acid anhydride constituent unit (c2). The antiglare laminate according to any one of <1> to <5> above, which comprises at least one selected from the group consisting of the resin (B6), which comprises ~ 35% by mass.
<7> The resin (B5) is based on the following general formula (4):

The antiglare laminate according to <6> above, which is a copolymer further containing the structural unit (J) represented by.
<8> The antiglare laminate according to any one of <1> to <7>, wherein the hard coat layer does not contain organic particles and inorganic particles.
<9> 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 R ⁶ may independently have a hydrogen atom, a halogen, or a substituent. It represents a good alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, and n is an integer of 0 to 4, wherein the substituent is a halogen, an alkyl group having 1 to 20 carbon atoms, and the like. Alternatively, it is an aryl group having 6 to 12 carbon atoms.)
The antiglare laminate according to any one of <1> to <8> above, which contains a component derived from monohydric phenol represented by.
<10> An in-vehicle display device including the antiglare laminate according to any one of <1> to <9> above.
<11> A touch panel front protective plate including the antiglare laminate according to any one of <1> to <9> above.
<12> A front plate for OA equipment, portable electronic equipment, or a television, which comprises the antiglare laminate according to any one of <1> to <9> above.
<13> The method for producing an antiglare laminate according to any one of <1> to <9> above.
A manufacturing method comprising a step of crimping a patterned PET film on the surface of the hard coat layer to transfer an uneven shape.

According to the present invention, it is possible to provide an antiglare laminate having excellent antiglare properties and touch feeling when a polycarbonate resin is used.

Hereinafter, the present invention will be described in detail by exemplifying manufacturing examples, examples, etc., but the present invention is not limited to the exemplified manufacturing examples, examples, etc., and does not deviate significantly from the contents of the present invention. If so, it can be changed to any method.

In the antiglare laminate according to this embodiment, a base material 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 laminating the antiglare laminate is preferably a base material layer-a high hardness resin layer-a 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 surface of the base material 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-a hard coat layer. Further, in one embodiment, a high hardness resin layer and a hard coat layer can be provided on the other surface of the base material layer. In this case, the antiglare laminate has a structure of a hard coat layer-a high hardness resin layer-a base material layer-a high hardness resin layer-a hard coat layer.

When the high hardness tree layer is provided on both sides of the base material layer, it is more desirable to use the same high hardness tree layer on both sides for shape stability. Further, when the hard coat layer is provided on both sides of the base material, it is more preferable to provide the same hard coat layer on both sides because the shape stability is improved. The base material layer, the high-hardness resin layer, the high-hardness resin layer, and the hard coat layer may be directly laminated or may be laminated via another layer, but are preferably directly laminated. ..

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

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

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

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

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

Further, in recent years, since there is an increasing demand for bending the front plate as well, it is preferable to use a monohydric phenol represented by the following general formula (5) as a terminal terminator as the polycarbonate resin (al). ..

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

Formula (5) or the number of carbon atoms of R ⁵ in the general formula (6) is more preferably within a specific numerical range. Specifically, 36 is preferred as the upper limit of the carbon number of R ^5, and more preferably 22, 18 is particularly preferred. Further, as the lower limit of the number of carbon atoms of ^{R 5,} 8 are preferred, 12 is more _preferred.

When the upper limit of the carbon number of R ⁵ is suitably in the general formula (5) or the general formula (6), there is a tendency for organic solvent solubility is high monovalent phenols (terminating agent), when the polycarbonate resin production This is preferable because it increases the productivity of the resin.

As an example, if the carbon number of R ⁵ is 36 or less, high productivity in manufacturing the polycarbonate resin may be economical. When the number of carbon atoms in the R ⁵ is 22 or less, monohydric phenols are especially excellent in solubility in an organic solvent, can be very high productivity in manufacturing the polycarbonate resin is also improved economy.

When in formula (5) or the general formula (6) suitable lower limit of the carbon number of R ⁵ is in, not the fact that the glass transition temperature of the polycarbonate resin is too high, since it has a suitable thermoformability preferable.

As R ⁵ for example in the general formula (6), when using a monohydric phenol which is alkyl group of 16 carbon atoms (terminating agent), a glass transition temperature, melt flowability, moldability, drawdown resistance, polycarbonate resin The monohydric phenol at the time of production is excellent in solvent solubility, and is particularly preferable as a terminal terminator used for the polycarbonate resin in the present invention.

Among the monovalent phenols (terminal terminators) represented by the general formula (5) or the general formula (6), one or both of the parahydroxybenzoic acid hexadecyl ester and the parahydroxybenzoic acid 2-hexyldecyl ester are terminated. It is particularly preferable to use 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 further preferably 20,000 to 65,000. preferable. When the weight average molecular weight of the polycarbonate resin (a1) is 15,000 or more, the impact resistance can be increased, which is preferable. On the other hand, when the weight average molecular weight is 75,000 or less, the base material layer can be formed with a small amount of heat source, and the thermal stability can be maintained even when the molding conditions become high temperature, which is preferable. In the present specification, the weight average molecular weight is a standard polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

The polycarbonate resin (a1) contained in the base material layer may be one type or two or more types.

The content of the polycarbonate resin (a1) in the base material layer is preferably 75% by mass or more with respect to the total mass of the base material layer, and is 90% by mass or more from the viewpoint of improving impact resistance. It is more preferable, and it is further preferable that it is 100% by mass.

[Additive]
The base material layer may further contain additives.

As the additive, those usually used in the antiglare laminate can be used. Additives include, for example, antioxidants, anticolorants, antichargers, mold release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, organic particles and inorganic particles. Such as reinforcing materials.

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 with respect to the total mass of the base material layer. ..

The method of mixing the additive and the resin is not particularly limited, and a method of compounding the entire amount, a method of dry-blending the masterbatch, a method of dry-blending the entire amount, and the like 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 a high hardness resin. In addition, the high hardness resin layer may further contain additives and the like, if 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 having high shape stability. Further, the high hardness resin layer may have a function of increasing the hardness of the antiglare laminate. In the present specification, the high hardness resin is a resin having a hardness higher than that of the polycarbonate resin used as a base material, and has a pencil hardness of HB or higher, preferably HB to 3H, more preferably H to 3H, and even more preferably. It means a resin of 2H to 3H. 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, the hardness is gradually increased with respect to the surface of the hard coat layer at an angle of 45 degrees and a load of 750 g, and the pencil is pressed against the surface, and the hardness of the hardest pencil that does not cause scratches 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 the resin (B1) to the resin (B6). The resins (B1) to (B6) may be referred to as resins (B1) to resins (B6) even in the case of a resin composition containing a plurality of types of resins.

(Resin (B1))
The resin (B1) is a copolymer containing a (meth) acrylic acid ester structural unit (a) represented by the general formula (1) and an aliphatic vinyl structural unit (b) represented by the general formula (2). It is a resin. At this time, the resin (B1) (copolymerized resin) may further have other constituent units. The total ratio of the (meth) acrylic acid ester structural unit (a) and the aliphatic vinyl structural unit (b) is 90 to 100 mol%, preferably 95 to 100 mol% of the total structural units of the copolymer resin. It is 100 mol%, more preferably 98 to 100 mol%. Further, the ratio of the (meth) acrylic acid ester structural unit (a) is 65 to 80 mol% of the total structural units of the copolymer resin. In addition, in this specification, (meth) acrylic means 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 thereof include a methyl group, an ethyl group, a butyl group, a lauryl group, a stearyl group, a cyclohexyl group and an isobornyl group. Of these, R ² is preferably a methyl group or an ethyl group, and more preferably a methyl group.

When R ² is a methyl group or an ethyl group, the (meth) acrylic acid ester structural unit (a) represented by the general formula (1) is 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 (meth) acrylic acid ester structural unit (a) represented by the general formula (1) may contain only one type or two or more types in the resin (B1).

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 the present specification, the "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 the general formula (2) is a vinyl cyclohexane structural unit.

The aliphatic vinyl constituent 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 unit is not particularly limited, but the resin (B1) is obtained by hydrogenating the aromatic double bond derived from the aromatic vinyl monomer after polymerizing the (meth) acrylic acid ester monomer and the aromatic vinyl monomer. Examples thereof include a structural unit derived from an aromatic vinyl monomer containing a non-hydrogenated aromatic double bond, which is generated in the process of producing the above. Specific other structural units include styrene structural units.

The other constituent units may contain only one type in the resin (B1) or may contain two or more types.

The total ratio of the (meth) acrylic acid ester structural unit (a) and the aliphatic vinyl structural unit (b) is 90 to 100 with respect to the total of all the structural units of the resin (B1) (copolymerized resin). It is mol%, preferably 95 to 100 mol%, and more preferably 98 to 100 mol%.

The content of the (meth) acrylic acid ester structural unit (a) represented by the general formula (1) is 65 to 80 mol% with respect to all the structural units of the resin (B1) (copolymerized resin). It is preferably 70 to 80 mol%. When the content of the (meth) acrylic acid ester structural unit (a) is 65 mol% or more, a resin layer having excellent adhesion to the base material layer and surface hardness can be obtained. On the other hand, when the content of the (meth) acrylic acid ester structural unit (a) is 80 mol% or less, the antiglare laminate is less likely to warp due to water absorption, which is preferable.

The content of the aliphatic vinyl constituent unit (b) represented by the general formula (2) is preferably 20 to 35 mol% with respect to all the constituent units of the resin (B1) (copolymerized resin). , More preferably 20 to 30 mol%. When the content of the aliphatic vinyl constituent unit (b) is 20 mol% or more, warpage under high temperature and high humidity can be prevented, which is preferable. On the other hand, when the content of the aliphatic vinyl constituent unit (b) is 35 mol% or less, peeling at the interface with the base material can be prevented, which is preferable.

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

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

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

The glass transition temperature of the resin (B1) is preferably 110 to 140 ° C, more preferably 110 to 135 ° C, and particularly preferably 110 to 130 ° C. When the glass transition point is 110 ° C. or higher, the resin sheet is less likely to be deformed or cracked in a thermal environment or a moist thermal environment, which is preferable. On the other hand, when the temperature is 140 ° C. or lower, the workability is excellent when molding is performed by continuous heat shaping using a mirror surface roll or a shaping roll, or batch type heat shaping using a mirror surface mold or a shaping die. The glass transition temperature in the present invention is a temperature when measured by a differential scanning calorimetry device at a sample of 10 mg and 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 Company). The above-mentioned resin (B1) may be used alone or in combination of two or more.

The method for producing the resin composition (B1) is not particularly limited, but after polymerizing at least one (meth) acrylic acid ester monomer and at least one aromatic vinyl monomer, the fragrance derived from the aromatic vinyl monomer is used. Those obtained by hydrogenating a group double bond are preferable.

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

A known method can be used for the polymerization of the (meth) acrylic acid ester monomer and the aromatic vinyl monomer. For example, it can be produced by a massive polymerization method, a solution polymerization method, or the like.

The massive polymerization method is carried out by a method in which a monomer composition containing the above-mentioned monomer and a polymerization initiator is continuously supplied to a complete mixing tank and continuously polymerized at 100 to 180 ° C. The monomer composition may contain a chain transfer agent, if necessary.

The polymerization initiator is not particularly limited, but is 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-hexylpropoxyisopropylmonocarbonate, t-amyl Organic peroxides such as peroxynormal octoate, t-butylperoxyisopropyl monocarbonate, di-t-butyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methyl) Butylnitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and other azo compounds can be mentioned. These can be used alone or in combination of two or more.

The chain transfer agent is not particularly limited, and examples thereof include α-methylstyrene dimer.

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

The solvent used for 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 above-mentioned polymerization solvent. 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, alcohol solvents such as methanol and isopropanol. Examples include solvents.

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

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

Examples of the catalyst used in the hydrogenation reaction include metals such as nickel, palladium, platinum, cobal, ruthenium, and rhodium, or oxides, salts, or complex compounds of these metals, such as carbon, alumina, silica, and silica. Examples thereof include a solid catalyst supported on a porous carrier such as alumina and diatomaceous earth.

It is preferable that 70% or more of the aromatic double bond derived from the aromatic vinyl monomer is 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 less than 5%. Is even more preferable. When the dehydrogenation rate is less than 30%, a resin having excellent transparency can be obtained, which is preferable. 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 the transparency is not impaired. That is, the resin (B1) is a resin composition containing the above-mentioned copolymer and other resins. Examples of the other resin include methyl methacrylate-styrene copolymer resin, polymethyl methacrylate, polystyrene, polycarbonate, cycloolephine (co) polymer resin, acrylonitrile-styrene copolymer resin, and acrylonitrile-butadiene-styrene copolymer resin. , Various elastomers and the like.

(Resin (B2))
The resin (B2) contains 35 to 65% by mass, preferably 40 to 60% by mass of the resin (B1), and 35 to 65% by mass, preferably 40 to 65% by mass of the styrene-unsaturated dicarboxylic acid-based copolymer (C). Contains 60% by mass. Further, the styrene-unsaturated dicarboxylic acid copolymer (C) contains a styrene-based structural unit (c1) in an amount of 65 to 90% by mass and an unsaturated dicarboxylic acid anhydride constituent unit (c2) in an amount of 10 to 35% by mass. .. That is, the resin (B2) is a resin composition containing two or more kinds of resins. The content of the resin (B1) and the content of the styrene-unsaturated dicarboxylic acid-based copolymer (C) are the contents of the resin (B2) with respect to the total mass.

・ Resin (B1)
As the resin (B1), the above-mentioned one is used. At this time, the resin (B1) may be used alone or in combination of two or more.

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

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

The content of the styrene-based 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-based copolymer (C).

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

The content of the unsaturated dicarboxylic acid anhydride constituent 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-based copolymer (C). %.

Specific examples of the styrene-unsaturated dicarboxylic acid-based copolymer (C) include XIBOND140, XIBOND160, XIRAN SO23110, and XIRAN SO26080 (manufactured by Polyscape). These styrene-unsaturated dicarboxylic acid-based 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-based monomer and 45 to 90% by mass of the styrene-unsaturated dicarboxylic acid-based copolymer (E). The styrene-unsaturated dicarboxylic acid-based copolymer (E) contains 50 to 80% by mass of the styrene-based constituent unit (e1), 10 to 30% by mass of the unsaturated dicarboxylic acid-based constituent unit (e2), and vinyl-based. The structural unit (e3) is contained in an amount of 5 to 30% by mass. That is, the resin (B3) is a resin composition containing two or more kinds of resins. The content of the resin (D) containing the vinyl-based monomer and the content of the styrene-unsaturated dicarboxylic acid-based copolymer (E) are the contents of the resin (B3) with respect to the total mass.

-Resin (D) containing a vinyl-based monomer
The resin (D) containing a vinyl-based monomer is not particularly limited, but is limited to acrylonitrile, metaacrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and methacrylic acid. , Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate and the like, which are homopolymerized vinyl monomers. Of these, the resin (D) containing a vinyl-based monomer preferably contains methyl methacrylate as a constituent unit. The resin (D) containing the vinyl-based monomer may be a polymer using one kind of the structural unit, or a copolymer using two or more kinds in combination.

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

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

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

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

The content of the styrene-based 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-based copolymer (E).

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

The content of the unsaturated dicarboxylic acid anhydride constituent 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-based copolymer (E). %.

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

The content of the vinyl-based 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-based copolymer (E).

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

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

(Resin (B4))
The resin (B4) is a resin copolymer containing 5 to 20% by mass of a styrene constituent unit, 70 to 90% by mass of a (meth) acrylic acid ester constituent unit, and 5 to 20% by mass of an N-substituted maleimide constituent unit. (G), or an alloy of the resin copolymer (G) and the styrene-unsaturated dicarboxylic acid-based 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-based monomer The styrene-based monomer is not particularly limited, and any known styrene-based monomer can be used. Specific examples of the styrene-based monomer include styrene, a-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene and the like. Of these, styrene is particularly preferable from the viewpoint of compatibility. These styrene-based monomers may be used alone or in combination of two or more.

The content of the styrene constituent unit is 5 to 20% by mass, preferably 5 to 15% by mass, and more preferably 5 with respect to the total mass of the resin (B4) (resin copolymer (G)). ~ 10% by mass.

(Meta) Acrylic Acid Ester Structural Unit The (meth) acrylic acid ester monomer is not particularly limited, and is not particularly limited, and is acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and methacrylic acid. , Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate and the like. Of these, methyl methacrylate is preferable. 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 constituent 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 Constituent Unit The N-substituted maleimide monomer is not particularly limited, but N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, Examples thereof include N-arylmaleimides such as N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, and N-tribromophenylmaleimide. Of these, N-phenylmaleimide is preferable from the viewpoint of compatibility with the (meth) acrylic acid constituent unit. 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, it is 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, but are not limited to, Delpet PM120N (manufactured by Asahi Kasei Chemical Co., Ltd.).

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-based copolymer (E).

At this time, it is preferable that the resin copolymer (G) and the styrene-unsaturated dicarboxylic acid-based copolymer (E) are alloys having a high glass transition temperature.

The alloy manufacturing method is not particularly limited, and examples thereof include a method of melt-kneading at a cylinder temperature of 240 ° C. using a twin-screw extruder having a screw diameter of 26 mm, extruding into strands, and pelletizing with a pelletizer.

(Resin (B5))
The resin (B5) contains a structural unit (H) represented by the general formula (3). The resin (B5) is preferably a copolymer further containing the structural unit (J) represented by the general formula (4). In addition, the polymer may further contain other structural units.

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

The content of the structural unit (J) represented by the general formula (4) is preferably 0 to 50 mol% and 0 to 40 mol% with respect to all the structural units of the resin (B5). Is more preferable, and 0 to 30 mol% is further preferable.

The content of the other constituent units is preferably 10 mol% or less, more preferably 5 mol% or less, and preferably 2 mol% or less, based on all the constituent units of the resin (B5). Especially preferable.

The total content of the constituent unit (H) and the constituent unit (J) is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, based on all the constituent units of the resin (B5). It is preferably 98 to 100 mol%, 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, and particularly preferably 25,000 to 65,000.

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

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

(Resin (B6))
The resin (B6) contains 35 to 65% by mass of the resin (D) containing a vinyl-based monomer and 35 to 65% by mass of the styrene-unsaturated dicarboxylic acid-based copolymer (C). Further, the styrene-unsaturated dicarboxylic acid copolymer (C) contains a styrene-based structural unit (c1) in an amount of 65 to 90% by mass and an unsaturated dicarboxylic acid anhydride constituent unit (c2) in an amount of 10 to 35% by mass. .. That is, the resin (B6) is a resin composition containing two or more kinds of resins. The content of the resin (D) containing the vinyl-based monomer and the content of the styrene-unsaturated dicarboxylic acid-based copolymer (C) are the contents of the resin (B6) with respect to the total mass.

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

-Styrene-unsaturated dicarboxylic acid copolymer (C)
As the styrene-unsaturated dicarboxylic acid copolymer (C), the same one as described in the above resin (B2) is used. The styrene-unsaturated dicarboxylic acid copolymer (C) may be used alone or in combination of two or more.

By containing at least one selected from the group consisting of the above-mentioned 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. Therefore, it is preferable.

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

The additive is not particularly limited, and those usually used in antiglare laminates can be used. Specific examples include antioxidants, anticolorants, antistatic agents, mold release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, organic particles and inorganic particles. Reinforcement materials and the like can be mentioned.

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 with respect to the total mass of the high hardness resin layer. preferable.

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

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

The total thickness of the base material layer and the high hardness resin layer is preferably 100 to 3500 μm, more preferably 100 to 3000 μm, still more preferably 500 to 3000 μm, and particularly preferably 1200 to 3000 μm. When the total thickness is 100 μm or more, the rigidity of the sheet can be maintained, which is preferable. On the other hand, when the total thickness is 3500 μm or less, it is possible to prevent the sensitivity of the touch sensor from deteriorating when the touch panel is installed under the sheet, which is preferable.

The ratio of the thickness of the base material layer to the total thickness of the base material layer and the high hardness resin layer is preferably 75% to 99%, more preferably 80 to 99%, and particularly preferably 85 to 99%. be. 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 is a method of superimposing the individually formed base material layer and the high-hardness resin layer and heat-bonding the two; individually formed groups. A method of superimposing a material layer and a high-hardness resin layer and adhering them with an adhesive; a method of co-extruding a base material layer and a high-hardness resin layer; Examples thereof include a method in which the base material layer is in-molded and integrated. Of these, the coextrusion molding method is preferable from the viewpoint of manufacturing cost and productivity.

The coextrusion method is not particularly limited. For example, in the feed block method, a high-hardness resin layer is placed on one side of a base material layer with a feed block, extruded into a sheet shape with a T-die, and then cooled while passing through a molding roll to form a desired laminate. do. Further, in the multi-manifold method, a high-hardness resin layer is arranged on one side of the base material layer in the multi-manifold die, extruded into a sheet shape, and then cooled while passing through a molding roll to form a desired laminated body. ..

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

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

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

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

When a photopolymerizer is contained, the content of the photopolymerizer is 0. It is preferably 001 to 7 parts by mass, more preferably 0.01 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass. In the present specification, the photopolymerization initiator refers to a photoradical generator.

[(Meta) Acrylic Monomer]
As the (meth) acrylic monomer, any one in which the (meth) acryloyl group is present as a functional group in the molecule can be used. Specific examples thereof include monofunctional monomers, bifunctional monomers, and trifunctional or higher functional monomers.

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

Specific examples of bifunctional and / or trifunctional or higher (meth) acrylic monomers include diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate. 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol diacrylate hydroxypivalate, neopentyl glycol di (meth) acrylate, 1,4-Butanediol diacrylate, 1,3-butylene glycol di (meth) acrylate, dicyclopentanyldi (meth) acrylate, polyethylene glycol diacrylate, 1,4-butanediol oligoacrylate, neopentyl glycol oligoacrylate , 1,6-Hexanediol oligo acrylate, trimethylol propanetri (meth) acrylate, trimethylol propane ethoxytri (meth) acrylate, trimethylol propanepropoxytri (meth) acrylate, pentaerythritol tri (meth) acrylate, glyceryl propoxytri Examples thereof include (meth) acrylate, trimethylolpropane trimethacrylate, trimethylolpropaneethylene oxide adduct triacrylate, glycerin propylene oxide adduct triacrylate, and pentaerythritol tetraacrylate.

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

[(Meta) Acrylic Oligomer]
As the (meth) acrylic oligomer, a bifunctional or higher polyfunctional urethane (meth) acrylate oligomer (hereinafter, also referred to as “polyfunctional urethane (meth) acrylate oligomer”) or a bifunctional or higher polyfunctional polyester (meth) acrylate oligomer. (Hereinafter, also referred to as “polyfunctional polyester (meth) acrylate oligomer”), bifunctional or higher functional epoxy (meth) acrylate oligomer (hereinafter, also referred to as “polyfunctional epoxy (meth) acrylate oligomer”) and the like can be mentioned.

As the polyfunctional urethane (meth) acrylate oligomer, a urethanization reaction product of a (meth) acrylate monomer having at least one (meth) acryloyloxy group and a hydroxyl group in one molecule and a polyisocyanate; polyols are poly. Examples thereof include a urethanization reaction product of an isocyanate compound obtained by reacting with isocyanate and a (meth) acrylate monomer having at least one (meth) acryloyloxy group and a hydroxyl group in one molecule.

Examples of the (meth) acrylate monomer having at least one (meth) acryloyloxy group and a hydroxyl group in one molecule used in the urethanization reaction include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. 2-Hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerindi (meth) acrylate, trimethylpropandi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta Examples include (meth) acrylate.

The polyisocyanate used in the urethanization reaction includes hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and diisocyanate obtained by hydrogenating aromatic isocyanates among these diisocyanates. (For example, diisocyanate such as hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate), di or tri polyisocyanate such as triphenylmethane triisocyanate, dimethylene triphenyl triisocyanate, or polyisocyanate obtained by increasing the amount of diisocyanate. Can be mentioned.

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

Usually, aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, trimethylolethane, trimethylolpropane, dimethylolheptan, and di. Examples thereof include methylolpropionic acid, dimethylolbutylionic acid, glycerin, and hydrogenated bisphenol A.

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

Examples of the polyether polyol include polyalkylene glycols and 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. The polyols used in the dehydration condensation reaction include 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimethylolheptan, dimethylolpropionic acid, and dimethylol. Butyrionic acid, trimethylolpropane, trimethylolpropane, pentaerythritol, dipentaerythritol and the like can be mentioned.

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 type or two or more types of (meth) acrylic oligomers.

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

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

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, and anionic surfactant.

Examples of the surfactant and the water- and oil-repellent agent include fluorine-containing surfactants such as fluorine-containing group / lipophilic group-containing oligomers, fluorine-containing groups / hydrophilic groups, lipophilic groups, and UV-reactive group-containing oligomers. Activators and water repellents and oil repellents can be mentioned.

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

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

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

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

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

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

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

Since the hard coat layer has an uneven shape, it is possible to obtain an antiglare laminate having excellent antiglare properties and touch comfort. Specifically, the hard coat layer has the following equations (1) to (3) for the arithmetic mean roughness (Ra), maximum mountain height (Rp), maximum valley depth (Rv), and skewness (Rsk). Fulfill. In the present specification, the arithmetic mean roughness (Ra), the maximum peak height (Rp), the maximum valley depth (Rv), and the skewness (Rsk) are measured by JIS B0601 1994 cutoff 0.8.

Regarding the above formula (1), the arithmetic mean roughness (Ra) is an index of antiglare. When Ra is 0.03 or less, light scattering is insufficient and antiglare is insufficient. On the other hand, when Ra is 0.10 or more, light scattering becomes excessive and whitening occurs, resulting in poor texture. The formula (1) more preferably satisfies 0.035 <Ra <0.095, and further preferably 0.040 <Ra <0.92.

Regarding the above formula (2), Rp / Rv indicates that the uneven shape of the hard coat layer has a deeper valley than the height of the mountain, and is an index for maintaining a balance between antiglare and finger slipperiness. When Rp / Rv is 0.15, the antiglare property is lowered. On the other hand, when Rp / Rv is 0.30 or more, the finger slipperiness deteriorates. The formula (2) more preferably satisfies 0.16 <Rp / Rv <0.29, and further preferably 0.17 <Rp / Rv <0.28.

Regarding the above equation (3), skewness (Rsk) is an index showing the symmetry of the peak portion and the valley portion. When the skewness (Rsk) becomes a negative value, it indicates that there are many valleys. Since the skewness (Rsk) is within the range of the equation (3), the uneven shape has more valleys than the peaks, and the balance between antiglare and finger slipperiness can be maintained. It is more preferable that the formula (3) satisfies −4.8 <Rsk <−2.5.

Further, the hard coat layer uses a tactile contact as a contact, and the dynamic friction coefficient (μk) measured at a load of 50 g, a scanning speed of 10 mm / sec, and a scanning distance of 90 mm satisfies the following formula (4). Unlike the felt and needle-shaped contacts that are normally used, the tactile contacts used in this measurement method are contacts that imitate human fingers, so it is possible to quantitatively evaluate finger slipperiness. can. The dynamic friction coefficient (μK) is specifically measured by the method described in Examples.

Regarding the above equation (4), the coefficient of dynamic friction (μk) is an index of finger slipperiness. When the coefficient of kinetic friction (μk) is in the range of the equation (4), an appropriate finger slipperiness can be obtained.

By satisfying the above formulas (1) to (3), the hard coat layer can be formed into an uneven shape mainly having excellent antiglare properties. Further, when the hard coat layer satisfies the above formula (4), it is possible to obtain mainly excellent finger slipperiness. As a result, it is possible to obtain an antiglare laminate having excellent antiglare properties and touch comfort.

_{In one embodiment, it is preferable that the reflectance (SCI 550} ) including the specularly reflected light and the reflectance (SCE ₅₅₀ ) excluding the specularly reflected light of the hard coat layer satisfy the following formula (5). In the present specification, the reflectance including the positively reflected light (SCI ₅₅₀ ) and the reflectance excluding the _{normally reflected light (SCE 550} ) are measured using a spectrocolorimeter SD7000 (manufactured by Nippon Denshoku). By treating the back surface with a black spray to blacken the back surface, it is possible to suppress the reflection on the back surface and measure only the reflection on the front surface.

Regarding the above formula (5), SCE ₅₅₀ / SCI ₅₅₀ is an index of anti-reflection performance. When SCE ₅₅₀ / SCI ₅₅₀ is more than 0.25, light can be preferably scattered and antiglare property is enhanced, which is preferable. On the other hand, when SCE ₅₅₀ / SCI ₅₅₀ is less than 0.60, light scattering does not become excessive, whitening can be prevented, and a suitable texture can be obtained, which is preferable.

[Method of 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 on a layer located below the hard coat layer (for example, a high hardness resin layer) and then photopolymerizing the hard coat layer. ..

The method of applying the hard coat liquid (polymerizable composition, reaction composition) is not particularly limited, and a known method can be used. For example, spin coating method, dip method, spray method, slide coating method, bar coating method, roll coating method, gravure coating method, meniscus coating method, flexographic printing method, screen printing method, beat coating method, handling method and the like can be mentioned. ..

As the lamp used for light irradiation in photopolymerization, a lamp having a light emission distribution with a light wavelength of 420 nm or less is used. Examples thereof include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, and metal halide lamps. Among these, high-pressure mercury lamps or metal halide lamps efficiently emit light in the active wavelength region of the initiator, and heat short-wavelength light or reaction compositions that reduce the viscoelastic properties of the obtained polymer by cross-linking. This is preferable because it does not emit a large amount of long-wavelength light that causes evaporation.

The irradiation intensity of the lamp is a factor that affects the degree of polymerization of the obtained polymer, and is appropriately controlled for each performance of the target product. When a cleavage-type initiator having a normal acetophenone group is blended, the illuminance 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 illuminance 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 to carry out light irradiation using a method that can eliminate the reaction inhibition due to oxygen. One such method is to cover the reactive composition with a film made of polyethylene terephthalate or Teflon to cut off contact with oxygen, and irradiate the reactive composition with light through the film. Further, the 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 keep the atmospheric oxygen concentration at a low level. Due to the introduction of this inert gas, an air flow is generated on the surface of the reactive composition, and monomer evaporation occurs. In order to suppress the level of monomer evaporation, the air velocity of the inert gas is preferably 1 m / sec or less as a relative velocity with respect to the laminate coated with the hard coat liquid moving under the atmosphere of the inert gas. It is more preferably 0.1 m / sec or less. By setting the airflow velocity within the above range, monomer evaporation due to the airflow is substantially suppressed.

The coated surface may be pretreated for the purpose of improving the adhesion of the hard coat layer. Known treatment examples include 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 (anti-glare treatment) is not particularly limited, but a method using a mold is preferable. For example, first, the high hardness resin layer, the coating film obtained by applying the reactive composition, and the mold are laminated in this order. Then, a method of photopolymerizing the reactive composition and demolding the mold can be mentioned. The photopolymer (hard coat layer) of the reactive composition has a shape that reflects the rough surface of the mold on the 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, or the like is used. In one embodiment, the mold includes a mold in which a transparent film and a transparent resin having a rough surface are laminated. Examples of the transparent film include a PET film. Examples of the transparent resin having the 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.) to the transparent resin, or by etching the transparent resin. It may be formed, or it may be formed by printing and curing a transparent resin. The shape of the rough surface is not particularly limited, but it is preferably a pattern from the viewpoint of being used for applications such as liquid crystal panels. The surface (concavo-convex shape) of the hard coat layer can be controlled by controlling the type of mold used (material, surface haze, thickness, shape, etc.), the amount of particles to be added, and the like. As a result, a hard coat layer satisfying the above formulas (1) to (4) can be formed. Further, preferably, a hard coat layer satisfying the above formula (5) can be formed.

Among the above-mentioned methods for forming the hard coat layer, it is preferable to press-bond a patterned PET film to transfer the uneven shape. That is, according to one embodiment of the present invention, there is provided a method for producing an antiglare laminate. At this time, the manufacturing method includes a step of pressing the patterned PET film on the surface of the hard coat layer to transfer the uneven shape. As the patterned PET film, for example, Unitika's emblem PTH, PTHA, PTHZ, Daicel's low-glare AG film PF11, PF23, and the like can be used.

<Physical characteristics of antiglare laminate>
In one embodiment, the antiglare laminate preferably has high shape stability. Specifically, the amount of change in warpage after being held at 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 75 μm or less is particularly preferable. When the amount of change in warpage is 350 μm or less, it is preferable because it can be suitably used even in a high temperature and high humidity environment. 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 antiglare laminate is stable even in a high temperature and high humidity environment. The material of the base material layer and the hard coat layer, the difference in the 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. The shape stability can also be controlled by appropriately changing the difference, the difference in hardness, and the like.

<Use>
Since the above-mentioned antiglare laminate is excellent in antiglare property and touch feeling, it is used as a protective plate or a front plate of a liquid crystal surface as described above. In one embodiment, an in-vehicle display device including an antiglare laminate is provided. Further, in another well embodiment, a touch panel front surface protective plate including an antiglare laminate is provided. Further, in another embodiment, a front plate for an OA device, a portable electronic device, or a television is provided.

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

<Surface roughness measurement>
Using the surface roughness measuring machine "SURFCOM 480A" manufactured by Tokyo Seimitsu Co., Ltd., the surface of the hard coat layer having an uneven surface is subjected to arithmetic average roughness (Ra) and maximum mountain height (Rp) in accordance with JIS B0601 1994. ), Maximum valley depth (Rv), and skewness (Rsk) were measured under the following conditions.

[Surface roughness measurement conditions]
Cut-off value: 0.8 mm
Evaluation length: 5 times the cutoff value Feeding speed of stylus: 0.3 mm / s
Spare length: twice the cutoff value

<Measurement of dynamic friction coefficient>
The coefficient of dynamic friction (μk) on the surface of the hard coat layer was measured under the following conditions using a static friction measuring machine "TL201Tt" manufactured by Trinity Lab.

[Dynamic friction coefficient measurement conditions]
Contact: Tactile contact Load: 50 g
Scanning speed: 10 mm / s
Scanning distance: 90 mm

<Reflectance measurement>
Using a spectrocolorimeter "SD7000" manufactured by Nippon Denshoku Co., Ltd., the reflectance (SCI) including the positively reflected light and the reflectance (SCE) excluding the positively reflected light of the hard coat layer were measured under the following conditions. The reflectances at a wavelength of 550 nm were defined as SCI ₅₅₀ and SCE ₅₅₀ , respectively. The back surface was treated black with a black color spray to suppress reflection on the back surface.

[Reflectance measurement conditions]
Light source / field of view: D65 / 2 °
Measurement diameter: φ8 mm (MAV)
Lighting and light receiving conditions: di 8 ° (SCI), de 8 ° (SCE)

<SW hardness>
For the hard coat layer having the uneven shape of the antiglare laminate, using steel wool # 0000 made by Nippon Steel Wool, the degree of damage when 15 reciprocations with a load of ^{100 g / cm 2 are visually evaluated on a 10-point scale.} bottom. It is described by RANK1 to RANK10. The measurement was performed twice, and if different results were obtained, the range was used as the measurement result.

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

<Shape stability>
The test piece (antiglare laminate) was cut out to a size of 100 mm × 60 mm. The cut out test piece was set in a two-point support type holder and put into an environmental tester set at a temperature of 23% and a relative humidity of 50% for 24 hours or more to adjust the state, and then the warp was measured (before processing). Next, the test piece was set in a holder and placed in an environmental tester set at a temperature of 85 ° C. and a relative humidity of 85%, and held in that state for 120 hours. Further, the holder was moved into an environmental tester set at a temperature of 23% and a relative humidity of 50%, and the warp was measured again after holding for 4 hours in that state (after treatment). To measure the warp, use a three-dimensional shape measuring machine equipped with an electric stage (KS-1000 manufactured by KEYENCE), place the taken-out test piece horizontally in a convex state upward, scan at 1 mm intervals, and scan the central part. The excitement was measured as a sled. Absolute value of the difference in the amount of warpage before and after treatment, that is, | (warp amount after treatment)-(warp amount before treatment) |
Was evaluated as shape stability.

[Example 1]
<Laminated body>
Synthetic resin using 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 extruders, and a multi-layer extruder having a T-die connected to the feed block. The laminate was molded. Optimas 7500 manufactured by Mitsubishi Gas Chemical Company was continuously introduced as a high-hardness resin (B1) into a single-screw extruder having a shaft diameter of 35 mm, and extruded under the conditions of a cylinder temperature of 240 ° C. and a discharge rate of 2.6 kg / h. In addition, polycarbonate resin (manufactured by Mitsubishi Engineering Plastics, trade name: Iupiron S-1000) is 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. rice field. The feed block connected to all extruders was equipped with two types and two layers of distribution pins, and a high hardness resin (B1) and a polycarbonate resin were introduced and laminated at a temperature of 270 ° C. A T-die with a temperature of 270 ° C connected to the tip extrudes it into a sheet, and three mirror-finishing rolls with temperatures of 120 ° C, 130 ° C, and 190 ° C are used to cool the resin while transferring the mirror surface. A laminate of the layer (B1) (high hardness resin layer) and the 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.

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

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

<PET film with pattern (Z-1)>
Acrylic UV curable resin (100% solid content, trade name: Light acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.) 40 parts by mass, silica dispersion (18% solid content, Z-AGD-6) with respect to 35 parts by mass of MEK. , 25 parts by mass of an average particle size of 2 μm, manufactured by Aika Kogyo Co., Ltd., and 3 parts by mass of a photoinitiator (trade name: Omnirad 184, manufactured by IGM Resins) were mixed and stirred to prepare a coating liquid (i). Next, the coating liquid (i) is applied to a PET (polyethylene terephthalate) film so as to have a dry film thickness of 2.5 μm, dried at 80 ° C. for 2 minutes, and then equipped with a high-pressure mercury lamp having a light source distance of 12 cm and an output of 80 W / cm. A patterned PET film (Z-1) was produced by irradiating ultraviolet rays on a conveyor at a line speed of 1.5 m / min and curing the film.

After curing the photocurable resin composition (Y-1) 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). Was applied using a bar coater so that the thickness of the coating film was 5 to 10 μm, and the patterned surface of the patterned PET film (Z-1) was covered and pressure-bonded so as to come into contact with the coating liquid. After that, a metal halide lamp (20 mW / cm) with a light source distance of 12 cm was irradiated for 30 seconds to cure, the patterned PET film was peeled off, and an antiglare antiglare provided with an uneven hard coat layer on the high hardness resin layer (B1). A sex 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 (B2) was used instead of the high hardness resin (B1).

The high hardness resin (B2) was prepared as follows. That is, 40% by mass of the high hardness resin (B1) and 60% by mass of XIBOND140 as a styrene-unsaturated dicarboxylic acid-based copolymer (C) were charged and mixed with a blender for 30 minutes. Next, using an extruder with a screw diameter of 26 mm (manufactured by Toshiba Machine Co., Ltd., TEM-26SS, L / D≈40), melt-kneading is performed at a cylinder temperature of 230 ° C., extruded into strands, and pelletized with a pelletizer. A resin composition (B2) was obtained. Pelletization was stable.

[Example 3]
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).

The high hardness resin (B3) was prepared as follows. That is, 75% by mass of R-100 as the styrene-unsaturated dicarboxylic acid-based copolymer (E) and 25% by mass of the methyl methacrylate resin Parapet HR-L as the resin (D) containing the vinyl-based monomer were charged and blended. Was mixed for 30 minutes. Next, using an extruder with a screw diameter of 26 mm (manufactured by Toshiba Machine Co., Ltd., TEM-26SS, L / D≈40), melt-kneading is performed at a cylinder temperature of 230 ° C., extruded into strands, and pelletized with a pelletizer. A high hardness resin (B3) was obtained. Pelletization was stable.

[Example 4]
An antiglare laminate was produced in the same manner as in Example 1 except that the following high hardness resin (B4) was used instead of the high hardness resin (B1).

The high hardness resin (B4) was prepared as follows. That is, as the styrene-unsaturated dicarboxylic acid-based copolymer (E), a copolymer of 21% by mass of methyl methacrylate constituent unit, 64% by mass of styrene constituent unit, and 15% by mass of maleic anhydride constituent unit (Registfy R100 (Registfy R100 (Registry R100) Denka)) 75% by mass, and as the resin copolymer (G), 7% by mass of the styrene constituent unit, 86% by mass of the methyl methacrylate constituent unit, and 7% by mass of the N-phenylmaleimide constituent unit, the copolymer Delpet. PM-120N (manufactured by Asahi Kasei) and 25% by mass were charged and mixed with a blender for 30 minutes. Next, using an extruder with a screw diameter of 26 mm (manufactured by Toshiba Machine Co., Ltd., TEM-26SS, L / D≈40), melt-kneading is performed at a cylinder temperature of 230 ° C., and the mixture is extruded into strands and pelletized with a pelletizer. A high-hardness resin (B4), which is an alloy of the resin copolymer (G) and the styrene-unsaturated dicarboxylic acid-based copolymer (E), was obtained. Pelletization was stable.

[Example 5]
Instead of the high hardness resin (B1), Iupiron KH3410UR (bisphenol C polycarbonate resin, manufactured by Mitsubishi Engineer Plastics), which is a high hardness resin (B5), is used, and a single shaft diameter of 35 mm is used to introduce the high hardness resin (B5). An antiglare laminate was produced in the same manner as in Example 1 except that the cylinder temperature of the shaft extruder was changed from 240 ° C. to 270 ° C.

[Example 6]
An antiglare laminate was produced in the same manner as in Example 1 except that the following high hardness resin (B6) was used instead of the high hardness resin (B1).

The high hardness resin (B6) was prepared as follows. That is, 50% by mass of XIBOND160 as a styrene-unsaturated dicarboxylic acid-based copolymer (C) and 50% by mass of methyl methacrylate resin Parapet HR-L as a resin (D) containing a vinyl-based monomer were charged, and 30% by blender was used. The mixture was mixed for a minute. Next, using an extruder with a screw diameter of 26 mm (manufactured by Toshiba Machine Co., Ltd., TEM-26SS, L / D ≈40), melt kneading was performed at a cylinder temperature of 230 ° C., extruded into strands, pelletized with a pelletizer, and made into a high hardness resin. (B6) was obtained. Pelletization was stable.

[Example 7]
An antiglare laminate was produced in the same manner as in Example 1 except that the following patterned PET film (Z-2) was used instead of the patterned PET film (Z-1).

<PET film with pattern (Z-2)>
Instead of the coating liquid (i), the following coating liquid (ii) was used to prepare a patterned PET film (Z-2).

The coating liquid (ii) contains 40 parts by mass of an acrylic ultraviolet curable resin (100% solid content, trade name: light acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.) and a silica dispersion liquid (solid content 18) with respect to 10 parts by mass of MEK. %, Z-AGD-6, average particle size 2 μm, manufactured by Aika Kogyo Co., Ltd.) 50 parts by mass, and photoinitiator (trade name Omnirad 184, manufactured by IGM Resins) were mixed and stirred by 3 parts by mass. ..

[Example 8]
An antiglare laminate was produced in the same manner as in Example 1 except that the following patterned PET film (Z-3) was used instead of the patterned PET film (Z-1).

<PET film with pattern (Z-3)>
Instead of the coating liquid (i), the following coating liquid (iii) was used to prepare a patterned PET film (Z-2).

The coating liquid (ii) is an acrylic ultraviolet curable resin (solid content 100%, trade name: light acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.), 40 parts by mass, and a silica dispersion liquid (solid content 18%, Z-AGD-). 6. 60 parts by mass of an average particle size of 2 μm, manufactured by Aika Kogyo Co., Ltd., and 3 parts by mass of a photoinitiator (trade name: Omnirad 184, manufactured by IGM Resins) were mixed and stirred as an external addition.

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

[Comparative Example 1]
Cosmoshine (registered trademark) A-4100 (PET film, thickness: 100 μm, haze: 0.9%, manufactured by Toyobo) (Z-4) was used instead of the patterned PET film (Z-1). An antiglare laminate was produced in the same manner as in Example 1 except for the above.

[Comparative Example 2]
Example 1 and Example 1 except that PS-27 (PET film, thickness: 100 μm, haze 34%, manufactured by Daicel) (Z-5) was used instead of the patterned PET film (Z-1). An antiglare laminate was produced in the same manner.

[Comparative Example 3]
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, with respect to 50 parts by mass of MEK, 50 parts by mass of acrylic ultraviolet curable resin (100% solid content product: light acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.), silica fine particles (octylsilane-treated fumed silica, average primary particle diameter 1). .9 μm, trade name: SE6050-SYB manufactured by Admatex Co., Ltd., and 3 parts by mass of photoinitiator (trade name: Irgacure 184 manufactured by Toyotsukemi Plus Co., Ltd.) are mixed and stirred to form a photocurable composition (Y-2). ) Was prepared.

The photocurable composition (Y-2) was applied onto the high hardness layer of the laminate (X-1) using a bar coater so that the coating thickness after curing was 2.5 μm, and at 80 ° C. It was dried for 2 minutes. An antiglare laminate was obtained by irradiating with a metal halide lamp (20 mW / cm) for 30 seconds at a light source distance of 12 cm and curing while purging nitrogen.

Table 1 below shows the antiglare laminates obtained in Examples 1 to 9 and Comparative Examples 1 to 3.

Further, in Examples 1 to 9 and Comparative Examples 1 to 3, the arithmetic mean roughness (Ra), the maximum mountain height (Rp), the maximum valley depth (Rv), Rp / Rv, the skewness (Rsk), and the dynamic friction coefficient ( μk), SCI ₅₀₀ , SCE ₅₀₀ , SCE ₅₅₀ / SCI ₅₀₀ , SW hardness, and shape stability were evaluated. The obtained results are shown in Table 2 below.

As is clear from the results in Table 2, in Examples 1 to 9, Ra, Rp / Rv, and Rsk satisfy the formulas (1) to (3), and μK satisfies the formula (4). It can be seen that it has excellent anti-glare properties and feel. Further, in Examples 1 to 9, _{it is confirmed that SCE 500} / SCI ₅₀₀ is excellent in antiglare property because it satisfies the formula (5). It was confirmed that Examples 1 to 8 using the high hardness resins (B1) to (B6) were also excellent in shape stability.

On the other hand, in Comparative Example 1, since Rp / Rv and Rsk did not satisfy the formulas (2) and (3) and μK did not satisfy the formula (4), the antiglare property and the touch feeling were insufficient. From the viewpoint of reflectance _{, it was confirmed that SCE 500} / SCI ₅₀₀ did not satisfy the formula (5) and had insufficient antiglare property.

Further, in Comparative Example 2, Ra and Rp / Rv did not satisfy the formulas (1) and (2), and μK did not satisfy the formula (4), so that the antiglare property and the touch feeling were insufficient. From the viewpoint of reflectance _{, it was confirmed that SCE 500} / SCI ₅₀₀ did not satisfy the formula (5) and had insufficient antiglare property.

Further, in Comparative Example 3, since Ra, Rp / Rv, and Rsk do not satisfy the formulas (1) to (3) and μK does not satisfy the formula (4), the antiglare property and the touch feeling are insufficient. rice field. Although SCE ₅₀₀ / SCI ₅₀₀ satisfied the formula (5), it was confirmed that the SW hardness was insufficient because the hard coat layer contained silica fine particles.

Claims

An antiglare laminate in which a base material layer containing at least a polycarbonate resin (a1), a high hardness resin layer containing a high hardness resin, and a hard coat layer are arranged in this order.
The arithmetic mean roughness (Ra), maximum peak height (Rp), maximum valley depth (Rv), and skewness (Rsk) of the hard coat layer are expressed by the following equations (1) to (3):

The filling,
Using a tactile contactor as the contactor of the hard coat layer, the dynamic friction coefficient (μk) measured at a load of 50 g, a scanning speed of 10 mm / sec, and a scanning distance of 90 mm is obtained by the following equation (4):

Anti-glare laminate that meets the requirements.
The reflectance (SCI 550 ) including the specularly reflected light and the reflectance (SCE 550 ) excluding the specularly reflected light of the hard coat layer at a wavelength of 550 nm are calculated by the following equation (5):

The antiglare laminate according to claim 1.
The antiglare laminate according to claim 1 or 2, wherein the amount of change in warpage after the antiglare laminate is held at a temperature of 85 ° C. and a relative humidity of 85% for 120 hours is 350 μm or less.
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 material layer and the high hardness resin layer is 100 to 3,000 μm.
High hardness resin (B)
The following general formula (1):

(In the formula, R 1 is a hydrogen atom or a methyl group, and R 2 is an alkyl group having 1 to 18 carbon atoms.)
The (meth) acrylic acid ester structural unit (a) represented by and the following general formula (2):

(In the formula, R 3 is a hydrogen atom or a methyl group, and R 4 is a cyclohexyl group which may have a hydrocarbon machine having 1 to 4 carbon atoms.)
It is a copolymer resin containing the aliphatic vinyl structural unit (b) represented by, and the total ratio of the (meth) acrylic acid ester structural unit (a) and the aliphatic vinyl structural unit (b) is the same. The resin (B1) is 90 to 100 mol% of all the constituent units of the polymerized resin, and the ratio of the (meth) acrylic acid ester constituent unit (a) is 65 to 80 mol% of all the constituent units of the copolymerized resin. ),
The resin (B1) is 35 to 65% by mass, the styrene-unsaturated dicarboxylic acid copolymer (C) is 35 to 65% by mass, and the styrene-unsaturated dicarboxylic acid copolymer (C) is styrene-based. The resin (B2), which contains the structural unit (c1) in an amount of 65 to 90% by mass and the unsaturated dicarboxylic acid anhydride structural unit (c2) in an amount of 10 to 35% by mass.
The resin (D) containing a vinyl monomer is contained in an amount of 55 to 10% by mass, and the styrene-unsaturated dicarboxylic acid-based copolymer (E) is contained in an amount of 45 to 90% by mass. The coalescence (E) is 50 to 80% by mass of the styrene-based constituent unit (e1), 10 to 30% by mass of the unsaturated dicarboxylic acid constituent unit (e2), and 5 to 30% by mass of the vinyl-based constituent unit (e3). Including, resin (B3),
A resin copolymer (G) containing 5 to 20% by mass of a styrene constituent unit, 70 to 90% by mass of a (meth) acrylic acid ester constituent unit, and 5 to 20% by mass of an N-substituted maleimide constituent unit, or a resin. A resin (B4), which is an alloy of the polymer (G) and a styrene-unsaturated dicarboxylic acid-based copolymer (E).
The following general formula (3):

35 to 65% by mass of the resin (B5) containing the structural unit (H) represented by, and the resin (D) containing a vinyl-based monomer, and the styrene-unsaturated dicarboxylic acid-based copolymer (C). 35 to 65% by mass, and the styrene-unsaturated dicarboxylic acid copolymer (C) contains 65 to 90% by mass of the styrene-based structural unit (c1) and 10 of the unsaturated dicarboxylic acid anhydride constituent unit (c2). The antiglare laminate according to any one of claims 1 to 5, which comprises at least one selected from the group consisting of resin (B6), which comprises ~ 35% by mass.
The resin (B5) has the following general formula (4):

The antiglare laminate according to claim 6, which is a copolymer further containing the structural unit (J) represented by.
The antiglare laminate according to any one of claims 1 to 7, wherein the hard coat layer does not contain organic particles and 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 R 6 may independently have a hydrogen atom, a halogen, or a substituent. It represents a good alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, and n is an integer of 0 to 4, wherein the substituent is a halogen, an alkyl group having 1 to 20 carbon atoms, and the like. Alternatively, it is an aryl group having 6 to 12 carbon atoms.)
The antiglare laminate according to any one of claims 1 to 8, which contains a component derived from monohydric phenol represented by.
An in-vehicle display device including the antiglare laminate according to any one of claims 1 to 9.
A touch panel front protective plate including the antiglare laminate according to any one of claims 1 to 9.
A front plate for OA equipment, portable electronic equipment, or a television, which comprises the antiglare laminate according to any one of claims 1 to 9.
The method for producing an antiglare laminate according to any one of claims 1 to 9.
A manufacturing method comprising a step of crimping a patterned PET film on the surface of the hard coat layer to transfer an uneven shape.