KR102507695B1 - Anti-glare hard coat laminate - Google Patents

Abstract

[Problem] To provide a laminate comprising a hard coat layer that is excellent in anti-glare properties and exhibits high scratch resistance, as well as excellent adhesion to a base material.
[Solution] An anti-glare hard coat laminate comprising a base material, a primer layer above the base material, and a hard coat layer above the primer layer, wherein the primer layer is a siloxane having a specific radical polymerizable double bond. It is made of a cured product of a composition for forming a primer layer containing an oligomer, and the hard coat layer is at both ends of a molecular chain containing (a) a polyfunctional monomer and (b) a poly(oxyperfluoroalkylene) group. , a perfluoropolyether bonded to an active energy ray polymerizable group via a poly(oxyalkylene) group or via a poly(oxyalkylene) group and one urethane bonding group in this order, (c) organic particulates, and (d) An anti-glare hard coat laminate made of a cured product of a curable composition containing a polymerization initiator and a method for producing the same.

Description

Anti-glare hard coat laminate

The present invention relates to an anti-glare hard coat laminate having a hard coat layer having excellent anti-glare properties (anti-glare function) and a manufacturing method thereof.

A large number of products with touch panels mounted on flat panel displays such as personal computers, mobile phones, portable game machines, and ATMs are being commercialized. In particular, with the advent of smart phones and tablet PCs, the number of capacitive touch panels with multi-touch functions is rapidly increasing.

On the surface of these touch panel displays, a method of attaching an anti-glare hard coat film having a hard coat layer of several μm with concavities and convexities formed on the surface is used to prevent deterioration in visibility due to external light shining on the screen. there is. As a method for forming irregularities on the surface, a method in which fine particles having a particle size of about several μm are contained in the hard coat layer is generally used.

By the way, in the capacitance-type touch panel, operation is performed by contacting with a human finger. For this reason, whenever an operation is performed, a fingerprint adheres to the surface of the touch panel, and the visibility of the image on the display is significantly impaired, or the appearance of the display is deteriorated. Fingerprints contain sweat-derived moisture and sebum-derived oil, and in order to make it difficult for both of them to adhere, it is strongly desired to impart water and oil repellency to the hard coat layer on the surface of the display.

However, capacitive touch panels are touched by people's fingers every day, so even if the antifouling properties in the initial stage have reached a considerable level, these functions often deteriorate due to scratches during use. In particular, in the case of the anti-glare hard coat layer, since it has irregularities on its surface, it is easy to catch and scratch easily. For this reason, durability of antifouling property in the process of use has been a problem.

Until now, as a hard coat layer having anti-glare and scratch resistance, as a component imparting antifouling and scratch resistance to the surface of the hard coat layer, a poly(oxyperfluoroalkylene) structure and a (meth)acryloyl group in the molecule A technique using methyl methacrylate-styrene copolymer (MS) resin fine particles as a surface modifier and a component imparting anti-glare properties to the hard coat layer is disclosed (Patent Document 1).

Japanese Unexamined Patent Publication No. 2013-257359

In the method specifically described in Patent Document 1, the problem is that the fluorine content of the surface modifier having a poly(oxyperfluoroalkylene) structure and a (meth)acryloyl group in the molecule is low, and sufficient antifouling and scratch resistance cannot be obtained. there was. In addition, when the amount of MS resin particles added to obtain scratch resistance is reduced, sufficient anti-glare properties cannot be obtained, and when MS resin particles are added to the extent that sufficient anti-glare properties are obtained, there is a problem that the scratch resistance is remarkably reduced. Furthermore, it was also a subject that the dispersibility of the resin particles in the hard coat layer was poor, forming aggregates and impairing the appearance of the coating film.

Moreover, it was also a subject that the hard coat layer using an acrylic resin was inferior in adhesiveness with a glass base material especially, and it peeled easily from a base material.

In this way, while being excellent in anti-glare properties and exhibiting high scratch resistance, a hard coat layer having excellent adhesion to a base material has been demanded.

As a result of repeated intensive studies in order to achieve the above object, the inventors of the present invention have found that a primer layer is provided between the substrate and the hard coat layer in order to improve the adhesion to the substrate, particularly in the material for forming the primer layer. It was found to employ a siloxane oligomer having a synthetic double bond. And, at both ends of the molecular chain containing the poly(oxyperfluoroalkylene) structure, through a poly(oxyalkylene) group or through a poly(oxyalkylene) group and one urethane bond group, an active energy ray By employing a curable composition in which a compound binding a polymerizable group is used as a fluorine-based surface modifier and organic particulates are added thereto as a material for forming a hard coat layer, excellent anti-glare properties and high scratch resistance are obtained on the primer layer, and It was discovered that a laminate having a hard coat layer having excellent adhesion was obtained, and the present invention was completed.

That is, the present invention, as a first aspect,

An anti-glare hard coat laminate comprising a base material, a primer layer above the base material, and a hard coat layer above the primer layer,

The primer layer,

(A) A siloxane oligomer having a radically polymerizable double bond obtained by hydrolytic condensation of an alkoxysilane containing at least alkoxysilane A represented by formula [1] and alkoxysilane B represented by formula [2]

Made of a cured product of a composition for forming a primer layer comprising

[Formula 1]

(Wherein, R ¹ represents a monovalent organic group having a radically polymerizable double bond, and R ³ is an alkyl group having 1 to 10 carbon atoms (the alkyl group is an amino group substituted with a fluorine atom or an alkyl group having at least 1 to 6 carbon atoms; It may be substituted with at least an amino group substituted with a phenyl group, or a ureido group.) or a phenyl group, R ² and R ⁴ each independently represent a methyl group or an ethyl group, a represents an integer of 1 or 2, and b represents an integer from 0 to 2.)

The hard coat layer,

(a) 100 parts by mass of an active energy ray-curable polyfunctional monomer;

(b) at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group via a poly(oxyalkylene) group or via a poly(oxyalkylene) group and one urethane bond group in this order 0.1 to 10 parts by mass of perfluoropolyether binding an active energy ray polymerizable group;

(c) 8 to 30 parts by mass of organic fine particles having an average particle diameter of 1 to 10 μm, and

(d) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays

Consisting of a cured product of a curable composition comprising

It relates to an anti-glare hard coat laminate.

As a second aspect, the siloxane oligomer of component (A) has a radically polymerizable double bond obtained by hydrolytic condensation of alkoxysilane A represented by formula [1] and alkoxysilane B represented by formula [2] It relates to the anti-glare hard coat laminate according to the first aspect, which is a siloxane oligomer.

[Formula 2]

(Wherein, R ¹ represents a monovalent organic group having a radically polymerizable double bond, R ³ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be substituted with a fluorine atom, and R ² and R ⁴ are each Independently, represents a methyl group or an ethyl group, a represents an integer of 1 or 2, and b represents an integer of 0 to 2.)

As a third aspect, it relates to the anti-glare hard coat laminate according to the first aspect or the second aspect, wherein R ¹ in Formula [1] is a monovalent organic group having a vinyl group or a (meth)acrylic group.

As a 4th viewpoint, it is related with the anti-glare hard-coat laminate as described in the 3rd viewpoint in which the said alkoxysilane A is a compound represented by following formula [3].

[Formula 3]

(In the formula, R ² represents the same definition as in the above formula [1], R ⁵ represents a hydrogen atom or a methyl group, and L ¹ represents an alkylene group having 1 to 10 carbon atoms.)

As a fifth aspect, it is described in any one of the first to fourth aspects, wherein the siloxane oligomer of component (A) having a radically polymerizable double bond is a siloxane oligomer containing 10 to 99 mol% of the alkoxysilane A unit. It relates to an anti-glare hard coat laminate.

As a sixth aspect, the poly(oxyperfluoroalkylene) group of the perfluoropolyether of component (b) is a group having -[OCF ₂ ]- and -[OCF ₂ CF ₂ ]- as repeating units; It relates to the anti-glare hard coat laminate according to any one of the first to fifth aspects.

As a seventh aspect, the anti-glare hard coat laminate according to any one of the first to sixth aspects, wherein the poly(oxyalkylene) group of the perfluoropolyether of component (b) is a poly(oxyethylene) group. It is about.

As an eighth aspect, the first to seventh aspects wherein the polyfunctional monomer of component (a) is at least one selected from the group consisting of a polyfunctional (meth)acrylate compound and a polyfunctional urethane (meth)acrylate compound. It relates to the anti-glare hard coat laminate according to any one of the viewpoints.

As a ninth aspect, it relates to the anti-glare hard coat laminate according to any one of the first to eighth aspects, wherein the organic fine particles of component (c) are spherical particles.

As a tenth aspect, it relates to the anti-glare hard coat laminate according to any one of the first to ninth aspects, wherein the organic fine particles of component (c) are polymethyl methacrylate particles.

As an eleventh aspect, it relates to the anti-glare hard coat laminate according to any one of the first to tenth aspects, wherein the polymerization initiator of the component (d) is an alkylphenone type polymerization initiator.

As a twelfth aspect, the hard coat layer has a thickness of 1 to 10/3 times the average particle diameter of the organic particulates of the component (c), the anti-glare hard according to any one of the first to eleventh aspects. It relates to a coat laminate.

As a 13th viewpoint, it is related with the anti-glare hard-coat laminated body in any one of the 1st viewpoint - the 12th viewpoint in which the said hard-coat layer has a film thickness of 1-20 micrometers.

As a 14th viewpoint, it is related with the anti-glare hard-coat laminated body as described in the 13th viewpoint in which the said hard-coat layer has a film thickness of 3-10 micrometers.

As a 15th viewpoint, it is related with the anti-glare hard-coat laminated body described in any one of the 1st viewpoint - 14th viewpoint in which the said base material is glass.

As a sixteenth aspect, a method for producing an anti-glare hard coat laminate comprising a primer layer on at least one side of a substrate and a hard coat layer above the primer layer,

A step of forming a coating film by applying a composition for forming a primer layer on a substrate;

A step of heating a coating film of the composition for forming a primer layer and curing the coating film to form a primer layer;

A step of forming a coating film by applying a curable composition on the primer layer, and

A step of irradiating the coating film of the curable composition with active energy rays and curing the coating film to form a hard coat layer;

The composition for forming the primer layer,

(A) A siloxane oligomer having a radically polymerizable double bond obtained by hydrolytic condensation of an alkoxysilane containing at least alkoxysilane A represented by formula [1] and alkoxysilane B represented by formula [2],

[Formula 4]

(Wherein, R ¹ represents a monovalent organic group having a radically polymerizable double bond, and R ³ is an alkyl group having 1 to 10 carbon atoms (the alkyl group is an amino group substituted with a fluorine atom or an alkyl group having at least 1 to 6 carbon atoms; It may be substituted with at least an amino group substituted with a phenyl group, or a ureido group.) or a phenyl group, R ² and R ⁴ each independently represent a methyl group or an ethyl group, a represents an integer of 1 or 2, and b represents an integer from 0 to 2.)

The curable composition,

(a) 100 parts by mass of an active energy ray-curable polyfunctional monomer;

(b) at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group via a poly(oxyalkylene) group or via a poly(oxyalkylene) group and one urethane bond group in this order 0.1 to 10 parts by mass of perfluoropolyether binding an active energy ray polymerizable group;

(c) 8 to 30 parts by mass of organic fine particles having an average particle diameter of 1 to 10 μm, and

(d) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays

including,

It relates to a method for manufacturing an anti-glare hard coat laminate.

According to the present invention, even in a thin film having a thickness of about 1 to 15 μm, a hard coat layer having excellent scratch resistance and high anti-glare property and excellent appearance, in particular, a primer layer containing a siloxane oligomer having a radically polymerizable double bond is formed on a substrate. By providing and providing the hard coat layer thereon, it is possible to provide a laminate having a hard coat layer excellent in adhesion to a so-called base material.

The anti-glare hard coat laminate of the present invention consists of a base material, a primer layer above the base material, and a hard coat layer above the primer layer.

And in the anti-glare hard coat laminate of the present invention, the primer layer is made of a cured product of a composition for forming a primer layer containing a siloxane oligomer having a radical polymerizable double bond, and the hard coat layer has an active energy It consists of a cured product of a curable composition containing a pre-curable polyfunctional monomer or the like.

Hereinafter, each layer constituting the anti-glare hard coat laminate of the present invention will be described in detail.

"write"

The substrate in the anti-glare hard coat laminate of the present invention is not particularly limited, and examples thereof include plastics (polycarbonate, polymethacrylate, polystyrene, polyester, PET (polyethylene terephthalate), polyolefin, epoxy resin, Melamine resin, triacetyl cellulose, ABS (acrylonitrile-butadiene-styrene copolymer), AS (acrylonitrile-styrene copolymer), norbornene resin, etc.), metal, wood, paper, glass, silicon dioxide, slate, etc. can be heard The shape of these substrates may be a plate shape, a film shape or a three-dimensional molded body.

Especially, in this invention, glass can be used suitably as a base material.

The thickness of the substrate is not particularly limited, but may be, for example, 10 to 1,000 μm.

<<primer layer>>

<Composition for Primer Layer Formation>

The primer layer in the anti-glare hard coat laminate of the present invention is made of a cured product of a composition for forming a primer layer containing the following component (A):

(A) A siloxane oligomer having a radically polymerizable double bond obtained by hydrolytic condensation of an alkoxysilane containing at least alkoxysilane A represented by formula [1] and alkoxysilane B represented by formula [2].

[Formula 5]

(Wherein, R ¹ represents a monovalent organic group having a radically polymerizable double bond, and R ³ is an alkyl group having 1 to 10 carbon atoms (the alkyl group is an amino group substituted with a fluorine atom or an alkyl group having at least 1 to 6 carbon atoms; It may be substituted with at least an amino group substituted with a phenyl group, or a ureido group.) or a phenyl group, R ² and R ⁴ each independently represent a methyl group or an ethyl group, a represents an integer of 1 or 2, and b represents an integer from 0 to 2.)

Hereinafter, the component (A) and each component that can be included in the composition for forming a primer layer will be described.

[(A) Siloxane Oligomer Having Radical Polymerizable Double Bond]

The (A) siloxane oligomer having a radically polymerizable double bond (hereinafter also simply referred to as (A) siloxane oligomer) is an alkoxysilane A represented by the following formula [1] and an alkoxysilane represented by the following formula [2] It is a siloxane oligomer obtained by containing B as an essential alkoxysilane unit at least and hydrolyzing and condensing these.

[Formula 6]

In the formula [1], R ¹ represents a monovalent organic group having a radically polymerizable double bond, R ² represents a methyl group or an ethyl group, and a represents an integer of 1 or 2.

In Formula [2], R ³ is an alkyl group of 1 to 10 carbon atoms (the alkyl group is substituted with a fluorine atom, an amino group substituted with an alkyl group of at least 1 to 6 atoms, an amino group substituted with at least a phenyl group, or a ureido group) or a phenyl group, preferably R ³ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be substituted with a fluorine atom, R ⁴ represents a methyl group or an ethyl group, and b is 0 to 2 represents an integer.

As the monovalent organic group having a radical polymerizable double bond, R ¹ in the formula [1] is preferably a monovalent organic group having a vinyl group or a (meth)acrylic group. In the present invention, a (meth)acrylic group refers to both an acryl group and a methacrylic group.

Further, an alkyl group having 1 to 10 carbon atoms represented by R ³ in the formula [2] (this alkyl group is substituted with a fluorine atom, an amino group substituted with an alkyl group having at least 1 to 6 atoms, an amino group substituted with at least a phenyl group, or a ureido group) may be), methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neo A pentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, etc. are mentioned.

In addition, as an amino group substituted with an alkyl group having at least 1 to 6 carbon atoms represented by R ³ in the formula [2], methylamino group, dimethylamino group, ethylamino group, diethylamino group, n-propylamino group, isopropylamino group, n- A butylamino group, tert-butylamino group, n-pentylamino group, n-hexylamino group, cyclohexylamino group, N-methyl-N-phenylamino group, etc. are mentioned.

Further, examples of the amino group substituted with at least a phenyl group represented by R ³ in the formula [2] include a phenylamino group and a diphenylamino group.

Among the alkoxysilanes A represented by the above formula [1], compounds represented by the following formula [3] are preferred.

[Formula 7]

In the formula, R ² represents the same meaning as defined in the above formula [1], R ⁵ represents a hydrogen atom or a methyl group, and L ¹ represents an alkylene group having 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms. An 8-carbon alkylene group, more preferably an alkylene group of 1 to 6 carbon atoms.

Examples of the alkylene group having 1 to 10 carbon atoms represented by L ¹ include a methylene group, an ethylene group, a trimethylene group, a methylethylene group, a tetramethylene group, a 1-methyltrimethylene group, a pentamethylene group, and a 2,2-dimethyl A trimethylene group, a hexamethylene group, an octamethylene group, a decamethylene group, etc. are mentioned. Among these, a trimethylene group is preferable.

Specific examples of such alkoxysilane A include trimethoxy(vinyl)silane, triethoxy(vinyl)silane, 3-(meth)acryloyloxypropyltrimethoxysilane, triethoxy(3-(meth) Acryloyloxypropyl)silane, 8-(meth)acryloyloxyoctyltrimethoxysilane, triethoxy(8-(meth)acryloyloxyoctyl)silane, 3-(meth)acryloyloxypropyl (dimethoxy)(methyl)silane, diethoxy(3-(meth)acryloyloxypropyl)(methyl)silane, trimethoxy(4-vinylphenyl)silane, triethoxy(4-vinylphenyl)silane, etc. can be heard

Among these, 3-(meth)acryloyloxypropyltrimethoxysilane and triethoxy(3-(meth)acryloyloxypropyl)silane are preferable.

Specific examples of the alkoxysilane B represented by the formula [2] include tetramethoxysilane, tetraethoxysilane, trimethoxy(methyl)silane, triethoxy(methyl)silane, ethyltrimethoxysilane, triethoxy(ethyl)silane, trimethoxy(propyl)silane, triethoxy(propyl)silane, trimethoxy(3,3,3-trifluoropropyl)silane, triethoxy(3,3,3 -trifluoropropyl)silane, butyltrimethoxysilane, butyltriethoxysilane, trimethoxy(pentyl)silane, triethoxy(pentyl)silane, hexyltrimethoxysilane, triethoxy(hexyl)silane, Trimethoxy(phenyl)silane, triethoxy(phenyl)silane, dimethoxydimethylsilane, diethoxydimethylsilane, diethyldimethoxysilane, diethoxydiethylsilane, dimethoxydipropylsilane, diethoxydipropylsilane, Dibutyldimethoxysilane, dibutyldiethoxysilane, dimethoxydipentylsilane, diethoxydipentylsilane, dihexyldimethoxysilane, diethoxydihexylsilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, trimetylsilane Toxy((phenylamino)methyl)silane, trimethoxy(3-(phenylamino)propyl)silane, triethoxy(3-(phenylamino)propyl)silane, dimethoxy(methyl)(3-(phenylamino) propyl) silane; and the like.

Among these, tetramethoxysilane, tetraethoxysilane, trimethoxy(3-(phenylamino)propyl)silane, and triethoxy(3-(phenylamino)propyl)silane are preferable.

(A) It is preferable that a siloxane oligomer is a siloxane oligomer containing 10-99 mol% of the said alkoxysilane A units out of all alkoxysilane units.

It is preferable that especially (A) a siloxane oligomer is a siloxane oligomer containing at least 10-99 mol% of structural units represented by following formula [4] among all structural units.

[Formula 8]

In the formula, R ² , R ⁵ and L ¹ represent the same definition as in formula [3].

The method for obtaining the siloxane oligomer (A) is not particularly limited.

For example, it is obtained by condensing an alkoxysilane including the alkoxysilane A and the alkoxysilane B in an organic solvent. As a method of polycondensing an alkoxysilane, the method of hydrolyzing and condensing an alkoxysilane in solvent, such as alcohol or glycol, is mentioned, for example. At this time, the hydrolysis/condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, theoretically, 0.5 times mole of water of all the alkoxy groups in the alkoxysilane should be added, but usually, it is preferable to add an excess amount of water from 0.5 times mole. In the present invention, the amount of water used in the reaction can be appropriately selected as necessary, but is usually preferably 0.5 to 2.5 times mole of all alkoxy groups in the alkoxysilane.

Also, usually, for the purpose of accelerating the hydrolysis/condensation reaction, formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, 2-ethylhexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, stearic acid , oleic acid, linoleic acid, linolenic acid, arachidonic acid, oxalic acid, malonic acid, methylmalonic acid, succinic acid, tartaric acid, maleic acid, fumaric acid, adipic acid, sebacic acid, citric acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trichloroacetic acid organic acids such as fluoroacetic acid, benzoic acid, p-aminobenzoic acid, salicylic acid, gallic acid, phthalic acid, mellitic acid, benzenesulfonic acid, and p-toluenesulfonic acid; inorganic acids and metal salts thereof, such as hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid; Catalysts such as alkalis such as ammonia, methylamine, ethylamine, ethanolamine and triethylamine are used. Moreover, it is also common to further accelerate the hydrolysis/condensation reaction by heating the solution in which the alkoxysilane is dissolved. At this time, the heating temperature and heating time can be appropriately selected as needed. For example, the method of heating and stirring at 50 degreeC for 24 hours, the method of heating and stirring under reflux for 1 hour, etc. are mentioned.

Further, as an alternative method, for example, a method of polycondensation by heating a mixture of an alkoxysilane, a solvent and oxalic acid is exemplified. Specifically, it is a method in which oxalic acid is added to alcohol beforehand to obtain an alcohol solution of oxalic acid, and then the alkoxysilane is mixed with the solution heated. At this time, the amount of oxalic acid used is preferably 0.05 to 5 mol% with respect to 1 mol of all alkoxy groups of the alkoxysilane. Heating in this method can be performed at a liquid temperature of 50 to 180°C. Preferably, it is a method of heating under reflux for several tens of minutes to several tens of hours so that evaporation or volatilization of the liquid does not occur.

The weight average molecular weight (Mw) of the siloxane oligomer (A) used in the composition for forming a primer layer used in the present invention measured in terms of polystyrene by gel permeation chromatography is 100 to 10,000, preferably 500 to 5,000.

In the present invention, by using the siloxane oligomer as the material for forming the primer layer, a partial hydrolytic condensation reaction between the oligomers proceeds at the time of forming the primer layer, and the alcohol produced at this time volatilizes, so that the primer layer has a gap. It appears to be a structure, and as a result, it is estimated that it contributes to improving the adhesion between the substrate and the hard coat layer of the entire primer layer.

[menstruum]

The composition for forming a primer layer used in the present invention may further contain a solvent and be in the form of a varnish.

The solvent used at this time may be any solvent that dissolves or disperses the component (A) and, if necessary, other components described later, and examples thereof include aromatic hydrocarbons such as toluene and xylene; Ethyl acetate, butyl acetate, isobutyl acetate, γ-butyrolactone, methyl pyruvate, ethyl pyruvate, ethyl hydroxyacetate, ethyl lactate, butyl lactate, 2-hydroxy-2-methylethylpropionate, 2-hydroxy-3 -Methylbutanoate, ethylethoxyacetate, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, methylcellosolveacetate, ethylcellosolveacetate esters or ester ethers such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monopropyl ether acetate; ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and propylene glycol monomethyl ether (PGME); ketones such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone, and cyclohexanone; alcohols such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and propylene glycol; Amides, such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide, and N-methyl-2-pyrrolidone (NMP), etc. can be used. These solvents can be used alone or in combination of two or more, or as a mixed solvent with water.

The solid content concentration in the composition for forming a primer layer used in the present invention is, for example, 0.01 to 70% by mass, 0.1 to 50% by mass, or 1 to 30% by mass. Here, the solid content is a value obtained by subtracting the solvent component from all components of the composition for forming a primer layer.

[Other additives]

In addition, to the composition for forming a primer layer used in the present invention, additives generally added as needed, for example, a photosensitizer, a polymerization inhibitor, a polymerization initiator, and a leveling agent, as long as the effects of the present invention are not impaired. , surfactants, adhesion imparting agents, plasticizers, ultraviolet absorbers, antioxidants, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes, and the like, and furthermore, active energy ray-curable polyfunctional monomers and the like may be appropriately blended.

[Active energy ray-curable polyfunctional monomer]

The composition for forming a primer layer used in the present invention may further contain an active energy ray-curable polyfunctional monomer in order to improve adhesion with the hard coat layer thereon.

As the active energy ray-curable polyfunctional monomer used in the composition for forming a primer layer, the polyfunctional (meth)acrylate compounds and polyfunctional urethane (meth) exemplified in <(a) Active energy ray-curable polyfunctional monomer> described later and monomers selected from the group consisting of acrylate compounds, polyfunctional epoxy (meth)acrylate compounds, polyfunctional polyester (meth)acrylate compounds, and unsaturated polyesters.

In addition, in this invention, a (meth)acrylate compound refers to both an acrylate compound and a methacrylate compound. For example, (meth)acrylic acid refers to acrylic acid and methacrylic acid.

In the composition for forming a primer layer used in the present invention, when an active energy ray-curable polyfunctional monomer is used, it is in an amount of 1 to 300 parts by mass, preferably 1 to 300 parts by mass, based on 100 parts by mass of the siloxane oligomer (A) described above. It is used in an amount of ˜200 parts by mass, particularly preferably in an amount of 10 to 100 parts by mass.

[Polymerization initiator that generates radicals by active energy rays]

In the case where the composition for forming a primer layer used in the present invention contains the above <active energy ray-curable multifunctional monomer>, it is exemplified in <(d) Polymerization Initiator Generating Radicals by Active Energy Ray> described later. Various polymerization initiators may be included.

In the composition for forming a primer layer used in the present invention, when the polymerization initiator is included, the amount is 0.1 to 25 parts by mass, preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the siloxane oligomer (A). It is used in an amount, particularly preferably in an amount of 1 to 20 parts by mass.

<<hard coat layer>>

<Curable composition>

The hard coat layer in the anti-glare hard coat laminate of the present invention is made of a cured product (ie cured film) of a curable composition containing the following (a) to (d).

(a) 100 parts by mass of an active energy ray-curable polyfunctional monomer;

(b) at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group via a poly(oxyalkylene) group or via a poly(oxyalkylene) group and one urethane bond group in this order 0.1 to 10 parts by mass of perfluoropolyether binding an active energy ray polymerizable group;

(c) 8 to 30 parts by mass of organic fine particles having an average particle diameter of 1 to 10 μm, and

(d) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays.

Hereinafter, each component of said (a)-(d) is demonstrated.

[(a) Active energy ray-curable polyfunctional monomer]

An active energy ray-curable polyfunctional monomer refers to a monomer that undergoes a polymerization reaction and is cured by irradiating active energy rays such as ultraviolet rays.

In the curable composition used in the present invention, the preferred active energy ray-curable polyfunctional monomer (a) is a monomer selected from the group consisting of polyfunctional (meth)acrylate compounds and polyfunctional urethane (meth)acrylate compounds.

Examples of the polyfunctional (meth)acrylate compound include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri( Meth) acrylate, pentaerythritol di(meth)acrylate monostearate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerin tri(meth)acrylate )Acrylate, propoxylated glycerin tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate , ethoxylated dipentaerythritol hexa(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, ethoxylated bisphenol F di(meth)acrylate, 1,3-propane Dioldi(meth)acrylate, 1,3-butanedioldi(meth)acrylate, 1,4-butanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, 2-methyl-1 ,8-Octanedioldi(meth)acrylate, 1,9-nonanedioldi(meth)acrylate, 1,10-decanedioldi(meth)acrylate, neopentylglycoldi(meth)acrylate, ethylene glycol Di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di (meth)acrylate, bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, tris(2-hydroxy Ethyl) isocyanurate tri(meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane dimethanol di(meth)acrylate, dioxane glycol di(meth)acrylate, 2-hydroxy-1- Acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1,3-di(meth)acryloyloxypropane, 9,9-bis[4-(2-(meth)acryloyl oxyethoxy)phenyl]fluorene, bis[4-(meth)arc Riloylthiophenyl] sulfide, bis[2-(meth)acryloylthioethyl]sulfide, 1,3-adamantanedioldi(meth)acrylate, 1,3-adamantanedimethanoldi(meth)acryl Rate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tris(2-(meth)acryloyloxyethyl)phosphate, ε-caprolactone modified tris(2-hydroxyethyl)iso Cyanurate tri(meth)acrylate etc. are mentioned.

Among them, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and the like are exemplified as preferred ones.

The polyfunctional urethane (meth)acrylate compound is a compound having a plurality of acryloyl groups or methacryloyl groups in one molecule and having at least one urethane bond (-NHCOO-).

For example, as the polyfunctional urethane (meth)acrylate compound, a polyfunctional isocyanate obtained by reaction of a (meth)acrylate having a hydroxyl group, a (meth)acrylate having a polyfunctional isocyanate and a hydroxyl group, and and those obtained by the reaction of polyols, but the polyfunctional urethane (meth)acrylate compounds usable in the present invention are not limited to these examples.

On the other hand, as said polyfunctional isocyanate, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate etc. are mentioned, for example.

Examples of the (meth)acrylate having the hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol Penta(meth)acrylate, tripentaerythritol hepta(meth)acrylate, etc. are mentioned.

Examples of the polyol include diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and dipropylene glycol; polyester polyols which are reaction products of these diols with aliphatic dicarboxylic acids or dicarboxylic acid anhydrides such as succinic acid, maleic acid, and adipic acid; polyether polyol; Polycarbonate diol etc. are mentioned.

In the present invention, as the (a) active energy ray-curable multifunctional monomer, one type alone or two types from the group consisting of the multifunctional (meth)acrylate compound and the multifunctional urethane (meth)acrylate compound are used. The above can be used in combination. From the viewpoint of scratch resistance of the resulting cured product, it is preferable to use a polyfunctional (meth)acrylate compound and a polyfunctional urethane (meth)acrylate compound in combination. Moreover, as said polyfunctional (meth)acrylate compound, it is preferable to use together the polyfunctional (meth)acrylate compound of 5 or more functional and the polyfunctional (meth)acrylate compound of 4 or less functional.

Further, when the polyfunctional (meth)acrylate compound and the polyfunctional urethane (meth)acrylate compound are used in combination, based on 100 parts by mass of the polyfunctional (meth)acrylate compound, the polyfunctional urethane (meth)acrylate It is preferable to use 20-100 mass parts of a rate compound, and it is more preferable to use 30-70 mass parts.

Furthermore, in the polyfunctional (meth)acrylate compound, when the pentafunctional or higher functional (meth)acrylate compound and the tetrafunctional or lower polyfunctional (meth)acrylate compound are used in combination, the pentafunctional or higher functional (meth)acrylate compound is used in combination. It is preferable to use 10-100 mass parts of tetrafunctional or less polyfunctional (meth)acrylate compounds with respect to 100 mass parts of polyfunctional (meth)acrylate compounds, and it is more preferable to use 20-60 mass parts.

In addition, 20 to 100 parts by mass of a polyfunctional urethane (meth)acrylate compound based on 100 parts by mass of a polyfunctional (meth)acrylate compound and 100 parts by mass of a polyfunctional (meth)acrylate compound having a pentafunctional or higher functional group of a tetrafunctional or less Using 10 to 100 parts by mass of a polyfunctional (meth)acrylate compound;

20 to 100 parts by mass of polyfunctional urethane (meth)acrylate compound based on 100 parts by mass of polyfunctional (meth)acrylate compound and 100 parts by mass of polyfunctional (meth)acrylate compound having 5 or more functional groups, polyfunctional less than or equal to tetrafunctional Using with 20 to 60 parts by mass of a (meth)acrylate compound;

30 to 70 parts by mass of polyfunctional urethane (meth)acrylate compound with respect to 100 parts by mass of polyfunctional (meth)acrylate compound and 100 parts by mass of polyfunctional (meth)acrylate compound having 5 or more functions, polyfunctional less than or equal to tetrafunctional Using in 10 to 100 parts by mass of a (meth)acrylate compound;

30 to 70 parts by mass of polyfunctional urethane (meth)acrylate compound with respect to 100 parts by mass of polyfunctional (meth)acrylate compound and 100 parts by mass of polyfunctional (meth)acrylate compound having 5 or more functions, polyfunctional less than or equal to tetrafunctional It is preferable to use with 20-60 mass parts of (meth)acrylate compounds.

[(b) at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group via a poly(oxyalkylene) group or a poly(oxyalkylene) group and one urethane bond group interposed in this order and a perfluoropolyether that binds an active energy ray polymerizable group]

In the present invention, as component (b), at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group, via a poly(oxyalkylene) group or a poly(oxyalkylene) group and one urethane A perfluoropolyether (hereinafter also simply referred to as "(b) perfluoropolyether having a polymerizable group at both ends") is used in which active energy ray polymerizable groups are bonded via a bonding group in this order. Component (b) plays a role as a surface modifier in the hard coat layer to which the curable composition used in the present invention is applied.

The number of carbon atoms of the alkylene group in the poly(oxyperfluoroalkylene) group is not particularly limited, but is preferably 1 to 4 carbon atoms. That is, the poly(oxyperfluoroalkylene) group refers to a group having a structure in which divalent fluorocarbon groups having 1 to 4 carbon atoms and oxygen atoms are alternately connected, and the oxyperfluoroalkylene group has 1 to 4 carbon atoms It refers to a group having a structure in which a divalent fluorocarbon group and an oxygen atom are connected. Specifically, -[OCF ₂ ]-(oxyperfluoromethylene group), -[OCF ₂ CF ₂ ]-(oxyperfluoroethylene group), -[OCF ₂ CF ₂ CF ₂ ]-(oxyperfluoroethylene group) lopropane-1,3-diyl group) and -[OCF ₂ C(CF ₃ )F]-(oxyperfluoropropane-1,2-diyl group).

The said oxyperfluoroalkylene group may be used individually by 1 type, or may be used in combination of 2 or more types, In that case, the bond of multiple types of oxyperfluoroalkylene group is a block bond and a random bond It can be any.

Among these, -[OCF ₂ ]-(oxyperfluoromethylene group) and -[OCF as poly(oxyperfluoroalkylene) groups from the viewpoint of obtaining a cured product (hard coat layer) having good scratch resistance. It is preferable to use a group having both ₂ CF ₂ ]-(oxyperfluoroethylene groups) as repeating units.

Among them, as the poly(oxyperfluoroalkylene) group, repeating units: -[OCF ₂ ]- and -[OCF ₂ CF ₂ ]-, in a molar ratio, [repeating unit: -[OCF ₂ ]-]: [Repeating unit: -[OCF ₂ CF ₂ ]-] It is preferably a group containing in a ratio of 2:1 to 1:2, more preferably a group containing in a ratio of approximately 1:1. The bonding of these repeating units may be any of block bonding and random bonding.

The number of repeating units of the oxyperfluoroalkylene group is preferably in the range of 5 to 30, and more preferably in the range of 7 to 21 as the total number of repeating units.

In addition, the weight average molecular weight (Mw) of the poly(oxyperfluoroalkylene) group measured in terms of polystyrene by gel permeation chromatography is 1,000 to 5,000, preferably 1,500 to 2,000.

The number of carbon atoms of the alkylene group in the poly(oxyalkylene) group is not particularly limited, but is preferably 1 to 4 carbon atoms. That is, the poly(oxyalkylene) group refers to a group having a structure in which an alkylene group having 1 to 4 carbon atoms and an oxygen atom are alternately connected, and the oxyalkylene group is a divalent alkylene group having 1 to 4 carbon atoms and an oxygen atom connected thereto. refers to a group having a structure. As said alkylene group, an ethylene group, 1-methylethylene group, a trimethylene group, a tetramethylene group, etc. are mentioned.

The said oxyalkylene group may be used individually by 1 type, or may be used in combination of 2 or more types, In that case, any of a block bond and a random bond may be sufficient as the coupling|bonding of multiple types of oxyalkylene groups.

Especially, it is preferable that the said poly(oxyalkylene) group is a poly(oxyethylene) group.

The number of repeating units of the oxyalkylene group in the poly(oxyalkylene) group is, for example, in the range of 1 to 15, for example, in the range of 5 to 12, for example, more preferably in the range of 7 to 12 do.

As the active energy ray polymerizable group bonded via the poly(oxyalkylene) group or via the poly(oxyalkylene) group and one urethane bonding group in this order, (meth)acryloyl group, urethane (meth) An acryloyl group, a vinyl group, etc. are mentioned.

The active energy ray polymerizable group is not limited to one having one active energy ray polymerizable moiety such as a (meth)acryloyl moiety, and may have two or more active energy ray polymerizable moieties, for example, Structures of A1 to A5 shown below and structures in which the acryloyl group in these structures is substituted with a methacryloyl group are exemplified.

[Formula 9]

Preferable examples of such (b) perfluoropolyethers having polymerizable groups at both ends are the compounds shown below and compounds in which the acryloyl group in these compounds is substituted with a methacryloyl group in view of easy industrial production. can be heard as On the other hand, in the structural formula, A represents one of the structures represented by the formula [A1] to formula [A5], PFPE represents the poly(oxyperfluoroalkylene) group, and n each independently represents an oxyethylene group. represents the number of repeating units of, preferably represents the number of 1 to 15, more preferably represents the number of 5 to 12, still more preferably represents the number of 7 to 12.

[Formula 10]

Among them, the (b) perfluoropolyether having a polymerizable group at both ends used in the present invention has poly(oxyalkylene) at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group. group and one urethane bond group in this order, that is, the poly (oxyalkylene) group is bonded to both ends of the molecular chain containing the poly (oxyperfluoroalkylene) group, respectively, and each poly ( It is preferable that it is a perfluoropolyether in which one urethane bond group is each bonded to an oxyalkylene) group, and active energy ray polymerizable groups are bonded to each urethane bond at both ends. Furthermore, in the above perfluoropolyether, it is preferable that the active energy ray polymerizable group is a perfluoropolyether group having at least two or more active energy ray polymerizable moieties.

In the present invention, (b) the perfluoropolyether having polymerizable groups at both ends is 0.1 to 10 parts by mass, preferably 0.2 parts by mass, based on 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer. It is preferable to use in a ratio of ~5 parts by mass.

The (b) perfluoropolyether having polymerizable groups at both ends is, for example, a compound having a hydroxyl group via a poly(oxyalkylene) group at both ends of a poly(oxyperfluoroalkylene) group. In the urethane isocyanate compound having a polymerizable group such as 2-(meth)acryloyloxyethyl isocyanate or 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate with respect to the hydroxyl groups at both ends thereof It is obtained by a method of oxidization, a method of dehydrochlorination of (meth)acrylic acid chloride or chloromethylstyrene, a method of dehydration of (meth)acrylic acid, a method of esterification of itaconic anhydride, and the like.

Among them, in the compound having a hydroxyl group via a poly(oxyalkylene) group at both ends of the poly(oxyperfluoroalkylene) group, with respect to the hydroxyl groups at both ends, 2-(meth)acrylo A method of urethanizing an isocyanate compound having a polymerizable group such as yloxyethyl isocyanate or 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate, or (meth)acrylic acid chloride for this hydroxyl group Alternatively, a method in which chloromethylstyrene is subjected to a dehydrochloric acid reaction is particularly preferred because the reaction is easy.

On the other hand, in the curable composition used in the present invention, (b) at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group, through a poly(oxyalkylene) group or a poly(oxyalkylene) group, and One end of the molecular chain containing a poly(oxyperfluoroalkylene) group is poly(oxyalkylene) in addition to the perfluoropolyether to which the active energy ray polymerizable group is bonded via one urethane bond group in this order. Via a group or via a poly(oxyalkylene) group and one urethane bonding group in this order, an active energy ray polymerizable group is bonded, and a hydroxyl group is also connected to the other end via a poly(oxyalkylene) group Purple purple Fluoropolyether or perfluoropolyether having a hydroxyl group via a poly(oxyalkylene) group at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group [not bonded to an active energy ray polymerizable group] compound] may be included.

[(c) organic fine particles having an average particle diameter of 1 to 10 μm]

In the curable composition used in the present invention, organic particulates having an average particle diameter of 1 to 10 μm (hereinafter also simply referred to as “(c) organic particulates”) have a concavo-convex surface on the surface of the hard coat layer formed from the curable composition. to impart anti-glare properties.

In addition, the organic fine particles can also play a role in controlling the haze value of the hard coat layer by controlling the difference between the refractive index and the refractive index of the curable composition as the hard coat layer forming material.

The shape of the organic fine particles is not particularly limited, but may be, for example, bead-shaped, substantially spherical, or may be irregular, such as powder, but is preferably substantially spherical, more preferably substantially spherical with an aspect ratio of 1.5 or less. It is a particle, Most preferably, it is a spherical particle.

Examples of the organic fine particles include polymethyl methacrylate particles (PMMA particles), silicon particles, polystyrene particles, polycarbonate particles, acrylic styrene particles, benzoguanamine particles, melamine particles, polyolefin particles, polyester particles, polyamide particles, polyimide particles, polyfluorinated ethylene particles, and the like. These organic particulates may be used individually by 1 type, or may use 2 or more types together.

Among them, polymethyl methacrylate particles can be suitably used as the organic fine particles.

The average particle diameter of the organic particulates used in the present invention is in the range of 1 to 10 μm, preferably in the range of 2 to 8 μm, more preferably in the range of 3 to 8 μm. Here, the average particle diameter (μm) is a 50% volume diameter (median diameter) obtained by measuring by a laser diffraction/scattering method based on the Mie theory. When the average particle diameter of the organic particulates is larger than the above numerical range, the image clarity of the display deteriorates, and when it is smaller than the above numerical range, sufficient anti-glare properties are not obtained, and the problem of increased glare tends to occur. Meanwhile, although the particle size distribution of the organic fine particles is not particularly limited, it is preferable that they are monodisperse fine particles having a uniform particle size.

The organic particulates are preferably organic particulates having a refractive index difference of 0 to 0.20 with the cured product of the (a) active energy ray-curable polyfunctional monomer, and further preferably 0 to 0.10.

In addition, the average particle diameter of the organic particulates is a cured product obtained from the curable composition used in the present invention described later, that is, the average particle diameter of the organic particulates b / film thickness a = 0.3 to 1.0 with respect to the film thickness of the hard coat layer. It is preferable to select to satisfy the range of

Commercially available products can be suitably used for the above-mentioned organic particulates. For example, Techpolymer (registered trademark) MBX series, SBX series, MSX series, SMX series, SSX series, BMX series, ABX series, the same ARX series, the same AFX series, the same MB series, the same MBP series, the same MB-C series, the same ACX series, the same ACP series [above, made by Sekisui Chemical Industry Co., Ltd.]; Tospearl (registered trademark) series [Momentive Performance Materials Japan (bronze) product]; Epostar (registered trademark) series, MA series, ST series, MX series [above, Nippon Catalyst Co., Ltd.]; Opto beads (registered trademark) series [manufactured by Nissan Chemical Industries, Ltd.]; Flow beads series (Sumitomo Seika Co., Ltd.); Toraypearl (registered trademark) PPS, copper PAI, copper PES, copper EP [above, manufactured by Toray Co., Ltd.]; 3M (registered trademark) Dionine TF micropowder series [manufactured by 3M Corporation]; Chemisno (registered trademark) MX series, MZ series, MR series, KMR series, KSR series, MP series, SX series, SGP series [above, manufactured by Soken Chemical Co., Ltd.]; Teftic (registered trademark) AR650 series, AR-750 series, FH-S series, A-20, YK series, ASF series, HU series, F series, C series, WS series [ above, manufactured by Toyobo Co., Ltd.]; Art Pearl (registered trademark) GR series, SE series, G series, GS series, J series, MF series, BE series [above, manufactured by Negami Kogyo Co., Ltd.]; Shin-Etsu Silicone (registered trademark) KMP series [manufactured by Shin-Etsu Chemical Co., Ltd.] can be used.

In the present invention, the organic fine particles (c) are preferably used in an amount of 8 to 30 parts by mass, preferably 8 to 20 parts by mass, based on 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer. do.

[(d) polymerization initiator that generates radicals by active energy rays]

In the curable composition used in the present invention, a polymerization initiator that generates radicals by an active energy ray (hereinafter, simply referred to as "(d) polymerization initiator"), which is preferable in the curable composition, is active, for example, by electron beams, ultraviolet rays, X-rays, etc. It is a polymerization initiator that generates radicals by energy rays, particularly by ultraviolet irradiation.

Examples of the (d) polymerization initiator include benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinonediazides, acylphosphine oxides, oxime esters, organic peroxides, benzophenones, biscoumarins, bisimidazoles, titanocenes, thiols, halogenated hydrocarbons, trichloromethyltriazines, or onium salts such as iodonium salts and sulfonium salts; and the like. You may use these individually by 1 type or in mixture of 2 or more types.

Among them, in the present invention, it is preferable to use an alkylphenone type polymerization initiator as the (d) polymerization initiator from the viewpoint of transparency, surface curability and thin film curability. By using an alkylphenone type polymerization initiator, a cured product (hard coat layer) having more improved scratch resistance can be obtained.

Examples of the alkylphenone polymerization initiator include 1-hydroxycyclohexyl=phenyl=ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1-( 4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl ) -2-methylpropan-1-one and other α-hydroxyalkyl phenones; 2-Methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1- α-aminoalkylphenones such as Onn; 2,2-dimethoxy-1,2-diphenylethan-1-one; Phenylglyoxylate methyl etc. are mentioned.

In the present invention, the (d) polymerization initiator is preferably used in an amount of 1 to 20 parts by mass, preferably 2 to 10 parts by mass, based on 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer. do.

[(e) Solvent]

The curable composition used in the present invention further contains (e) a solvent, that is, it can be in the form of a varnish (film-forming material).

The solvent is appropriately selected in consideration of workability during coating required for dissolving and dispersing the components (a) to (d) and forming a cured product (hard coat layer) described later, drying property before and after curing, and the like. What is necessary is just that, For example, Aromatic hydrocarbons, such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirits, and cyclohexane; halides such as methyl chloride, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichlorethylene, perchlorethylene, and o-dichlorobenzene; esters or ester ethers such as ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate; Diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether ethers such as propylene glycol monoisopropyl ether and propylene glycol mono-n-butyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, and cyclohexanone; alcohols such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol, and ethylene glycol; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; sulfoxides such as dimethyl sulfoxide; heterocyclic compounds such as N-methyl-2-pyrrolidone, and mixed solvents of two or more thereof.

Further, for the purpose of controlling the dispersibility of the fine particles during drying after coating, a solvent having a high boiling point may be used.

Examples of such solvents include cyclohexyl acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, 1,6-hexanediol diacetate, and ethylene glycol monobutyl ether. Acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethylene glycol, diethylene glycol, propylene glycol, 1,3-butylene glycol , Diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, Tripropylene glycol monobutyl ether, 3-methoxybutanol, dipropylene glycol dimethyl ether, dipropylene glycol = methyl = propyl = ether, etc. are mentioned.

The amount of these (e) solvents used is not particularly limited, but is used at a concentration such that the solid content concentration in the curable composition used in the present invention is 1 to 70% by mass, preferably 5 to 50% by mass. Here, the solid content concentration (also referred to as non-volatile content concentration) is the solid content (total components excluding the solvent component from).

[Other additives]

In addition, to the curable composition used in the present invention, as long as the effect of the present invention is not impaired, additives generally added as needed, for example, polymerization accelerators, polymerization inhibitors, photosensitizers, leveling agents, surfactants , adhesion imparting agents, plasticizers, ultraviolet absorbers, antioxidants, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes and the like can be appropriately blended.

In addition, inorganic fine particles such as titanium oxide may be blended for the purpose of controlling the haze value of the cured product (hard coat layer).

《Anti-glare hard coat laminate》

As described above, the anti-glare hard coat laminate of the present invention is a three-layer laminate comprising a substrate, a primer layer above the substrate, and a hard coat layer above the primer layer.

The anti-glare hard coat laminate of the present invention,

(i) a step of forming a coating film by applying a composition for forming a primer layer on a substrate;

(ii) a step of heating and curing the coating film of the composition for forming a primer layer to form a primer layer;

(iii) a step of forming a coating film by applying a curable composition on the primer layer, and

(iv) a coating film of the curable composition is irradiated with active energy rays and cured to form a hard coat layer;

Here, as the composition for forming a primer layer and the curable composition, each of the above compositions can be applied.

The coating methods of the composition for forming a primer layer and the curable composition in the steps (i) and (iii) include a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a bar coating method, and a die coating method. A coating method, a spray coating method, a curtain coating method, an inkjet method, a printing method (relief, intaglio, flat plate, screen printing, etc.) can be appropriately selected. It is preferable to use the spin coating method from the advantage that it can be applied easily and uniformly. In addition, it is preferable to use a roll coating method, a die coating method, or a spray coating method from the advantages of being able to apply easily and being able to form a smooth coating film without uneven coating over a large area. As the composition for forming a primer layer and the curable composition used here, those in the form of the varnish described above can be suitably used. On the other hand, it is preferable to filter the composition for forming a primer layer and the curable composition using a filter having a pore diameter of about 2 μm in advance, and then apply the coating.

After the coating of the composition for forming a primer layer in step (i), heat treatment is performed with a hot plate or an oven as step (ii) to cure the coating film to form a primer layer. As the heat treatment conditions at this time, it is preferable to set it at 40-150 degreeC for about 30 seconds - 10 minutes, for example.

On the other hand, when the composition for forming a primer layer contains an active energy ray-curable polyfunctional monomer or a polymerization initiator that generates radicals by active energy rays, an active energy ray irradiation step applied to a coating film of a curable composition described later may be applied. do.

After coating the curable composition in step (iii), preferably subsequently pre-drying on a hot plate or in an oven, photocuring is performed by irradiating active energy rays such as ultraviolet rays as step (iv) to form a hard coat layer. do. As an active energy ray, an ultraviolet-ray, an electron beam, X-ray, etc. are mentioned. As a light source used for ultraviolet irradiation, solar rays, chemical lamps, low pressure mercury lamps, high pressure mercury lamps, metal halide lamps, xenon lamps, UV-LEDs and the like can be used.

Thereafter, polymerization and polycondensation can be completed by post-baking, specifically by heating using a hot plate, oven, or the like.

In the laminate of the present invention thus obtained, the thickness of the primer layer is not particularly limited, but may be, for example, in the range of 0.01 to 1 μm.

In addition, the hard coat layer is preferably set to be 1 to 10/3 times thicker than the average particle diameter of the organic fine particles (c). For example, the thickness of the hard coat layer is in the range of 1 to 30 μm, preferably 1 to 20 μm, and more preferably 3 to 10 μm.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.

On the other hand, in the examples, the equipment and conditions used for the preparation of the sample and the analysis of the physical properties are as follows.

(1) Spin coat

Apparatus: Spin coater LabSpin6TT manufactured by Suss Microtech

(2) Hot plate

Device: As One Co., Ltd. MH-180CS, MH-3CS

(3) UV irradiation

Device: UV curing device US5-0401 manufactured by Eye Graphics Co., Ltd. 4 kW × 1 light

(4) scratch test

Device: Reciprocating wear tester TRIBOGEARTYPE: 30S manufactured by Heydon Scientific Co., Ltd.

Load: 250g/cm ²

Scanning speed: 3m/min

(5) Gel permeation chromatography (GPC)

Device: Tosoh Corporation HLC-8220GPC

Column: Showa Denko Co., Ltd. Shodex (registered trademark) GPC KF-804L, GPC KF-805L

Column temperature: 40°C

Eluent: tetrahydrofuran

Detector: RI

(6) Film thickness

Device: Nikon Digital Measuring Instrument Digimicro MH-15M + Counter TC-101A

(7) Glossiness

Device: Gloss meter GM-268Plus manufactured by Konica Minolta Co., Ltd.

Measuring angle: 60 degrees

(8) Total light transmittance, haze

Apparatus: Haze meter NDH5000 manufactured by Nippon Denshoku Kogyo Co., Ltd.

(9) Contact angle

Apparatus: Kyowa Interface Science Co., Ltd. DropMaster DM-501

Measurement temperature: 20℃

In addition, the abbreviation symbol shows the following meaning.

PFPE1: perfluoropolyether [Fluorolink 5147X manufactured by Solbase Specialty Polymers] having a hydroxyl group via a poly(oxyalkylene) group (8 to 9 repeating units) at both terminals.

BEI: 1,1-bis(acryloyloxymethyl)ethyl isocyanate [Karenz (registered trademark) BEI manufactured by Showa Denko Co., Ltd.]

DBTDL: Dibutyltin dilaurate [manufactured by Tokyo Chemical Industry Co., Ltd.]

HTES: triethoxy (hexyl) silane [Shin-Etsu Silicone (registered trademark) KBE-3063 manufactured by Shin-Etsu Chemical Co., Ltd.]

MPTES: triethoxy(3-methacryloyloxypropyl)silane [Shin-Etsu Silicone (registered trademark) KBE-503 manufactured by Shin-Etsu Chemical Co., Ltd.]

TEOS: Tetraethoxysilane [TSL8124 manufactured by Momentive Performance Materials Japan (East)]

DPHA: dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture [KAYALAD DPHA manufactured by Nippon Kayaku Co., Ltd.]

PETA: pentaerythritol triacrylate/pentaerythritol tetraacrylate mixture [NK Ester A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]

UA: hexafunctional aliphatic urethane acrylate oligomer [EBECRYL (registered trademark) 5129 manufactured by Daicel Allnex Co., Ltd.]

SM2: UV-reactive fluorine-based surface modifier having a perfluoropolyether structure [Megafak (registered trademark) RS-75 manufactured by DIC Co., Ltd., active ingredient 40% by mass MEK/MIBK solution]

FP1: Cross-linked polymethyl methacrylate spherical particles [Sekisui Chemical Industry Co., Ltd. Techpolymer (registered trademark) SSX-105, average particle diameter 5 μm]

FP2: cross-linked polymethyl methacrylate spherical particles [Sekisui Chemical Industry Co., Ltd. Techpolymer (registered trademark) SSX-103, average particle diameter 3 μm]

FP3: cross-linked polymethyl methacrylate spherical particles [Sekisui Chemical Industry Co., Ltd. Techpolymer (registered trademark) SSX-102, average particle diameter 2 μm]

I2959: 2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one [IRGACURE 2959 manufactured by BASF Japan Co., Ltd.]

EPA: ethyl p-dimethylaminobenzoate [KAYACURE EPA manufactured by Nippon Kayaku Co., Ltd.]

EtOH: ethanol

MEK: methyl ethyl ketone

MIBK: methyl isobutyl ketone

PGME: propylene glycol monomethyl ether

[Production Example 1] Production of perfluoropolyether SM1 having poly(oxyalkylene) groups at both ends and acryloyl groups via one urethane bond

To the screw tube, 1.05 g (0.5 mmol) of PFPE1, 0.26 g (1.0 mmol) of BEI, 10 mg (0.016 mmol) of DBTDL, and 1.30 g of MEK were added. This mixture was stirred at room temperature (about 23°C) for 24 hours using a stirrer tip. This reaction mixture was diluted with 3.93 g of MEK to obtain a 20% by mass MEK solution of the target compound SM1.

The weight average molecular weight Mw of the obtained SM1 measured in terms of polystyrene by GPC was 3,400, and the degree of dispersion: Mw (weight average molecular weight)/Mn (number average molecular weight) was 1.2.

[Production Examples 2-1 to 2-3] Preparation of primer composition (composition for forming primer layer)

An alkoxysilane and ethanol were added to the reaction flask according to the description in Table 1, and stirred for 5 minutes under a nitrogen stream to prepare an alkoxysilane/ethanol solution. To this solution, an oxalic acid-water/ethanol solution prepared separately according to the description in Table 1 was added dropwise over 10 minutes. After stirring this solution for 30 minutes, it was heated and stirred for 1 hour until the inner liquid was refluxed (about 80°C). The reaction mixture was cooled to room temperature (about 23°C), and primer compositions (PR1 to PR3) having a siloxane oligomer concentration of 40% by mass were obtained.

The weight average molecular weight Mw and dispersion degree: Mw/Mn measured in terms of polystyrene by GPC of the obtained siloxane oligomer were 1,400, 1.1 (PR1), 1,500, 1.1 (PR2), and 1,500, 1.1 (PR3), respectively.

[Table 1]

[Production Examples 3-1 to 3-4] Preparation of hard coat composition (curable composition)

According to the description of Table 2, the following components were mixed to prepare hard coat compositions (HC1 to HC4) having a solid content concentration of 40% by mass. In addition, solid content refers to components other than a solvent here. In addition, in a table|surface, [part] shows [mass part].

(1) Polyfunctional monomer: DPHA 50 parts by mass, UA 30 parts by mass, and PETA 20 parts by mass

(2) Surface modifier: 1 part by mass of the surface modifier listed in Table 2 (solid content or active ingredient conversion)

(3) Organic particulates: Organic particulates listed in Table 2 in the amount shown in Table 2

(4) polymerization initiator: I2959 5 parts by mass

(5) Polymerization accelerator: EPA 0.1 part by mass

(6) Solvent: amount shown in PGME Table 2

[Table 2]

[Examples 1-8, Comparative Examples 1-3]

The primer composition diluted with PGME to the solid content concentration (siloxane oligomer concentration) shown in Table 3 was spin-coated (1,000 rpm for 30 seconds) on a glass substrate (10 cm × 10 cm, thickness 0.7 mm) to obtain a coating film. By heating this coating film on a 120 degreeC hot plate for 1 hour, the primer layer (cured film) of the thickness shown in Table 3 was formed.

On this primer layer, the hard coat composition shown in Table 3 was spin-coated (number of revolutions shown in Table 3 for 30 seconds) to obtain a coating film. This coating film was dried on a hot plate at 120°C for 3 minutes to remove the solvent. The obtained film was irradiated with UV light at an exposure amount of 500 mJ/cm ² in a nitrogen atmosphere and exposed to produce a hard coat laminate having a hard coat layer (cured film) having a thickness shown in Table 3.

Anti-glare properties, adhesion, scratch resistance, total light transmittance, haze, and contact angles of water and oleic acid of the obtained hard coat laminate were evaluated. The order of evaluation of anti-glare property, adhesiveness, abrasion resistance, and a contact angle is shown below. In addition, a result is combined with Table 4 and shown.

[Bang Hyeon-seong]

The obtained hard-coat laminate was placed on a black platform having a glossiness Gs (60°) of 11.8, and the glossiness Gs (60°) of the surface of the hard-coat layer was measured and evaluated according to the following criteria. On the other hand, when actual use is assumed as a hard coat laminate, at least B is required, and A is preferable.

A: Gs(60°)≤120

B: 120<Gs(60°)≤125

C: Gs(60°)>125

[Adhesion]

On the hard coat layer, use a guide [Cross Cut Guide CCI-2 manufactured by Kotech Co., Ltd.] to cut a 25-division (5 × 5, 2 mm gap) right-angled lattice pattern sheath, and then tape the transparent tape [Nichiban] with a width of 18 mm. Co., Ltd. Cellotape (registered trademark) CT-18] was used and evaluated according to the following criteria using the cross-cut method (based on JIS 5600-5-6).

A: All 25 grids are not peeled off

B: 1 to 11 graduations peel off

C: 12 scales or more are peeling

[Scratch resistance]

The surface of the hard coat layer was rubbed 1,000 reciprocally by applying a load of 250 g/cm ² with steel wool [Bornstar (registered trademark) #0000 (ultra-fine) manufactured by Bornstar Sales Co., Ltd.] mounted on a reciprocating abrasion tester, and the rubbed part Then, a line was drawn with an oil-based marker [using Maki extra-fine (blue), thin sides manufactured by Zebra Co., Ltd.]. Then, the drawn lines were wiped off with a nonwoven fabric wiper [BEMCOT (registered trademark) M-1 manufactured by Asahi Kasei Co., Ltd.], and the degree of scratches was visually confirmed and evaluated according to the following criteria. On the other hand, when actual use is assumed as a hard coat laminate, at least B is required, and A is preferable.

A: No scratches, lines drawn with an oil-based marker are wiped clean

B: Slightly scratched, but lines drawn with an oil-based marker are wiped clean

C: The ink of the oil-based marker is scratched and not wiped off

[contact angle]

1 µL of water or oleic acid was applied to the surface of the hard coat layer, and the contact angle θ after 5 seconds was measured at 5 points, and the average value was used as the contact angle value.

[Table 3]

Table 3

[Table 4]

As shown in Tables 1 to 4, the hard coat layer using perfluoropolyether SM1 as a surface modifier that binds an acryloyl group via a poly(oxyalkylene) group and one urethane bond group at both ends. In the formation, in the laminates 1 to 6, laminate 10 and laminate 11 of Examples 1 to 8 provided with a primer layer, anti-glare properties are excellent, and adhesion and scratch resistance are also satisfactory in practical use. It is a quality that can be obtained, and furthermore, it has become a laminate with excellent transparency.

On the other hand, in the case of using a siloxane oligomer (a siloxane oligomer deviating from the provisions of the present invention) having no radically polymerizable double bond in the primer layer (Comparative Example 1), and in the case of not providing a primer layer (Comparative Example 2), hard As a result, the adhesion of the coating layer to the glass substrate was low and the scratch resistance was poor.

In addition, in the case of using the UV-reactive fluorine-based surface modifier SM2 having a perfluoropolyether structure as a surface modifier in the hard coat layer (Comparative Example 3), satisfactory anti-glare properties and adhesiveness were obtained, but desired scratch resistance was obtained. couldn't get

As shown in the results of the above examples, in the laminate having a hard coat layer employing a specific perfluoropolyether as a surface modifier, a material containing a specific siloxane oligomer having a radically polymerizable double bond By providing a primer layer made of cargo, a laminate satisfying all the performances of anti-glare property, scratch resistance and adhesion to a substrate can be obtained.

Claims (16)

An anti-glare hard coat laminate comprising a base material, a primer layer above the base material, and a hard coat layer above the primer layer,
The primer layer,
A siloxane oligomer having a radically polymerizable double bond obtained by hydrolytic condensation of an alkoxysilane containing at least alkoxysilane A represented by formula [1] and alkoxysilane B represented by formula [2] as component (A)
Made of a cured product of a composition for forming a primer layer comprising

(Wherein, R ¹ represents a monovalent organic group having a radically polymerizable double bond, and R ³ is an alkyl group having 1 to 10 carbon atoms (the alkyl group is an amino group substituted with a fluorine atom or an alkyl group having at least 1 to 6 carbon atoms; It may be substituted with at least an amino group substituted with a phenyl group, or a ureido group.) or a phenyl group, R ² and R ⁴ each independently represent a methyl group or an ethyl group, a represents an integer of 1 or 2, and b represents an integer from 0 to 2.)
The hard coat layer,
As component (a), 100 parts by mass of an active energy ray-curable polyfunctional monomer;
As component (b), a poly(oxyalkylene) group and one urethane bond group are added to both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group via a poly(oxyalkylene) group or a poly(oxyalkylene) group and one urethane bond group in this order. 0.1 to 10 parts by mass of perfluoropolyether that binds an active energy ray polymerizable group through
As component (c), 8 to 30 parts by mass of organic particulates having an average particle diameter of 1 to 10 μm, and
As component (d), 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays
It consists of a cured product of a curable composition comprising,
The active energy ray is ultraviolet rays, electron rays or X-rays,
Anti-glare hard coat laminate. According to claim 1,
The radically polymerizable double bond obtained by the siloxane oligomer having a radically polymerizable double bond of the component (A) hydrolytically condensing alkoxysilane A represented by formula [1] and alkoxysilane B represented by formula [2] A siloxane oligomer having a, anti-glare hard coat laminate.

(Wherein, R ¹ represents a monovalent organic group having a radically polymerizable double bond, R ³ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be substituted with a fluorine atom, and R ² and R ⁴ are each Independently, represents a methyl group or an ethyl group, a represents an integer of 1 or 2, and b represents an integer of 0 to 2.) According to claim 1 or 2,
The anti-glare hard coat laminate wherein R ¹ in Formula [1] is a monovalent organic group having a vinyl group or a (meth)acrylic group. According to claim 3,
The alkoxysilane A is a compound represented by the following formula [3], the anti-glare hard coat laminate.

(In the formula, R ² represents the same definition as in the above formula [1], R ⁵ represents a hydrogen atom or a methyl group, and L ¹ represents an alkylene group having 1 to 10 carbon atoms.) According to claim 1 or 2,
An anti-glare hard coat laminate wherein the siloxane oligomer having a radical polymerizable double bond of the component (A) is a siloxane oligomer containing 10 to 99 mol% of the alkoxysilane A unit. According to claim 1 or 2,
The poly(oxyperfluoroalkylene) group of the perfluoropolyether of component (b) is a group having -[OCF ₂ ]- and -[OCF ₂ CF ₂ ]- as repeating units, laminated with an anti-glare hard coat. sifter. According to claim 1 or 2,
The anti-glare hard coat laminate wherein the poly(oxyalkylene) group of the perfluoropolyether of the component (b) is a poly(oxyethylene) group. According to claim 1 or 2,
The anti-glare hard coat laminate wherein the multifunctional monomer of component (a) is at least one selected from the group consisting of polyfunctional (meth)acrylate compounds and polyfunctional urethane (meth)acrylate compounds. According to claim 1 or 2,
The anti-glare hard coat laminate wherein the organic particulates of component (c) are spherical particles. According to claim 1 or 2,
The anti-glare hard coat laminate wherein the organic fine particles of component (c) are polymethyl methacrylate particles. According to claim 1 or 2,
The polymerization initiator of the component (d) is an alkylphenone polymerization initiator, an anti-glare hard coat laminate. According to claim 1 or 2,
The hard coat layer has a thickness of 1 to 10/3 times the average particle diameter of the organic particulates of the component (c), the anti-glare hard coat laminate. According to claim 1 or 2,
The hard coat layer has a film thickness of 1 to 20 μm, an anti-glare hard coat laminate. According to claim 13,
The hard coat layer has a film thickness of 3 to 10 μm, an anti-glare hard coat laminate. According to claim 1 or 2,
The anti-glare hard coat laminate in which the base material is glass. A method for producing an anti-glare hard coat laminate comprising a primer layer on at least one surface of a substrate and a hard coat layer above the primer layer,
A step of forming a coating film by applying a composition for forming a primer layer on a substrate;
A step of heating a coating film of the composition for forming a primer layer and curing the coating film to form a primer layer;
A step of forming a coating film by applying a curable composition on the primer layer, and
A step of irradiating the coating film of the curable composition with active energy rays and curing the coating film to form a hard coat layer;
The composition for forming the primer layer,
As component (A), a siloxane oligomer having a radically polymerizable double bond obtained by hydrolytic condensation of an alkoxysilane containing at least alkoxysilane A represented by formula [1] and alkoxysilane B represented by formula [2] include,

(Wherein, R ¹ represents a monovalent organic group having a radically polymerizable double bond, and R ³ is an alkyl group having 1 to 10 carbon atoms (the alkyl group is an amino group substituted with a fluorine atom or an alkyl group having at least 1 to 6 carbon atoms; It may be substituted with at least an amino group substituted with a phenyl group, or a ureido group.) or a phenyl group, R ² and R ⁴ each independently represent a methyl group or an ethyl group, a represents an integer of 1 or 2, and b represents an integer from 0 to 2.)
The curable composition,
As component (a), 100 parts by mass of an active energy ray-curable polyfunctional monomer;
As component (b), a poly(oxyalkylene) group and one urethane bond group are added to both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group via a poly(oxyalkylene) group or a poly(oxyalkylene) group and one urethane bond group in this order. 0.1 to 10 parts by mass of perfluoropolyether that binds an active energy ray polymerizable group through
As component (c), 8 to 30 parts by mass of organic particulates having an average particle diameter of 1 to 10 μm, and
As component (d), 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays
Including,
The active energy ray is ultraviolet rays, electron rays or X-rays,
Method for producing an anti-glare hard coat laminate.