WO2018070426A1 - Anti-glare hard coat laminate - Google Patents

Abstract

[Problem] To provide a laminate that has excellent anti-glare properties, that achieves high scratch resistance, and that is provided with a hard coat layer having excellent adhesion to a substrate. [Solution] An anti-glare hard coat laminate comprising a substrate, a primer layer above the substrate, and a hard coat layer above the primer layer. The primer layer comprises a cured product of a primer layer-forming composition containing a siloxane oligomer that has a specific radical-polymerizable double bond. The hard coat layer comprises a cured product of a curable composition containing (a) a polyfunctional monomer, (b) a perfluoropolyether in which an active energy ray-polymerizable group is bonded via a poly(oxyalkylene) group or via a poly(oxyalkylene) group and one urethane bonding group in this order to both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group, (c) organic fine particles, and (d) a polymerization initiator. Also provided is a method for producing the anti-glare hard coat laminate.

Description

Antiglare hard coat laminate

The present invention relates to an antiglare hard coat laminate comprising a hard coat layer excellent in antiglare property (antiglare function) and a method for producing the same.

A large number of products in which a touch panel is mounted on a flat panel display such as a personal computer, a mobile phone, a mobile game machine, and an ATM have been commercialized. In particular, with the advent of smartphones and tablet PCs, the number of capacitive touch panels having a multi-touch function is rapidly increasing.

An anti-glare hard coat film having a hard coat layer of about several μm with irregularities formed on the surface is bonded to the surface of these touch panel displays in order to prevent a decrease in visibility due to reflection of external light on the screen. The method is used. 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 a hard coat layer is generally used.

By the way, the capacitive touch panel is operated by touching it with a human finger. For this reason, fingerprints are attached to the surface of the touch panel every time an operation is performed, causing problems that the visibility of the image on the display is remarkably impaired and the appearance of the display is impaired. The fingerprint contains moisture derived from sweat and oil derived from sebum, and it is strongly desired to impart water repellency and oil repellency to the hard coat layer on the display surface in order to prevent both of them from adhering. ing.
However, since capacitive touch panels are touched by a finger every day, even if the initial antifouling property has reached a considerable level, their functions often deteriorate due to scratches during use. . In particular, the antiglare hard coat layer has irregularities on its surface, so that it tends to be caught and easily damaged. Therefore, the durability of the antifouling property in the process of use has been a problem.

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

JP 2013-257359 A

In the method specifically described in Patent Document 1, 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 antifouling properties are obtained. There was a problem that it was impossible to obtain scratch resistance. Also, if the amount of MS resin particles added is reduced to obtain scratch resistance, sufficient antiglare properties cannot be obtained, and if MS resin particles are added to such an extent that sufficient antiglare properties can be obtained, scratch resistance can be obtained. There was a problem that the remarkably decreased. Furthermore, the dispersibility of the resin particles in the hard coat layer is poor, and it becomes an agglomerate, and the appearance of the coating film is impaired.
Moreover, the hard cord layer using an acrylic resin is particularly inferior in adhesion to a glass substrate, and it has been a subject to be easily peeled off from the substrate.
Thus, there has been a demand for a hard coat layer that is excellent in antiglare properties, exhibits high scratch resistance, and has excellent adhesion to a substrate.

As a result of intensive studies to achieve the above object, the present inventors have provided a primer layer between the base material and the hard coat layer in order to improve the adhesion to the base material, particularly the formation of the primer layer. It has been found that a siloxane oligomer having a radical polymerizable double bond is employed as a material. An active energy ray polymerizable group is attached to both ends of a molecular chain containing a poly (oxyperfluoroalkylene) structure via a poly (oxyalkylene) group or via a poly (oxyalkylene) group and one urethane bond group. By using a curable composition in which a compound that binds as a fluorine-based surface modifier and further adding organic fine particles to the hard coat layer forming material, excellent anti-glare properties and The present invention was completed by finding that the laminate was provided with a hard coat layer having high scratch resistance and excellent adhesion.

That is, the present invention provides the first aspect as follows:
An antiglare 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 is
(A) having a radical polymerizable double bond obtained by hydrolytic condensation of an alkoxysilane containing at least an alkoxysilane A represented by the formula [1] and an alkoxysilane B represented by the formula [2] It consists of a cured product of a primer layer forming composition containing a siloxane oligomer,

(In the formula, R ¹ represents a monovalent organic group having a radical polymerizable double bond, R ³ represents an alkyl group having 1 to 10 carbon atoms (the alkyl group is a fluorine atom, at least 1 to 6 carbon atoms) An amino group substituted with an alkyl group, an amino group substituted with at least a phenyl group, or an ureido group) or a phenyl group, wherein R ² and R ⁴ are each independently methyl A group or an ethyl group, a represents an integer of 1 or 2, and b represents an integer of 0 to 2.)
The hard coat layer is
(A) 100 parts by mass of an active energy ray-curable polyfunctional monomer,
(B) Active energy rays via a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane bonding group in this order at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group 0.1 to 10 parts by mass of perfluoropolyether to which a polymerizable group is bonded,
(C) From a cured product of a curable composition comprising 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. Become,
The present invention relates to an antiglare hard coat laminate.
As a second aspect, the siloxane oligomer of the component (A) is a radical obtained by hydrolytic condensation of an alkoxysilane A represented by the formula [1] and an alkoxysilane B represented by the formula [2]. The antiglare hard coat laminate according to the first aspect, which is a siloxane oligomer having a polymerizable double bond.

(In the formula, R ¹ represents a monovalent organic group having a radical polymerizable double bond, and R ³ represents an alkyl group having 1 to 6 carbon atoms which may be substituted with a fluorine atom, or a phenyl group. , R ² and R ⁴ 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, R ¹ in the formula [1] is a monovalent organic group having a vinyl group or a (meth) acryl group, and the antiglare hard coat laminate according to the first aspect or the second aspect. About the body.
As a fourth aspect, the present invention relates to the antiglare hard coat laminate according to the third aspect, in which the alkoxysilane A is a compound represented by the following formula [3].

(In the formula, R ² represents the same meaning as defined in the 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, any one of the first to fourth aspects, wherein the siloxane oligomer having a radical polymerizable double bond as the component (A) is a siloxane oligomer containing 10 to 99 mol% of the alkoxysilane A unit. The antiglare hard coat laminate according to one item.
As a sixth aspect, the poly (oxyperfluoroalkylene) group of the perfluoropolyether of the component (b) is a group having — [OCF ₂ ] — and — [OCF ₂ CF ₂ ] — as repeating units. It is related with the anti-glare hard-coat laminated body as described in any one among a 1st viewpoint thru | or a 5th viewpoint.
As a seventh aspect, the poly (oxyalkylene) group of the perfluoropolyether of the component (b) is a poly (oxyethylene) group, as described in any one of the first aspect to the sixth aspect. The present invention relates to a dazzling hard coat laminate.
As an eighth aspect, the polyfunctional monomer of the 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 is related with the anti-glare hard-coat laminated body as described in any one of viewpoints.
As a ninth aspect, the present invention relates to the antiglare hard coat laminate according to any one of the first aspect to the eighth aspect, wherein the organic fine particles of the component (c) are spherical particles.
As a tenth aspect, the present invention relates to the antiglare hard coat laminate according to any one of the first aspect to the ninth aspect, wherein the organic fine particles of the component (c) are polymethyl methacrylate particles.
As an eleventh aspect, the present invention relates to the antiglare hard coat laminate according to any one of the first aspect to the tenth aspect, wherein the polymerization initiator of the component (d) is an alkylphenone polymerization initiator.
As a twelfth aspect, any one of the first to eleventh aspects, wherein the hard coat layer has a thickness of 1 to 10/3 times the average particle diameter of the organic fine particles of the component (c). The antiglare hard coat laminate according to one item.
As a thirteenth aspect, the present invention relates to the antiglare hard coat laminate according to any one of the first to twelfth aspects, wherein the hard coat layer has a thickness of 1 to 20 μm.
As a fourteenth aspect, the present invention relates to the antiglare hard coat laminate according to the thirteenth aspect, wherein the hard coat layer has a thickness of 3 to 10 μm.
As a fifteenth aspect, the present invention relates to the antiglare hard coat laminate according to any one of the first aspect to the fourteenth aspect, in which the substrate is glass.
As a sixteenth aspect, a method for producing an antiglare hard coat laminate comprising a primer layer on at least one surface of a substrate and a hard coat layer above the primer layer,
Applying a primer layer forming composition on a substrate to form a coating film;
Heating the coating film of the primer layer forming composition to cure the coating film and forming a primer layer;
A step of applying a curable composition on the primer layer to form a coating film, and a step of irradiating the coating film of the curable composition with active energy rays to cure the coating film to form a hard coat layer Including,
The primer layer forming composition is
(A) having a radical polymerizable double bond obtained by hydrolytic condensation of an alkoxysilane containing at least an alkoxysilane A represented by the formula [1] and an alkoxysilane B represented by the formula [2] Containing siloxane oligomers,

(In the formula, R ¹ represents a monovalent organic group having a radical polymerizable double bond, R ³ represents an alkyl group having 1 to 10 carbon atoms (the alkyl group is a fluorine atom, at least 1 to 6 carbon atoms) An amino group substituted with an alkyl group, an amino group substituted with at least a phenyl group, or an ureido group) or a phenyl group, wherein R ² and R ⁴ are each independently methyl A group or an ethyl group, a represents an integer of 1 or 2, and b represents an integer of 0 to 2.)
The curable composition is
(A) 100 parts by mass of an active energy ray-curable polyfunctional monomer,
(B) Active energy rays via a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane bonding group in this order at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group 0.1 to 10 parts by mass of perfluoropolyether to which a polymerizable group is bonded,
(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.
The present invention relates to a method for producing an antiglare hard coat laminate.

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

The antiglare hard coat laminate of the present invention comprises a substrate, a primer layer above the substrate, and a hard coat layer above the primer layer.
In the antiglare hard coat laminate of the present invention, the primer layer comprises a cured product of a primer layer forming composition containing a siloxane oligomer having a radical polymerizable double bond, and the hard coat layer has an active energy. It consists of hardened | cured material of the curable composition containing a linear curable polyfunctional monomer etc.
Hereinafter, each layer constituting the antiglare hard coat laminate of the present invention will be described in detail.

"Base material"
The base material in the antiglare hard coat laminate of the present invention is not particularly limited. For example, plastic (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 and the like. The shape of these base materials may be a plate shape, a film shape, or a three-dimensional molded body.
Especially, in this invention, glass can be used conveniently as a base material.
The thickness of the substrate is not particularly limited, but can be, for example, 10 to 1,000 μm.

《Primer layer》
<Primer layer forming composition>
The primer layer in the antiglare hard coat laminate of the present invention comprises a cured product of a primer layer forming composition containing the following component (A):
(A) having a radical polymerizable double bond obtained by hydrolytic condensation of an alkoxysilane containing at least an alkoxysilane A represented by the formula [1] and an alkoxysilane B represented by the formula [2] Siloxane oligomer.

(In the formula, R ¹ represents a monovalent organic group having a radical polymerizable double bond, R ³ represents an alkyl group having 1 to 10 carbon atoms (the alkyl group is a fluorine atom, at least 1 to 6 carbon atoms) An amino group substituted with an alkyl group, an amino group substituted with at least a phenyl group, or an ureido group) or a phenyl group, wherein R ² and R ⁴ are each independently methyl A group or an ethyl group, a represents an integer of 1 or 2, and b represents an integer of 0 to 2.)

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

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

In the above formula [1], R ¹ represents a monovalent organic group having a radical polymerizable double bond, R ² represents a methyl group or an ethyl group, and a represents an integer of 1 or 2.
In the formula [2], R ³ represents an alkyl group having 1 to 10 carbon atoms (the alkyl group is substituted with a fluorine atom, an amino group substituted with at least an alkyl group having 1 to 6 carbon atoms, or at least a phenyl 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 represents an integer of 0 to 2.

The monovalent organic group having a radically polymerizable double bond of R ^{1 in} the above formula [1] is preferably a monovalent organic group having a vinyl group or a (meth) acryl group. In the present invention, the (meth) acryl group means both an acryl group and a methacryl group.
In addition, the alkyl group having 1 to 10 carbon atoms represented by R ³ in the above formula [2] (the alkyl group is a fluorine atom, an amino group substituted with at least an alkyl group having 1 to 6 carbon atoms, and at least a phenyl group). And may be substituted with a substituted amino group or ureido group.) As methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Examples thereof include a butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, cyclohexyl group, n-octyl group and n-decyl group.
In addition, the amino group substituted with at least an alkyl group having 1 to 6 carbon atoms represented by R ³ in the above formula [2] includes a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, and n-propylamino. Group, isopropylamino group, n-butylamino group, tert-butylamino group, n-pentylamino group, n-hexylamino group, cyclohexylamino group, N-methyl-N-phenylamino group and the like.
Furthermore, examples of the amino group substituted with at least a phenyl group represented by R ³ in the above formula [2] include a phenylamino group and a diphenylamino group.

Among the alkoxysilanes A represented by the above formula [1], a compound represented by the following formula [3] is preferable.

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, L ¹ represents an alkylene group having 1 to 10 carbon atoms, preferably 1 to 1 carbon atom. 8 represents an alkylene group, more preferably an alkylene group having 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 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 and the like.
Among these, 3- (meth) acryloyloxypropyltrimethoxysilane and triethoxy (3- (meth) acryloyloxypropyl) silane are preferable.

Specific examples of the alkoxysilane B represented by the above 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, dimethoxy Toxidimethylsilane, diethyldimethoxysilane, diethoxydiethylsilane, dimethoxydipropylsilane, diethoxydipropylsilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dimethoxydipentylsilane, diethoxydipentylsilane, dihexyldimethoxysilane, diethoxydihexylsilane , Dimethoxydiphenylsilane, diethoxydiphenylsilane, trimethoxy ((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) The siloxane oligomer is preferably a siloxane oligomer containing 10 to 99 mol% of the alkoxysilane A unit in the total alkoxysilane units.

In particular, the (A) siloxane oligomer is preferably a siloxane oligomer containing at least 10 to 99 mol% of the structural unit represented by the following formula [4] in all the structural units.

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

The method for obtaining the (A) siloxane oligomer is not particularly limited.
For example, it can be obtained by condensing an alkoxysilane containing the alkoxysilane A and alkoxysilane B in an organic solvent. Examples of the method of polycondensing alkoxysilane include a method of hydrolyzing and condensing alkoxysilane in a solvent such as alcohol or glycol. At that time, the hydrolysis / condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, theoretically, it is sufficient to add 0.5 times mole of water of all alkoxy groups in the alkoxysilane, but it is usually preferable to add an excess amount of water more than 0.5 times mole. In the present invention, the amount of water used in the above reaction can be appropriately selected as desired, but it is usually preferably 0.5 to 2.5 times mol of all alkoxy groups in alkoxysilane.
Usually, for the purpose of promoting 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, stearin 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, Organic acids such as trichloroacetic acid, trifluoroacetic acid, benzoic acid, p-aminobenzoic acid, salicylic acid, gallic acid, phthalic acid, mellitic acid, benzenesulfonic acid, p-toluenesulfonic acid; hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, Inorganic acids such as phosphoric acid and metal salts thereof; ammonia, methylamine, ethylamine, ethanolamine, triethylamine Catalysts such as alkali emissions and the like are used. In addition, it is also common to further promote the hydrolysis / condensation reaction by heating the solution in which the alkoxysilane is dissolved. At that time, the heating temperature and the heating time can be appropriately selected as desired. For example, a method of heating / stirring at 50 ° C. for 24 hours, a method of heating / stirring under reflux for 1 hour, and the like can be mentioned.
As another method, for example, a method of heating and polycondensing a mixture of alkoxysilane, a solvent and oxalic acid can be mentioned. Specifically, after adding oxalic acid to alcohol in advance to make an alcohol solution of oxalic acid, the alkoxysilane is mixed while the solution is heated. At that 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. A method of heating for several tens of minutes to several tens of hours under reflux is preferred so that the liquid does not evaporate or volatilize.

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

In the present invention, by using the above siloxane oligomer as the primer layer forming material, a partial hydrolysis condensation reaction proceeds between the oligomers at the time of forming the primer layer, and the alcohol generated at this time volatilizes, so that the primer layer has gaps. As a result, it is presumed that it contributes to improving the adhesion between the primer layer as a whole and the hard coat layer.

[solvent]
The composition for forming a primer layer used in the present invention may further include a solvent to form a varnish.
The solvent used at this time may be any solvent that dissolves or disperses the component (A) and other components described later if desired. For example, aromatic hydrocarbons such as toluene and xylene; ethyl acetate, butyl acetate , Isobutyl acetate, γ-butyrolactone, methyl pyruvate, ethyl pyruvate, hydroxyethyl acetate, ethyl lactate, butyl lactate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, ethyl ethoxyacetate , Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), pro Esters or ester ethers such as lenglycol monopropyl ether acetate; ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME); methyl ethyl ketone (MEK) ), Ketones such as methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone; methanol, ethanol, n-propanol, 2-propanol, n-butanol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, propylene glycol Alcohols such as N, N-dimethylformamide (DMF), N, N-dimethyla Amides such as cetamide and N-methyl-2-pyrrolidone (NMP) can be used. These solvents can be used alone or in combination of two or more or in a mixed solvent with water.

The solid content concentration in the primer layer forming composition 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 obtained by removing the solvent component from all the components of the primer layer forming composition.

[Other additives]
Furthermore, additives that are generally added to the composition for forming a primer layer used in the present invention as needed, for example, photosensitizers, polymerization inhibitors, polymerizations, as long as the effects of the present invention are not impaired. Initiators, leveling agents, surfactants, adhesion promoters, plasticizers, UV absorbers, antioxidants, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes, etc., and active energy ray curing A functional polyfunctional monomer or the like may be appropriately blended.

[Active energy ray-curable polyfunctional monomer]
The primer layer forming composition used in the present invention may further contain an active energy ray-curable polyfunctional monomer in order to improve the adhesion with the hard coat layer thereabove.
Examples of the active energy ray-curable polyfunctional monomer used in the primer layer forming composition include polyfunctional (meth) acrylate compounds and polyfunctional urethanes exemplified in <(a) Active energy ray-curable polyfunctional monomer> described below. Examples include monomers selected from the group consisting of (meth) acrylate compounds, polyfunctional epoxy (meth) acrylate compounds, polyfunctional polyester (meth) acrylate compounds, and unsaturated polyesters.
In the present invention, the (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 preferably in an amount of 1 to 300 parts by mass with respect to 100 parts by mass of the above-mentioned (A) siloxane oligomer. Is used in an amount of 1 to 200 parts by weight, particularly preferably in an amount of 10 to 100 parts by weight.

[Polymerization initiator that generates radicals by active energy rays]
When the composition for forming a primer layer used in the present invention contains the above <active energy ray-curable polyfunctional monomer>, it is further exemplified in <(d) polymerization initiator that generates radicals by active energy rays> 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, it is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the (A) siloxane oligomer, preferably 0. Used in an amount of 1 to 20 parts by weight, particularly preferably in an amount of 1 to 20 parts by weight.

《Hard coat layer》
<Curable composition>
The hard coat layer in the antiglare hard coat laminate of the present invention comprises a cured product (that is, a 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) the active energy at both ends of the molecular chain containing the poly (oxyperfluoroalkylene) group via the poly (oxyalkylene) group or via the poly (oxyalkylene) group and one urethane bond group in this order; 0.1 to 10 parts by mass of perfluoropolyether to which a linear polymerizable group is bonded,
(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, the components (a) to (d) will be described.

[(A) Active energy ray-curable polyfunctional monomer]
The active energy ray-curable polyfunctional monomer refers to a monomer that is cured by a polymerization reaction that proceeds by irradiation with an active energy ray such as ultraviolet rays.
Preferred (a) active energy ray-curable polyfunctional monomer in the curable composition used in the present invention is a monomer selected from the group consisting of polyfunctional (meth) acrylate compounds and polyfunctional urethane (meth) acrylate compounds. is there.

Examples of the polyfunctional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol diester. (Meth) acrylate monostearate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, propoxylated glycerin tri (meth) acrylate, Ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated pet Taerythritol 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-propanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2-methyl- 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (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-hydroxyethyl) 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-methacryloyloxy-propane, 2-hydroxy-1 3-di (meth) acryloyloxypropane, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, bis [4- (meth) acryloylthiophenyl] sulfide, bis [2- ( (Meth) acryloylthioethyl] sulfide, 1,3-adamantanediol di (meth) acrylate, 1,3-adamantane dimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tris (2- (meth) acryloyloxyethyl) phosphate, ε-caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, and the like.
Among them, preferred are pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like.

The polyfunctional urethane (meth) acrylate compound is a compound having a plurality of acryloyl groups or methacryloyl groups in one molecule and one or more urethane bonds (—NHCOO—).
For example, the polyfunctional urethane (meth) acrylate compound is obtained by a reaction between a polyfunctional isocyanate and a (meth) acrylate having a hydroxy group, or a reaction between a polyfunctional isocyanate and a (meth) acrylate having a hydroxy group and a polyol. However, the polyfunctional urethane (meth) acrylate compound that can be used in the present invention is not limited to such examples.

Examples of the polyfunctional isocyanate include tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and hexamethylene diisocyanate.
Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth). An 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; these diols, succinic acid, malein Examples include polyester polyols which are reaction products with aliphatic dicarboxylic acids or dicarboxylic anhydrides such as acids and adipic acid; polyether polyols; polycarbonate diols and the like.

In the present invention, as the (a) active energy ray-curable polyfunctional monomer, one kind is selected from the group consisting of the polyfunctional (meth) acrylate compound and the polyfunctional urethane (meth) acrylate compound, or two or more kinds are used. 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, it is preferable to use together 5 or more functional polyfunctional (meth) acrylate compound and 4 or less polyfunctional (meth) acrylate compound as said polyfunctional (meth) acrylate compound.
Moreover, when using the said polyfunctional (meth) acrylate compound and the said polyfunctional urethane (meth) acrylate compound in combination, the polyfunctional urethane (meth) acrylate compound 20 with respect to 100 mass parts of polyfunctional (meth) acrylate compounds. It is preferable to use ˜100 parts by mass, and it is more preferable to use 30 to 70 parts by mass.
Furthermore, in the polyfunctional (meth) acrylate compound, when the polyfunctional (meth) acrylate compound having 5 or more functions and the polyfunctional (meth) acrylate compound having 4 or less functions are used in combination, the polyfunctional (meth) acrylate compound has 5 or more functions. It is preferable to use 10 to 100 parts by mass of a tetrafunctional or lower polyfunctional (meth) acrylate compound with respect to 100 parts by mass of the functional (meth) acrylate compound, and it is more preferable to use 20 to 60 parts by mass.
In addition, polyfunctional urethane (meth) acrylate compound 20 to 100 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound and polyfunctional (meth) acrylate compounds having a functionality of 4 or less with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound. (Meth) acrylate compound to be used at 10 to 100 parts by mass,
Polyfunctional (meth) acrylate compound 20 to 100 parts by mass with respect to 100 parts by mass of polyfunctional (meth) acrylate compound and polyfunctional (meth) acrylate compound with a functionality of 4 or less with respect to 100 parts by mass of polyfunctional (meth) acrylate compound having 5 or more functions ) Use at 20-60 parts by mass of acrylate compound,
Polyfunctional (meth) acrylate compound 100 parts by mass Polyfunctional urethane (meth) acrylate compound 30 to 70 parts by mass and pentafunctional or higher polyfunctional (meth) acrylate compound 100 parts by mass ) Use at 10 to 100 parts by mass of acrylate compound,
Polyfunctional (meth) acrylate compound 100 parts by mass Polyfunctional urethane (meth) acrylate compound 30 to 70 parts by mass and pentafunctional or higher polyfunctional (meth) acrylate compound 100 parts by mass ) The acrylate compound is preferably used in an amount of 20 to 60 parts by mass.

[(B) Active via a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane bond group in this order at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group Perfluoropolyether binding energy beam polymerizable groups]
In the present invention, as the component (b), a poly (oxyalkylene) group and one urethane bonding group are bonded to both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group. Through this order, a perfluoropolyether (hereinafter also referred to as “(b) a perfluoropolyether having a polymerizable group at both ends”) to which an active energy ray polymerizable group is bonded is used. The component (b) serves 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 preferably 1 to 4 carbon atoms. That is, the poly (oxyperfluoroalkylene) group refers to a group having a structure in which a divalent fluorocarbon group having 1 to 4 carbon atoms and oxygen atoms are alternately connected, and the oxyperfluoroalkylene group is a carbon atom. This refers to a group having a structure in which a divalent fluorocarbon group of formulas 1 to 4 and an oxygen atom are linked. Specifically, — [OCF ₂ ] — (oxyperfluoromethylene group), — [OCF ₂ CF ₂ ] — (oxyperfluoroethylene group), — [OCF ₂ CF ₂ CF ₂ ] — (oxyperfluoropropane) -1,3-diyl group) and-[OCF ₂ C (CF ₃ ) F]-(oxyperfluoropropane-1,2-diyl group).
The above oxyperfluoroalkylene groups may be used alone or in combination of two or more. In such a case, the bonds of plural types of oxyperfluoroalkylene groups are block bonds and random bonds. Any of these may be used.

Among these, from the viewpoint of obtaining a cured product (hard coat layer) having good scratch resistance, as the poly (oxyperfluoroalkylene) group,-[OCF ₂ ]-(oxyperfluoromethylene group) and-[ It is preferable to use a group having both of OCF ₂ CF ₂ ]-(oxyperfluoroethylene group) as a repeating unit.
Among them, as the poly (oxyperfluoroalkylene) group, the repeating unit: — [OCF ₂ ] — and — [OCF ₂ CF ₂ ] — are represented by a molar ratio of [Repeating unit: — [OCF ₂ ] —]: [Repeating Unit: — [OCF ₂ CF ₂ ] —] = 2: 1 to 1: 2 is preferable, and a group including about 1: 1 is more preferable. The bond of these repeating units may be either a block bond or a random bond.
The number of repeating units of the oxyperfluoroalkylene group is preferably in the range of 5 to 30, more preferably in the range of 7 to 21, as the total number of repeating units.
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 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 oxygen atoms are alternately connected, and the oxyalkylene group is a divalent alkylene having 1 to 4 carbon atoms. A group having a structure in which a group and an oxygen atom are linked. Examples of the alkylene group include an ethylene group, a 1-methylethylene group, a trimethylene group, and a tetramethylene group.
The oxyalkylene groups may be used singly or in combination of two or more. In that case, the bonds of the plural oxyalkylene groups may be either block bonds or random bonds. May be.
Among these, the poly (oxyalkylene) group is preferably 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, and more preferably in the range of 5 to 12, for example, 7 to 12.

Examples of the active energy ray-polymerizable group that bonds the poly (oxyalkylene) group or the poly (oxyalkylene) group and one urethane bond group in this order include a (meth) acryloyl group and a urethane (meth) acryloyl group. Group, vinyl group and the like.

The active energy ray polymerizable group is not limited to one having one active energy ray polymerizable portion such as a (meth) acryloyl moiety, and may have two or more active energy ray polymerizable portions, For example, the following structures A1 to A5 and structures in which the acryloyl group in these structures is substituted with a methacryloyl group can be mentioned.

As the perfluoropolyether having a polymerizable group at both ends (b), the following compounds and compounds obtained by substituting acryloyl groups in these compounds with methacryloyl groups from the viewpoint of easy industrial production Can be mentioned as a preferred example. In the structural formula, A represents one of the structures represented by the formulas [A1] to [A5], PFPE represents the poly (oxyperfluoroalkylene) group, and n is independently selected. Represents the number of repeating units of the oxyethylene group, preferably a number of 1 to 15, more preferably a number of 5 to 12, and still more preferably a number of 7 to 12.

Among them, the (b) perfluoropolyether having a polymerizable group at both ends used in the present invention has a poly (oxyalkylene) group and one at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group. Through the urethane bonding groups in this order, that is, poly (oxyalkylene) groups are bonded to both ends of the molecular chain containing the poly (oxyperfluoroalkylene) group, respectively, and each poly (oxyalkylene) group at each end is bonded to each end. It is preferably a perfluoropolyether in which one urethane bond group is bonded and active energy ray polymerizable groups are bonded to the urethane bonds at both ends. Further, in the perfluoropolyether, the active energy ray polymerizable group is preferably a perfluoropolyether which is a group having at least two active energy ray polymerizable moieties.

In the present invention, (b) the perfluoropolyether having a polymerizable group at both ends is 0.1 to 10 parts by weight, preferably 100 parts by weight, preferably 100 parts by weight of the active energy ray-curable polyfunctional monomer. It is desirable to use at a ratio of 0.2 to 5 parts by mass.

The perfluoropolyether having a polymerizable group at both ends (b) is, for example, a compound having a hydroxy group at both ends of a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group. A urethanization reaction of an isocyanate compound having a polymerizable group such as 2- (meth) acryloyloxyethyl isocyanate or 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate with respect to the hydroxy group of (meth) It can be obtained by a method of dehydrochlorinating acrylic acid chloride or chloromethylstyrene, a method of dehydrating (meth) acrylic acid, a method of esterifying itaconic anhydride, and the like.
In particular, in a compound having a hydroxy group at both ends of a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group, 2- (meth) acryloyloxyethyl isocyanate or 1 , 1-bis ((meth) acryloyloxymethyl) ethyl isocyanate or other isocyanate compounds having a polymerizable group, or (meth) acrylic acid chloride or chloromethylstyrene is removed from the hydroxy group. The method of reacting with hydrochloric acid is particularly preferable because the reaction is easy.

The curable composition used in the present invention includes (b) a poly (oxyalkylene) group at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group or a poly (oxyalkylene) group and In addition to the perfluoropolyether to which the active energy ray polymerizable group is bonded through one urethane bonding group in this order, a poly (oxyalkylene) group is added to one end of the molecular chain containing the poly (oxyperfluoroalkylene) group. Or a poly (oxyalkylene) group and one urethane bond group in this order to bind an active energy ray-polymerizable group and a perfluoro group having a hydroxy group at the other end via a poly (oxyalkylene) group Via a poly (oxyalkylene) group at both ends of a molecular chain containing a polyether or poly (oxyperfluoroalkylene) group Compound unbound active energy ray-polymerizable group] perfluoropolyether having a hydroxy group 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 fine particles having an average particle diameter of 1 to 10 μm (hereinafter also simply referred to as “(c) organic fine particles”) are hard coat layers formed from the curable composition. The anti-glare property is imparted by making the surface of the surface uneven.
The organic fine particles can also play a role of 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 that is the hard coat layer forming material.

The shape of the organic fine particles is not particularly limited, but may be, for example, a bead-like substantially spherical shape or an irregular shape such as a powder, but is preferably substantially spherical, more preferably an aspect. A substantially spherical particle having a ratio of 1.5 or less, and most preferably a true spherical particle.

Examples of the organic fine particles include polymethyl methacrylate particles (PMMA particles), silicone particles, polystyrene particles, polycarbonate particles, acrylic styrene particles, benzoguanamine particles, melamine particles, polyolefin particles, polyester particles, polyamide particles, polyimide particles, polyfluoride particles. And ethylene oxide particles. These organic fine particles may be used alone or in combination of two or more.
Among them, polymethyl methacrylate particles can be suitably used as the organic fine particles.

The average particle size of the organic fine particles 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 measurement by a laser diffraction / scattering method based on the Mie theory. When the average particle size of the organic fine particles is larger than the above numerical range, the image sharpness of the display is deteriorated, and when the average particle size is smaller than the above numerical range, sufficient antiglare property cannot be obtained and glare increases. It becomes easy. The organic fine particles are not particularly limited in terms of particle size distribution, but are preferably monodispersed fine particles having a uniform particle size.
The organic fine particles are preferably organic fine particles having a refractive index of 0 to 0.20 in refractive index difference from the cured product of the active energy ray-curable polyfunctional monomer (a). The refractive index difference is preferably 0 to 0.10.
Further, the organic fine particles have an average particle diameter b / film with respect to the cured product obtained from the curable composition used in the present invention described later, that is, the film thickness of the hard coat layer. The thickness a is preferably selected so as to satisfy the range of 0.3 to 1.0.

Commercially available products can be suitably used as the organic fine particles. For example, Techpolymer (registered trademark) MBX series, SBX series, MSX series, SMX series, SSX series, BMX series, ABX series, Same ARX series, Same AFX series, Same MB series, Same MBP series, Same MB-C series, Same ACX series, Same ACP series [above, manufactured by Sekisui Plastics Co., Ltd.]; Tospearl (registered trademark) series [Momentive・ Performance Materials Japan (same)]; Eposter (registered trademark) series, MA series, ST series, MX series [above, Nippon Shokubai Co., Ltd.]; Opt Beads (registered trademark) series [ Nissan Chemical Industries, Ltd.]; Flow beads series [Sumitomo Seika Co., Ltd.] Trepearl (registered trademark) PPS, PAI, PES, EP (above, manufactured by Toray Industries, Inc.); 3M (registered trademark) Dionion TF micro powder series (produced by 3M); Chemisnow (registered trademark) MX series, MZ series, MR series, same KMR series, same KSR series, same MP series, same SX series, same SGP series [above, manufactured by Soken Chemical Co., Ltd.]; Tuftic (registered trademark) AR650 series, same AR-750 series FH-S Series, A-20, YK Series, 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 Leeds [above, Negami Chemical Industrial Co., Ltd.]; Shin-Etsu Silicone can be used (registered trademark) KMP series [Shin-Etsu Chemical Co., Ltd.] or the like.

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

[(D) Polymerization initiator that generates radicals by active energy rays]
In the curable composition used in the present invention, preferred polymerization initiators that generate radicals by active energy rays (hereinafter also simply referred to as “(d) polymerization initiator”) include, for example, electron beams, ultraviolet rays, and X-rays. It is a polymerization initiator that generates radicals by active energy rays, particularly when irradiated with ultraviolet rays.
Examples of the above (d) polymerization initiator include benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinonediazides, acylphosphine oxides, oxime esters, organic peroxides, benzophenones. Biscumarins, bisimidazoles, titanocenes, thiols, halogenated hydrocarbons, trichloromethyltriazines, or onium salts such as iodonium salts and sulfonium salts. 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 polymerization initiator as the polymerization initiator (d) from the viewpoints of transparency, surface curability, and thin film curability. By using an alkylphenone polymerization initiator, a cured product (hard coat layer) with 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 Α-hydroxyalkylphenones such as 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Α-aminoalkylphenones such as butan-1-one; 2,2-dimethoxy-1,2-diphenylethane-1-one; And methyl phenylglyoxylate.

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

[(E) Solvent]
The curable composition used in the present invention may further include (e) a solvent, that is, a varnish (film forming material).
As the above-mentioned solvent, the components (a) to (d) are dissolved and dispersed, and the workability at the time of coating for forming a cured product (hard coat layer) to be described later and the drying property before and after curing are taken into consideration. For example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit and cyclohexane; Halides such as methyl, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene; ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate , Ethyl cellosolve acetate, propylene glycol monomethyl ether Esters such as cetate or ester ethers; 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, propylene Ethers such as 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; methanol, ethanol, n-propanol, isopropyl alcohol, n- Butanol, isobutyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, ben Alcohols such as 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; Moreover, these 2 or more types of mixed solvents are mentioned.

In addition, a solvent having a high boiling point can be used for the purpose of controlling the dispersibility of the fine particles during drying after coating.
Examples of such solvents include cyclohexyl acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, 1,6-hexanediol diacetate, 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. Can be mentioned.

The amount of these (e) solvents to be used is not particularly limited. For example, the solvent is used in such a concentration that the solid content 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 based on the total mass (total mass) of the components (a) to (e) (and other additives as required) of the curable composition used in the present invention. It represents the content of solid content (excluding solvent components from all components).

[Other additives]
In addition, additives that are generally added as necessary to the curable composition used in the present invention, for example, a polymerization accelerator, a polymerization inhibitor, and a photosensitizer, as long as the effects of the present invention are not impaired. , Leveling agents, surfactants, adhesion-imparting agents, plasticizers, ultraviolet absorbers, antioxidants, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes, and the like may be appropriately blended.
Moreover, you may mix | blend inorganic fine particles, such as a titanium oxide, in order to control the haze value of hardened | cured material (hard-coat layer).

<Anti-glare hard coat laminate>
As described above, the antiglare 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 antiglare hard coat laminate of the present invention is
(I) applying a primer layer forming composition on a substrate to form a coating film;
(Ii) heating and curing the coating film of the primer layer forming composition to form a primer layer;
(Iii) applying a curable composition on the primer layer to form a coating film; and (iv) irradiating the coating film of the curable composition with an active energy ray to form a hard coat layer. The manufacturing process is included.
Here, the respective compositions described above can be applied to the primer layer forming composition and the curable composition.

The primer layer forming composition and the curable composition coating method in the steps (i) and (iii) are cast coating method, spin coating method, blade coating method, dip coating method, roll coating method, bar coating method, Die coating method, spray coating method, curtain coating method, ink jet method, printing method (letter plate, intaglio plate, planographic plate, screen printing, etc.) can be selected as appropriate, and even a highly volatile solution can be applied in a short time. It is desirable to use a spin coat method because of the advantage that it can be used and uniform coating can be easily performed. In addition, it is desirable to use a roll coating method, a die coating method, or a spray coating method because of the advantage that it can be applied easily and a smooth coating film can be formed without coating unevenness in a large area. As the primer layer forming composition and the curable composition used here, those in the form of the aforementioned varnish can be suitably used. It is preferable that the primer layer forming composition and the curable composition are filtered in advance using a filter having a pore diameter of about 2 μm in advance and then used for coating.

After the coating of the composition for forming the primer layer in the step (i), as a step (ii), heat treatment is performed with a hot plate or an oven to cure the coating film and form a primer layer. The heat treatment conditions at this time are preferably 40 to 150 ° C. and about 30 seconds to 10 minutes, for example.
If the primer layer forming composition contains an active energy ray-curable polyfunctional monomer or a polymerization initiator that generates radicals by active energy rays, the active energy applied to the coating film of the curable composition described later. A beam irradiation process may be applied.

After the coating of the curable composition in the step (iii), preferably followed by preliminary drying with a hot plate or oven, etc., and then (iv) irradiation with active energy rays such as ultraviolet rays for photocuring and hard coating Form a layer. Examples of active energy rays include ultraviolet rays, electron beams, and X-rays. As a light source used for ultraviolet irradiation, sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a UV-LED, or the like can be used.
Thereafter, by post-baking, specifically, polymerization and polycondensation can be completed by heating using a hot plate, oven, or the like.

In the thus obtained laminate of the present invention, the thickness of the primer layer is not particularly limited, but can be, for example, in the range of 0.01 to 1 μm.
The hard coat layer is preferably set to have a thickness of 1 to 10/3 times 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, more preferably 3 to 10 μm.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
In the examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows.

(1) Spin coater: spin coater LabSpin6TT manufactured by SUSS Microtech
(2) Hot plate equipment: MH-180CS, MH-3CS manufactured by AS ONE Corporation
(3) UV irradiation device: Eye Graphics Co., Ltd. eye ultraviolet curing device US5-0401 4kW x 1 lamp (4) Scratch test device: Shinto Kagaku Co., Ltd. reciprocating wear tester TRIBOGEAR TYPE: 30S
Load: 250 g / cm ²
Scanning speed: 3m / min (5) Gel permeation chromatography (GPC)
Equipment: HLC-8220GPC manufactured by Tosoh Corporation
Column: Shodex (registered trademark) GPC KF-804L, GPC KF-805L manufactured by Showa Denko K.K.
Column temperature: 40 ° C
Eluent: Tetrahydrofuran Detector: RI
(6) Film thickness Equipment: Nikon Digital Length Measuring Machine Digimicro MH-15M + Counter TC-101A
(7) Glossiness Device: Glossmeter GM-268Plus manufactured by Konica Minolta Co., Ltd.
Measurement angle: 60 degrees (8) Total light transmittance, haze Device: Nippon Denshoku Industries Co., Ltd. Haze meter NDH5000
(9) Contact angle device: DropMaster DM-501, manufactured by Kyowa Interface Science Co., Ltd.
Measurement temperature: 20 ° C

Abbreviations represent the following meanings.
PFPE1: Perfluoropolyether having a hydroxy group via a poly (oxyalkylene) group (repeating unit number 8 to 9) at both ends [Fluorolink 5147X manufactured by Solvay Specialty Polymers]
BEI: 1,1-bis (acryloyloxymethyl) ethyl isocyanate [Karenz (registered trademark) BEI manufactured by Showa Denko KK]
DBTDL: Dibutyltin dilaurate [manufactured by Tokyo Chemical Industry Co., Ltd.]
HTES: Triethoxy (hexyl) silane [Shin-Etsu Chemical Co., Ltd. Shin-Etsu Silicone (registered trademark) KBE-3063]
MPTES: Triethoxy (3-methacryloyloxypropyl) silane [Shin-Etsu Silicone (registered trademark) KBE-503, manufactured by Shin-Etsu Chemical Co., Ltd.]
TEOS: Tetraethoxysilane [Momentive Performance Materials Japan (same) TSL8124]
DPHA: Dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate mixture [KAYALAD DPHA manufactured by Nippon Kayaku Co., Ltd.]
PETA: Pentaerythritol triacrylate / pentaerythritol tetraacrylate mixture [Shin-Nakamura Chemical Co., Ltd. NK ester A-TMM-3LM-N]
UA: Hexafunctional aliphatic urethane acrylate oligomer [EBECRYL (registered trademark) 5129, manufactured by Daicel Ornex Co., Ltd.]
SM2: UV-reactive fluorine-based surface modifier having a perfluoropolyether structure [Megafac (registered trademark) RS-75, manufactured by DIC Corporation, 40% by mass MEK / MIBK solution]
FP1: Cross-linked polymethyl methacrylate true spherical particles [Techpolymer (registered trademark) SSX-105, manufactured by Sekisui Plastics Co., Ltd., average particle size: 5 μm]
FP2: Cross-linked polymethyl methacrylate true spherical particles [Techpolymer (registered trademark) SSX-103, manufactured by Sekisui Plastics Co., Ltd., average particle size: 3 μm]
FP3: Cross-linked polymethyl methacrylate true spherical particles [Techpolymer (registered trademark) SSX-102, average particle diameter 2 μm, manufactured by Sekisui Plastics Co., Ltd.]
I2959: 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one [IRGACURE 2959 manufactured by BASF Japan 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 a poly (oxyalkylene) group at both ends and an acryloyl group via one urethane bond In a screw tube, 1.05 g (0.5 mmol) of PFPE1 and BEI 0. 26 g (1.0 mmol), DBTDL 10 mg (0.016 mmol), and MEK 1.30 g were charged. The mixture was stirred for 24 hours at room temperature (approximately 23 ° C.) using a stirrer tip. This reaction mixture was diluted with 3.93 g of MEK to obtain a 20 mass% MEK solution of SM1, which is the target compound.
The weight average molecular weight Mw measured by GPC of the obtained SM1 in terms of polystyrene 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 (primer layer forming composition) A reaction flask was charged with alkoxysilane and ethanol according to the description in Table 1, and stirred under a nitrogen stream for 5 minutes. A silane / ethanol solution was prepared. To this solution, an oxalic acid-water / ethanol solution separately prepared according to the description in Table 1 was added dropwise over 10 minutes. The solution was stirred for 30 minutes, then heated until the internal solution was refluxed (approximately 80 ° C.) and stirred for 1 hour. The reaction mixture was cooled to room temperature (approximately 23 ° C.) to obtain a primer composition (PR1 to PR3) having a siloxane oligomer concentration of 40% by mass.
Weight average molecular weight Mw and dispersity Mw / Mn measured by polystyrene conversion by GPC of the obtained siloxane oligomer are 1,400, 1.1 (PR1), 1,500, 1.1 (PR2), respectively. 1,500, 1.1 (PR3).

[Production Examples 3-1 to 3-4] Preparation of Hard Coat Composition (Curable Composition) According to the description in Table 2, the following components were mixed to obtain a hard coat composition (HC 1 to HC4) was prepared. In addition, solid content refers to components other than a solvent here. In the table, [part] represents [part by mass].
(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 described in Table 2 (in terms of solid content or active ingredient)
(3) Organic fine particles: Organic fine particles described in Table 2 in the amount described in Table 2 (4) Polymerization initiator: I2959 5 parts by mass (5) Polymerization accelerator: EPA 0.1 parts by mass (6) Solvent: PGME Amounts listed in Table 2

[Examples 1 to 8, Comparative Examples 1 to 3]
A primer composition diluted with PGME so as to have a solid content concentration (siloxane oligomer concentration) shown in Table 3 is spin-coated (1,000 rpm × 30) on a glass substrate (10 cm × 10 cm, thickness 0.7 mm). Second) to obtain a coating film. This coating film was heated on a hot plate at 120 ° C. for 1 hour to form a primer layer (cured film) having the thickness shown in Table 3.
On this primer layer, the hard coat composition shown in Table 3 was spin-coated (the number of revolutions shown in Table 3 × 30 seconds) to obtain a coating film. The coating film was dried on a hot plate at 120 ° C. for 3 minutes to remove the solvent. The obtained film is exposed to UV light with an exposure amount of 500 mJ / cm ^{2 in} a nitrogen atmosphere to expose a hard coat laminate having a hard coat layer (cured film) with the thickness shown in Table 3. did.

The obtained hard coat laminate was evaluated for antiglare properties, adhesion, scratch resistance, total light transmittance, haze, and contact angles of water and oleic acid. The procedure for evaluating the antiglare property, adhesion, scratch resistance, and contact angle is shown below. The results are also shown in Table 4.

[Anti-glare]
The obtained hard coat laminate was placed on a black table having a gloss Gs (60 °) of 11.8, and the gloss Gs (60 °) of the hard coat layer surface was measured and evaluated according to the following criteria. In addition, when an actual use is assumed as a hard-coat laminated body, it is calculated | required that it is at least B, and it is desirable that it is A.
A: Gs (60 °) ≦ 120
B: 120 <Gs (60 °) ≦ 125
C: Gs (60 °)> 125

[Adhesion]
The hard coat layer was cut with a square grid pattern of 25 squares (5 × 5, 2 mm spacing) using a guide [Cortech Co., Ltd. Cross Cut Guide CCI-2], and a transparent tape [Nichiban ( The cross-cut method (based on JIS 5600-5-6) using Cellotape (registered trademark) CT-18] manufactured by Co., Ltd. was used, and evaluation was performed according to the following criteria.
A: All 25 squares do not peel B: 1-11 squares peel C: 12 squares or more peel

[Abrasion resistance]
The hard coat layer surface was rubbed back and forth 1,000 times with a load of 250 g / cm ² with steel wool [Bonster Sales Co., Ltd. Bonstar (registered trademark) # 0000 (super extra fine)] attached to a reciprocating wear tester. A line was drawn on the rubbed portion with an oil-based marker [Mckey extra fine (blue), using fine side made by Zebra Co., Ltd.]. Subsequently, the drawn line was wiped off with a non-woven 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. In addition, when an actual use is assumed as a hard-coat laminated body, it is calculated | required that it is at least B, and it is desirable that it is A.
A: The line drawn with the oil-based marker can be wiped clean without scratching B: The line drawn with the oil-based marker can be wiped off cleanly, but the ink drawn with the oil-based marker enters the scratch and cannot be wiped off

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

As shown in Tables 1 to 4, a hard coat layer using a perfluoropolyether SM1 that binds an acryloyl group via a poly (oxyalkylene) group and one urethane bond group at both ends as a surface modifier. In the formation of the laminated body 1 to the laminated body 6, the laminated body 10 and the laminated body 11 of Example 1 to Example 8 provided with the primer layer, the antiglare property is excellent, and the adhesion and scratch resistance are also good. It became a satisfactory quality in actual use, and it became a laminate with excellent transparency.
On the other hand, when a siloxane oligomer having no radical polymerizable double bond (a siloxane oligomer deviating from the definition of the present invention) is used for the primer layer (Comparative Example 1), and when no primer layer is provided (Comparative Example 2) As a result, the adhesion of the hard coat layer to the glass substrate was low, and the scratch resistance was poor.
Further, when the UV reactive fluorine-based surface modifier SM2 having a perfluoropolyether structure is used as the surface modifier for the hard coat layer (Comparative Example 3), the antiglare property and the adhesion are satisfactory. Although obtained, the desired scratch resistance could not be obtained.

As described above, as shown in the results of Examples, in a laminate having a hard coat layer employing a specific perfluoropolyether as a surface modifier, a material containing a specific siloxane oligomer having a radical polymerizable double bond By providing a primer layer made of a cured product, a laminate satisfying all the properties of antiglare property, scratch resistance, and adhesion to a substrate can be obtained.

Claims (16)

1. An antiglare 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 is
   (A) having a radical polymerizable double bond obtained by hydrolytic condensation of an alkoxysilane containing at least an alkoxysilane A represented by the formula [1] and an alkoxysilane B represented by the formula [2] It consists of a cured product of a primer layer forming composition containing a siloxane oligomer,
   

   

   (In the formula, R ¹ represents a monovalent organic group having a radical polymerizable double bond, R ³ represents an alkyl group having 1 to 10 carbon atoms (the alkyl group is a fluorine atom, at least 1 to 6 carbon atoms) An amino group substituted with an alkyl group, an amino group substituted with at least a phenyl group, or an ureido group) or a phenyl group, wherein R ² and R ⁴ are each independently methyl A group or an ethyl group, a represents an integer of 1 or 2, and b represents an integer of 0 to 2.)
   The hard coat layer is
   (A) 100 parts by mass of an active energy ray-curable polyfunctional monomer,
   (B) Active energy rays via a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane bonding group in this order at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group 0.1 to 10 parts by mass of perfluoropolyether to which a polymerizable group is bonded,
   (C) From a cured product of a curable composition comprising 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. Become,
   Antiglare hard coat laminate.
2. The radical polymerizable double bond obtained by hydrolyzing and condensing the alkoxysilane A represented by the formula [1] and the alkoxysilane B represented by the formula [2] with the siloxane oligomer of the component (A) The antiglare hard coat laminate according to claim 1, which is a siloxane oligomer having
   

   

   (In the formula, R ¹ represents a monovalent organic group having a radical polymerizable double bond, and R ³ represents an alkyl group having 1 to 6 carbon atoms which may be substituted with a fluorine atom, or a phenyl group. , R ² and R ⁴ 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.)
3. The antiglare hard coat laminate according to claim 1 or 2, wherein R ¹ in the formula [1] is a monovalent organic group having a vinyl group or a (meth) acryl group.
4. The antiglare hard coat laminate according to claim 3, wherein the alkoxysilane A is a compound represented by the following formula [3].
   

   

   (In the formula, R ² represents the same meaning as defined in the 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.)
5. The siloxane oligomer having a radically polymerizable double bond as the component (A) is a siloxane oligomer containing 10 to 99 mol% of the alkoxysilane A unit. Antiglare hard coat laminate.
6. The poly (oxyperfluoroalkylene) group of the perfluoropolyether of the component (b) is a group having — [OCF ₂ ] — and — [OCF ₂ CF ₂ ] — as repeating units. Item 6. The antiglare hard coat laminate according to any one of Items 5.
7. The antiglare hard coat laminate according to any one of claims 1 to 6, wherein the poly (oxyalkylene) group of the perfluoropolyether of the component (b) is a poly (oxyethylene) group. body.
8. The polyfunctional monomer of the component (a) is at least one selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound. The antiglare hard coat laminate according to one item.
9. The antiglare hard coat laminate according to any one of claims 1 to 8, wherein the organic fine particles of the component (c) are true spherical particles.
10. The antiglare hard coat laminate according to any one of claims 1 to 9, wherein the organic fine particles of the component (c) are polymethyl methacrylate particles.
11. The antiglare hard coat laminate according to any one of claims 1 to 10, wherein the polymerization initiator of the component (d) is an alkylphenone polymerization initiator.
12. The hard coat layer according to any one of claims 1 to 11, wherein the hard coat layer has a thickness of 1 to 10/3 times the average particle size of the organic fine particles of the component (c). Antiglare hard coat laminate.
13. The antiglare hard coat laminate according to any one of claims 1 to 12, wherein the hard coat layer has a thickness of 1 to 20 µm.
14. The antiglare hard coat laminate according to claim 13, wherein the hard coat layer has a thickness of 3 to 10 µm.
15. The antiglare hard coat laminate according to any one of claims 1 to 14, wherein the substrate is glass.
16. A method for producing an antiglare hard coat laminate comprising a primer layer on at least one surface of a substrate and a hard coat layer above the primer layer,
    Applying a primer layer forming composition on a substrate to form a coating film;
    Heating the coating film of the primer layer forming composition to cure the coating film and forming a primer layer;
    A step of applying a curable composition on the primer layer to form a coating film, and a step of irradiating the coating film of the curable composition with active energy rays to cure the coating film to form a hard coat layer Including,
    The primer layer forming composition is
    (A) having a radical polymerizable double bond obtained by hydrolytic condensation of an alkoxysilane containing at least an alkoxysilane A represented by the formula [1] and an alkoxysilane B represented by the formula [2] Containing siloxane oligomers,
    

    

    (In the formula, R ¹ represents a monovalent organic group having a radical polymerizable double bond, R ³ represents an alkyl group having 1 to 10 carbon atoms (the alkyl group is a fluorine atom, at least 1 to 6 carbon atoms) An amino group substituted with an alkyl group, an amino group substituted with at least a phenyl group, or an ureido group) or a phenyl group, wherein R ² and R ⁴ are each independently methyl A group or an ethyl group, a represents an integer of 1 or 2, and b represents an integer of 0 to 2.)
    The curable composition is
    (A) 100 parts by mass of an active energy ray-curable polyfunctional monomer,
    (B) Active energy rays via a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane bonding group in this order at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group 0.1 to 10 parts by mass of perfluoropolyether to which a polymerizable group is bonded,
    (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.
    A method for producing an antiglare hard coat laminate.