KR20070003655A - Curable resin composition and cured film formed from same - Google Patents

Abstract

Provided are a curing resin composition which can form a cured film of multilayered structure having a low refractive index layer and a high refractive index layer into a single film, and a cured film prepared from the composition. The curing resin composition comprises (A) a tin-containing indium oxide particle; (B) a fluorine-containing polymer containing an ethylenically unsaturated group; (C) a solvent which has a high solubility to the fluorine-containing polymer containing an ethylenically unsaturated group; and (D) a solvent which has a high dispersion stability to a tin-containing indium oxide particle and is compatible with the solvent (C). The relative evaporation velocity of the solvent (C) is higher than that of the solvent (D).

Description

Curable resin composition and cured film formed therefrom {CURABLE RESIN COMPOSITION AND CURED FILM FORMED FROM SAME}

BRIEF DESCRIPTION OF THE DRAWINGS The figure which shows the typical example of the anti-reflective film containing the cured film formed from curable resin composition of this invention.

2 is an electron microscope image showing a typical example of evaluation criteria of layer separability.

3 is an electron microscope image showing a typical example (cured film of Example 4) of a cured film cross section of the present invention, which is separated from two layers.

[Patent Document 1] Japanese Unexamined Patent Publication No. 57-34107

[Patent Document 2] Japanese Unexamined Patent Publication No. 59-189108

[Patent Document 3] Japanese Unexamined Patent Publication No. 60-67518

[Patent Document 4] Japanese Patent Application Laid-Open No. 6-35559

The present invention relates to a curable resin composition and a cured film formed therefrom, in particular, a curable resin composition capable of forming a cured film having a multilayer structure of two or more layers, such as a low refractive index layer and a high refractive index layer, in one coating film, and It relates to the cured film formed therefrom.

Various display panels, such as a liquid crystal display panel, a cold cathode ray tube panel, and a plasma display, have low refractive index, abrasion resistance, and coating property, in order to prevent external light from shining and to improve image quality. And a low refractive index layer containing a cured product excellent in durability. In order to remove the fingerprint, dust, etc. which adhered to these display panels, the surface is often wiped with the gauze impregnated with ethanol, and scratch resistance is calculated | required. In particular, in the liquid crystal display panel, the antireflection film is provided on the liquid crystal unit in a state of being bonded to the polarizing plate. In addition, although triacetyl cellulose etc. are used as a base material, for example, in order to increase the adhesiveness at the time of bonding with a polarizing plate, it is necessary to saponify normally with aqueous alkali solution. Therefore, the antireflection film excellent in alkali resistance especially in durability is calculated | required for the use of a liquid crystal display panel.

As the material for the low refractive index layer of the antireflection film, for example, a fluorine resin paint containing a hydroxyl group-containing fluorine-containing polymer is known, which is disclosed in Patent Document 1, Patent Document 2, Patent Document 3 and the like. However, in such a fluororesin paint, in order to cure the coating film, it is necessary to crosslink by heating a hydroxyl group-containing fluorine-containing polymer and a curing agent such as a melamine resin under an acid catalyst, and the curing time is excessive depending on the heating conditions. There was a problem that the length of the substrate or the type of the substrate that can be used is limited. Moreover, also in the obtained coating film, although it was excellent in weather resistance, there existed a problem that it was lacking in abrasion resistance and durability.

Therefore, in order to solve the above problem, Patent Document 4 discloses an isocyanate group-containing unsaturated compound having at least one isocyanate group and at least one addition polymerizable unsaturated group, in which a hydroxyl group-containing fluorine-containing polymer and the number of hydroxyl groups / hydroxyl groups of the isocyanate group There is proposed a coating composition comprising an unsaturated group-containing fluorine-containing vinyl polymer obtained by reacting at a ratio of 0.01 to 1.0.

In the conventional anti-reflection film made of a fluorine-based material, it was necessary to form a low-refractive-index layer containing a fluorine-based material in the high refractive index layer provided on the substrate, and it was necessary to separately provide a coating step for forming these layers.

Moreover, the scratch resistance of the low refractive index layer which is a surface layer was not enough.

This invention is made on the background of the above situation, The objective is to provide the curable resin composition which can be hardened by an ultraviolet-ray which can manufacture a low refractive index layer and a high refractive index layer efficiently. Another object of the present invention is to provide a cured film having a lower reflectance, higher transparency, greater adhesion to a substrate, excellent scratch resistance, and excellent environmental resistance than before.

<Start of invention>

In order to achieve the above object, the present inventors earnestly study and mix 2 types of tin-containing indium oxide particles with the ethylenically unsaturated group containing fluorine-containing polymer hardened | cured by irradiation of an ultraviolet-ray, and have specific physical properties. When the composition combining the solvent is applied to the substrate and the solvent is evaporated, the layer containing the tin-containing indium oxide particles at a high density or the layer containing the ITO particles at a high density and the tin-containing indium oxide particles hardly exist. It has been found to separate into two or more layers of layers. Moreover, the cured film obtained by irradiating and hardening an ultraviolet-ray discovered that it was excellent in scratch resistance and transparency, and excellent in weatherability, and completed this invention.

That is, this invention provides the following curable resin composition and the cured film which hardens it.

[1] the following ingredients:

(A) tin-containing indium oxide particles,

(B) an ethylenically unsaturated group-containing fluorine-containing polymer,

(C) (B) Highly soluble solvent of ethylenically unsaturated group containing fluorine-containing polymer, and

(D) Solvent which is high in the dispersion stability of (A) tin-containing indium oxide particle, and is compatible with the solvent of (C)

And the relative evaporation rate of the solvent of (C) is higher than the relative evaporation rate of the solvent of (D).

[2] The curable resin composition according to the above [1], wherein the (A) tin-containing indium oxide particles are derived from an isopropanol dispersion sol of tin-containing indium oxide.

[3] The above-mentioned [1] or [2], wherein the (B) ethylenically unsaturated group-containing fluorine-containing polymer is

Hydroxyl group-containing fluorine-containing polymer,

Compound containing functional group and ethylenically unsaturated group which can react with hydroxyl group

It is obtained by reacting with curable resin composition characterized by the above-mentioned.

[4] The above-mentioned [3], wherein the hydroxyl group-containing fluorine-containing polymer is 100% by mass of the entire fluoropolymer, wherein (a) 5 to 90% by mass of the structural unit represented by the following formula (1), (b) Curable resin composition containing 0.3-90 mass% of structural units represented by following formula (2), and (c) 1-65 mass% of structural units represented by following formula (3).

[In Formula 1, R ¹ represents a group represented by a fluorine atom, a fluoroalkyl group, or -OR ² (wherein R ² represents an alkyl group or a fluoroalkyl group.)

In Formula 2, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group,-(CH ₂ ) _x -OR ⁵ or -OCOR ⁵ (wherein R ⁵ represents an alkyl group or a fluoroalkyl group, x is Represents a group represented by 0 or 1), a carboxyl group or an alkoxycarbonyl group]

In Formula 3, R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents — (CH ₂ ) _v —OR ²⁷ Or -OCOR ²⁷ (wherein R ²⁷ represents a hydrogen atom, a hydroxyalkyl group or a glycidyl group, v represents a number from 0 to 2).

[5] The above-mentioned [3] or [4], wherein the hydroxyl group-containing fluorine-containing polymer is derived from an azo group-containing polysiloxane compound when the total fluorine polymer is 100 mass%, and is represented by the following general formula (4). Curable resin composition containing 0.1-10 mass% of structural units further.

[In Formula 4, R <^8> and R <^9> may be same or different and represents a hydrogen atom, an alkyl group, a halogenated alkyl group, or an aryl group.

[6] The curable resin composition according to any one of [3] to [5], wherein the functional group capable of reacting with the hydroxyl group is selected from the group consisting of an isocyanate group, a carboxyl group, an acid halide group and an acid anhydride group.

[7] The curable resin composition according to any one of [1] to [6], wherein the ethylenically unsaturated group-containing fluorine-containing polymer contains 40% by mass or more of fluorine.

[8] The solvent of any of the above [1] to [7], wherein the solvent of (C) is a solvent having low dispersion stability of the (A) tin-containing indium oxide particles,

The solvent of (D) is a solvent with low solubility of the (B) ethylenically unsaturated group containing fluoropolymer, Curable resin composition characterized by the above-mentioned.

[9] The polyfunctional (meth) acrylate compound and / or one or more (meth), according to any one of the above [1] to [8], containing (E) two or more (meth) acryloyl groups. Curable resin composition containing the fluorine-containing (meth) acrylate compound containing an acryloyl group further.

[10] The curable resin composition according to any one of the above [1] to [9], further comprising (F) a radical photopolymerization initiator.

[11] A cured film obtained by curing the curable resin composition according to any one of the above [1] to [10] and having a multilayer structure of two or more layers.

[12] The one or more layers according to the above [11], wherein the (A) tin-containing indium oxide particles are present at a high density, and the one or more layers in which the (A) tin-containing indium oxide particles are not substantially present. Cured film which has a layer structure of two or more layers containing a layer.

Since the curable resin composition of this invention can form the cured film which has a multilayer structure of arbitrary two or more layers, such as a low refractive index layer and a high refractive index layer, from one coating film, the manufacturing process of the cured film which has a multilayered structure can be simplified. have.

Since the curable resin composition of this invention does not perform hardening reaction by the heat which hydrolysis involves, it can provide the cured film excellent in environmental resistance (moisture heat resistance etc.).

The curable resin composition of this invention can be used advantageously for formation of optical materials, such as an anti-reflective film and a selective permeable film filter, and also uses the thing with high fluorine content, The coating material for a base material with which weather resistance is required, weather resistance It can be used preferably as a film material, a coating material, etc. Moreover, since the said cured film is excellent in adhesiveness with respect to a base material, high scratch resistance, has antistatic performance, and gives favorable antireflection effect, it is very useful as an antireflection film, and its visibility is applicable by applying to various display apparatuses. Can be improved.

Moreover, the reflectance of the laminated body obtained can be improved by raising the fluorine content of an ethylenically unsaturated group containing fluorine-containing polymer.

Also, by not introducing a reactive surfactant into the ethylenically unsaturated group-containing fluorine-containing polymer, variations in layer separation properties (layers are separated or not separated) due to differences between lots of tin-containing indium oxide particles are also improved. can do.

Best Mode for Carrying Out the Invention

Hereinafter, the curable resin composition, the cured film, and a laminated body of this invention are demonstrated concretely.

I. Curable Resin Composition

Curable resin composition of this invention,

(A) tin-containing indium oxide particles,

(B) an ethylenically unsaturated group-containing fluorine-containing polymer,

(C) (B) Highly soluble solvent (high volatile solvent) of ethylenically unsaturated group containing fluorine-containing polymer, and

(D) A solvent (low volatility solvent) which is high in the dispersion stability of (A) tin-containing indium oxide particle, and is compatible with the solvent of (C).

It is characterized by containing.

1. Each structural component of curable resin composition of this invention is demonstrated concretely.

(A) Tin-containing indium oxide particles

The tin-containing indium oxide particles (A) used in the present invention can make the cured film obtained by curing the curable resin composition of the present invention high refractive index.

The tin-containing indium oxide particles (A) used in the present invention are dispersions of isopropanol (hereinafter sometimes referred to as "IPA") or propylene glycol monomethyl ether (hereinafter sometimes referred to as "PGME"). desirable. The solvent dispersion liquid of tin containing indium oxide particle (A) can be used individually by 1 type or in combination of 2 or more types in which particle concentration differs.

As a commercial item of the IPA dispersion liquid of a tin containing indium oxide particle (A), JX1002-ITV (made by Shokubai Kasei Kagaku Kogyo Co., Ltd., IPA: 20 mass% dispersion), JX1003-ITV (Shokubai Kasei Chemical Co., Ltd.) Kagaku Kogyo Co., Ltd. product, PGME: 20 mass% dispersion liquid, NID-20 (Fuji Chemical Co., Ltd. product, IPA: 20 mass% dispersion liquid), etc. are mentioned.

The number average particle diameter of the tin-containing indium oxide particles (A) is preferably 0.001 µm to 2 µm, more preferably 0.001 µm to 0.2 µm, particularly preferably 0.001 µm to 0.1 µm by measurement by electron microscopy. . When the number average particle diameter exceeds 2 µm, transparency tends to deteriorate when made into a cured product or surface condition deteriorates when made into a film. Moreover, in order to improve the dispersibility of particle | grains, various surfactant and amines can also be added. When the particle shape was a rod shape (referring to a shape whose aspect ratio exceeds 1 and 10 or less), the short diameter was used as the particle size.

The shape of the tin-containing indium oxide particles (A) is spherical, hollow, porous, rod-shaped (an aspect ratio exceeding 1 and 10 or less), plate-like, fibrous or irregular, preferably spherical.

The tin-containing indium oxide particles (A) can be used in a dry powder form or in a state dispersed in water or an organic solvent. In particular, it is preferable to use the dispersion liquid of tin containing indium oxide particle for the use which the outstanding transparency is calculated for hardened | cured material.

In the curable resin composition, the amount of the mixture (containing) of the tin-containing indium oxide particles (component (A)) is 100 mass%, excluding the organic solvent, and preferably within the range of 10 to 90 mass%, 20 It is more preferable that it is the range of -80 mass%, and it is more preferable that it is the range which is 30-70 mass%. If it is less than 10 mass%, the hardness of a cured film may be inadequate or the layer with a high refractive index may not be obtained. When it exceeds 90 mass%, film formability may become inadequate. In addition, the quantity of tin containing indium oxide particle (component (A)) means solid content, and when a tin containing indium oxide particle (component (A)) is used in the form of a dispersion liquid, it does not include the quantity of a dispersion medium in the compounding quantity. .

(B) fluorine-containing polymer containing ethylenically unsaturated groups

The ethylenically unsaturated group-containing fluorine-containing polymer used in the present invention is obtained by reacting a hydroxyl group-containing fluorine-containing polymer with a compound containing a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated group. The ethylenically unsaturated group-containing fluorine-containing polymer used in the present invention usually contains 30% by mass or more of fluorine, and preferably 40% by mass or more. If fluorine content is 40 mass% or more, the cured film with a lower refractive index can be obtained. The fluorine-containing content can be calculated from the composition obtained by performing the compositional analysis of the polymer by ¹³ C-NMR.

Here, as a compound containing a functional group and ethylenically unsaturated group which can react with a hydroxyl group, the compound containing one isocyanate group and 1 or more ethylenically unsaturated group, or an ethylenically unsaturated group containing carboxylic acid compound, or its derivative (s) can be mentioned. All.

(1) hydroxyl-containing fluorine-containing polymer

It is preferable that a hydroxyl-containing fluorine-containing polymer contains the following structural unit (a) 5-90 mass%, (b) 0.3-90 mass%, and (c) 1-65 mass%.

(a) The structural unit represented by following formula (1).

(b) The structural unit represented by following formula (2).

(c) The structural unit represented by following formula (3).

By configuring in this way, the coating film excellent in low refractive index, scratch resistance, coating property, and durability can be obtained.

<Formula 1>

[In Formula 1, R ¹ represents a group represented by a fluorine atom, a fluoroalkyl group, or -OR ² (wherein R ² represents an alkyl group or a fluoroalkyl group.)

<Formula 2>

In Formula 2, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group,-(CH ₂ ) _x -OR ⁵ or -OCOR ⁵ (wherein R ⁵ represents an alkyl group or a fluoroalkyl group, x is Represents a group represented by 0 or 1), a carboxyl group or an alkoxycarbonyl group]

<Formula 3>

In the formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents-(CH ₂ ) _v -OR ²⁷ or -OCOR ²⁷ (wherein R ²⁷ represents a hydrogen atom, a hydroxyalkyl group or a glycidyl group) , v represents a number from 0 to 2).

1) structural unit (a)

In Formula 1, R ¹ And a fluoroalkyl group of R ² , having from 1 to 3 carbon atoms, such as a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorocyclohexyl group The fluoroalkyl group of 6 is mentioned. Moreover, as an alkyl group of R <^2> , C1-C6 alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a cyclohexyl group, are mentioned.

The structural unit (a) can be introduced by using a fluorine-containing vinyl monomer as the polymerization component. The fluorine-containing vinyl monomer is not particularly limited as long as it is a compound having at least one polymerizable unsaturated double bond and at least one fluorine atom. Examples thereof include fluoroolefins such as tetrafluoroethylene, hexafluoropropylene and 3,3,3-trifluoropropylene; Alkyl perfluorovinyl ether or alkoxyalkyl perfluorovinyl ether; Perfluoros such as perfluoro (methylvinylether), perfluoro (ethylvinylether), perfluoro (propylvinylether), perfluoro (butylvinylether), perfluoro (isobutylvinylether) (Alkyl vinyl ether) s; 1 type of perfluoro (alkoxy alkyl vinyl ether), such as perfluoro (propoxy propyl vinyl ether), or 2 or more types of these are mentioned.

Among these, hexafluoropropylene and perfluoro (alkyl vinyl ether) or perfluoro (alkoxy alkyl vinyl ether) are more preferable.

In addition, the content rate of the structural unit (a) is preferably 5 to 90 mass%, when the total amount of the hydroxyl group-containing fluorine-containing polymer is 100 mass%. The reason is that when the content is less than 5% by mass, the fluorine-containing content of the fluorine-containing polymer is low, and the expression of low refractive index, which is an optical characteristic of the fluorine-containing material, intended by the present invention may be difficult. It is because solubility, transparency, or adhesiveness to a base material of a hydroxyl-containing fluorine-containing polymer to an organic solvent may fall when content rate exceeds 90 mass%.

For this reason, the content of the structural unit (a) is more preferably 10 to 70% by mass, more preferably 15 to 60% by mass relative to the total amount of the hydroxyl group-containing fluorine-containing polymer. Do.

2) structural unit (b)

In the formula (2), examples of the alkyl group represented by R ⁴ or R ⁵ include alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, hexyl group, cyclohexyl group and lauryl group, and alkoxycarbonyl group of R ⁴ . As a methoxycarbonyl group, an ethoxycarbonyl group, etc. are mentioned, As a fluoroalkyl group of R <^5> , a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoro butyl group, a perfluoro Hexyl group, 2- (trifluoromethyl) ethyl group, 2- (perfluoroethyl) ethyl group, 2- (perfluoropropyl) ethyl group, 2- (perfluorobutyl) ethyl group, 2- (perfluoropentyl The ethyl group, 2- (perfluorohexyl) ethyl group, 2- (perfluorooctyl) ethyl group, 2- (perfluorononyl) ethyl group, 2- (perfluorodecyl) ethyl group, etc. are mentioned.

The structural unit (b) can be introduced by using the above-described vinyl monomer having a substituent as a polymerization component. Examples of such vinyl monomers are methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n Alkyl vinyl ethers or cycloalkyl vinyl ethers such as -hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether and cyclohexyl vinyl ether; Allyl ethers such as ethyl allyl ether and butyl allyl ether; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl versatate and vinyl stearate; Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth (Meth) acrylic acid esters, such as a) acrylate and 2- (n-propoxy) ethyl (meth) acrylate; Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid; And those having the following structural formulas.

In addition, "(meth) acrylate" means an acrylate or a methacrylate.

(In formula, ^R28 is a hydrogen atom or a methyl group, w shows the number of 0-2.)

These can be used individually by 1 type or in combination of 2 or more types.

In addition, when the content rate of a structural unit (b) assumes 100 mass% of the total amount of a hydroxyl-containing fluorine-containing polymer, it is preferable to set it as 0.3-90 mass%. This is because the solubility in the organic solvent of a hydroxyl-containing fluorine-containing polymer may fall when content rate is less than 0.3 mass%, and when a content rate exceeds 90 mass%, the hydroxyl group-containing fluorine-containing polymer may be reduced. It is because optical characteristics, such as transparency and low reflectivity, may fall.

For this reason, the content of the structural unit (b) is more preferably 0.4 to 70% by mass and more preferably 0.5 to 60% by mass relative to the total amount of the hydroxyl group-containing fluorine-containing polymer. .

3) structural unit (c)

In the general formula (3), as the hydroxyalkyl group of R ²⁷ , 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 5-hydroxy A hydroxypentyl group, 6-hydroxyhexyl group, etc. are mentioned.

The structural unit (c) can be introduced by using a hydroxyl group-containing vinyl monomer as a polymerization component. Examples of such hydroxyl group-containing vinyl monomers include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5 Hydroxyl group-containing allyl ethers such as hydroxyl group-containing vinyl ethers such as hydroxypentyl vinyl ether and 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether And allyl alcohol.

Moreover, as a hydroxyl-containing vinyl monomer, in addition to the above, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and caprolactone (meth) Acrylate, polypropylene glycol (meth) acrylate, etc. can be used.

In addition, in this invention, since a hydroxyl group is produced by hydrolysis, it is considered that glycidyl group contains a hydroxyl group. Glycidyl (meth) acrylate can be used as a monomer containing a glycidyl group.

In addition, the content rate of the structural unit (c) is preferably 1 to 65% by mass when the total amount of the hydroxyl group-containing fluorine-containing polymer is 100% by mass. This is because the solubility in the organic solvent of a hydroxyl-containing fluorine-containing polymer may fall when content rate is less than 1.0 mass%, On the other hand, when content rate exceeds 65 mass%, the hydroxyl group-containing fluorine-containing polymer may be reduced. It is because optical characteristics, such as transparency and low reflectivity, may fall.

For this reason, the content of the structural unit (c) is more preferably 1 to 45% by mass, more preferably 1 to 30% by mass based on the total amount of the hydroxyl group-containing fluorine-containing polymer. .

4) structural unit (d) and structural unit (e)

It is preferable that the said hydroxyl-containing fluorine-containing polymer contains 0.1-10 mass% of following structural units (d) derived from an azo-group containing polysiloxane compound.

(d) The structural unit represented by following formula (4).

<Formula 4>

[In Formula 4, R <^8> and R <^9> may be same or different and represents a hydrogen atom, an alkyl group, a halogenated alkyl group, or an aryl group.

By including the structural unit (d), scratch resistance is improved.

Moreover, in the ethylenically unsaturated group containing fluorine-containing polymer of this invention, it is preferable to include the said structural unit (d) as a part of following structural unit (e).

(e) A structural unit represented by the formula (6).

In Formula 6, R ¹¹ to R ¹⁴ may be the same or different, and represent a hydrogen atom, an alkyl group or a cyano group, and R ¹⁵ to R ¹⁸ may be the same or different, and a hydrogen atom or an alkyl group, a halogenated alkyl group or an aryl. And p and q represent a number from 1 to 6, s and t represent a number from 0 to 6, and y represents a number from 1 to 200.

Hereinafter, the structural units (d) and (e) will be described.

In the general formula (4), examples of the alkyl group of R ⁸ or R ⁹ include alkyl groups having 1 to 3 carbon atoms such as methyl group, ethyl group and propyl group, and halogenated alkyl groups include trifluoromethyl, perfluoroethyl and perfluoro C1-C4 fluoroalkyl groups, such as a ropropyl group and a perfluoro butyl group, etc. are mentioned, A benzyl group, a naphthyl group, etc. are mentioned as an aryl group, respectively.

The structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the general formula (4). As an example of such an azo-group containing polysiloxane compound, the compound represented by following formula (7) is mentioned.

[In Formula 7, R ^{11 To} R ¹⁴ , R ^{15 To} R ¹⁸ , p, q, s, t and y are the same as the above Formula 6, z is a number of 1 to 20.

In the case of using the compound represented by the formula (7), the structural unit (d) is included in the hydroxyl group-containing fluorine-containing polymer as part of the structural unit (e). In this case, in the formula (7), examples of the alkyl group of R ¹¹ to R ¹⁴ include alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, hexyl group and cyclohexyl group, and R ¹⁵ to R ^{18 group} . As an alkyl group, C1-C3 alkyl groups, such as a methyl group, an ethyl group, and a propyl group, are mentioned.

In the present invention, the compound represented by the following formula (8) is particularly preferable as the azo group-containing polysiloxane compound represented by the formula (7).

[In Formula 8, y and z are the same as that of Formula 7].

Moreover, when the content rate of a structural unit (d) makes 100 mass% the total amount of a hydroxyl-containing fluorine-containing polymer, it is preferable to set it as 0.1-10 mass%. The reason for this is that when the content is less than 0.1% by mass, the surface lubricity of the coating film after curing may decrease, and the scratch resistance of the coating film may decrease. On the other hand, when the content is more than 10% by mass, the hydroxyl group-containing fluorine-containing This is because when the transparency of the polymer is deteriorated and used as a coating material, cratering or the like may easily occur during coating.

For this reason, the content of the structural unit (d) is more preferably 0.1 to 5% by mass, more preferably 0.1 to 4% by mass relative to the total amount of the hydroxyl group-containing fluorine-containing polymer. . For the same reason, the content rate of the structural unit (e) is preferably determined so that the content rate of the structural unit (d) contained therein is within the above range.

5) Frame unit (f)

The hydroxyl group-containing fluorine-containing polymer may also contain 0.1 to 30 mass% of the following structural unit (f) when the total amount of the hydroxyl group-containing fluorine-containing polymer is 100 mass%.

(f) The structural unit represented by following formula (5).

In formula (5), R ¹⁰ represents a group having an emulsifying action.

By including the structural unit (f), the coatability is improved.

However, when (B) ethylenically unsaturated group containing fluorine-containing polymer contains a structural unit (f), the application layer formed by apply | coating curable resin composition of this invention to a base material etc., (A) tin-containing indium oxide particle | grains Is separated from one or more layers having high density and (A) one or less layers in which tin-containing indium oxide particles are substantially absent (layer separation property). When it is expected that the introduction of the structural unit (f) is not preferred.

Hereinafter, the structural unit (f) will be described.

In the formula (5), a group having an emulsifying action of R ¹⁰ is preferably a group having both a hydrophobic group and a hydrophilic group and a hydrophilic group having a polyether structure such as polyethylene oxide and polypropylene oxide.

Examples of the group having such an emulsification action include groups represented by the following formula (9).

[Wherein n is a number from 1 to 20, m is a number from 0 to 4, u represents a number from 3 to 50].

The structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component. Examples of such reactive emulsifiers include compounds represented by the following general formula (10).

[In Formula 10, n, m, and u are the same as that of Formula 9].

Moreover, when the content rate of a structural unit (f) makes 100 mass% the total amount of a hydroxyl-containing fluorine-containing polymer, it is preferable to set it as 0.1-30 mass%. The reason is that when the content is 0.1% by mass or more, the solubility of the hydroxyl group-containing fluorine-containing polymer in the solvent is improved, while when the content is within 30% by mass, the adhesiveness of the curable resin composition does not increase excessively and is easy to handle. This is because the moisture resistance is not lowered even when used as a coating material.

For this reason, the content of the structural unit (f) is more preferably 0.1 to 25% by mass, more preferably 1 to 20% by mass relative to the total amount of the hydroxyl group-containing fluorine-containing polymer. .

6) Molecular Weight

The hydroxyl group-containing fluorine-containing polymer preferably has a polystyrene reduced number average molecular weight of 5,000 to 500,000 as measured by gel permeation chromatography (hereinafter referred to as "GPC") using tetrahydrofuran (hereinafter referred to as "THF") as a solvent. Do. The reason is that when the number average molecular weight is less than 5,000, the mechanical strength of the hydroxyl group-containing fluorine-containing polymer may decrease, while when the number average molecular weight exceeds 500,000, the viscosity of the curable resin composition described later increases, This is because the thin film coating may be difficult.

For this reason, the polystyrene reduced number average molecular weight of the hydroxyl group-containing fluorine-containing polymer is more preferably 10,000 to 300,000, more preferably 10,000 to 100,000.

(2) a compound containing one isocyanate group and one or more ethylenically unsaturated groups

The compound containing one isocyanate group and at least one ethylenically unsaturated group is not particularly limited as long as it is a compound containing one isocyanate group and at least one ethylenically unsaturated group in the molecule.

Moreover, when two or more isocyanate groups are contained, there exists a possibility of gelatinization when reacting with a hydroxyl-containing fluorine-containing polymer.

Moreover, since the curable resin composition mentioned later can be hardened more easily, the compound which has a (meth) acryloyl group as said ethylenically unsaturated group is more preferable. Here, "(meth) acryloyl group" means acryloyl group or methacryloyl group.

As such a compound, 1 type of 2- (meth) acryloyloxy ethyl isocyanate and 2- (meth) acryloyloxypropyl isocyanate is independent, or 2 or more types of these are mentioned.

Moreover, such a compound can also be synthesize | combined by making a diisocyanate and hydroxyl-containing (meth) acrylate react.

In this case, examples of the diisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5 Naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3, 3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexyl isocyanate), 2,2,4-trimethyl Hexamethylene diisocyanate, bis (2-isocyanate ethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, 1, 3-bis (isosia One kind alone or a combination of two or more thereof, such as a methylate of methyl) cyclohexane, tetramethylxylylene diisocyanate, and 2,5 (or 2,6) -bis (isocyanatemethyl) -bicyclo [2.2.1] heptane Can be mentioned.

In this, 2, 4- tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylenebis (4-cyclohexyl isocyanate), and 1, 3-bis (isocyanate methyl) cyclohexane are especially preferable.

Examples of hydroxyl group-containing (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and caprolactone (meth). ) Acrylate, polypropylene glycol (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, isocyanur Single 1 type, such as acid EO modified di (meth) acrylate, or 2 or more types of these combinations are mentioned.

Among these, 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are especially preferable.

In addition, as a commercial item of a hydroxyl-containing polyfunctional (meth) acrylate, For example, brand name HEA of Osaka Yuki Kagaku Co., Ltd. brand name KAYARAD DPHA, PET-30, Toagosei (manufactured by Nippon Kayaku Co., Ltd. product) Note) It can obtain as brand names Alonics M-215, M-233, M-305, M-400, etc. of manufacture.

When synthesize | combining from diisocyanate and hydroxyl group containing polyfunctional (meth) acrylate, it is preferable to make the addition amount of a hydroxyl group containing polyfunctional (meth) acrylate 1-1.2 mol with respect to 1 mol of diisocyanate.

As a synthesis | combining method of such a compound, the method of adding a diisocyanate and a hydroxyl group containing (meth) acrylate collectively and making it react, the method of dropping and reacting diisocyanate in a hydroxyl group containing (meth) acrylate, etc. are mentioned.

(3) an ethylenically unsaturated group-containing carboxylic acid compound or a derivative thereof

Examples of the ethylenically unsaturated group-containing carboxylic acid compound or a derivative thereof include a compound having an ethylenically unsaturated group and a carboxylic acid in a molecule thereof, or an acid halide, an acid anhydride thereof, and the like to form an ester with a hydroxyl group-containing fluorine-containing polymer. The compound is not particularly limited.

Moreover, since curable resin composition can be hardened more easily, the compound which has a (meth) acryloyl group as said ethylenically unsaturated group is more preferable.

As such a compound, (meth) acrylic acid, (meth) acrylic acid chloride, (meth) acrylic acid bromide, (meth) acrylic anhydride, etc. are mentioned. Here, "(meth) acrylic acid" means acrylic acid or methacrylic acid.

(4) reaction molar ratio

In the ethylenically unsaturated group-containing fluorine-containing polymer of the present invention, the molar ratio of the hydroxyl group-containing fluorine-containing polymer and the isocyanate group / hydroxyl group is 0.1 to 1.9. It is preferable to react with phosphorus ratio. This is because if the molar ratio is less than 0.1, the scratch resistance and durability may decrease. On the other hand, if the molar ratio exceeds 1.9, the scratch resistance after immersion of the aqueous alkali solution of the coating film of the curable resin composition may decrease. .

For this reason, the molar ratio of isocyanate group / hydroxyl group is preferably 0.3 to 1.5, and more preferably 0.5 to 1.5.

For the same reason, the ethylenically unsaturated group-containing carboxylic acid compound or derivative thereof is reacted at a rate where the molar ratio of the hydroxyl group-containing fluorine-containing polymer and the ethylenically unsaturated group-containing carboxylic acid compound or derivative / hydroxyl group thereof is 0.1 to 1.9. It is preferable. However, when the carboxylic acid derivative is an acid anhydride, since it is possible to react with two hydroxyl groups in one molecule, the molar ratio of the acid anhydride / hydroxyl group of the ethylenically unsaturated group-containing carboxylic acid compound is in the ratio of 0.05 to 0.95. It is desirable to.

In the curable resin composition of this invention, although the addition amount of an ethylenically unsaturated group containing fluorine-containing polymer (B) is not specifically limited, It is 1-80 mass% normally with respect to the composition whole quantity other than the organic solvent. The reason is that the refractive index of the cured coating film of curable resin composition may become high that the addition amount is less than 1 mass%, and sufficient antireflection effect may not be obtained. On the other hand, when the addition amount exceeds 80 mass%, curable resin This is because the scratch resistance of the cured coating film of the composition may not be obtained.

Moreover, for this reason, it is more preferable to make the addition amount of (E) component into 2 to 70 mass%, and it is still more preferable to set it as the value within the range of 3 to 60 mass%.

(C) (B) Solvent having high solubility of ethylenically unsaturated group-containing fluorine-containing polymer (highly volatile solvent)

The (C) high volatile solvent contained in curable resin composition of this invention is a high solubility of the said (B) ethylenically unsaturated group containing fluorine-containing polymer. Here, the high solubility of an ethylenically unsaturated group containing fluorine-containing polymer is visually when (B) ethylenically unsaturated group containing fluorine-containing polymer is added to each solvent so that it may become 50 mass%, and it stirred at room temperature for 8 hours. It means to be a uniform solution. The low solubility means that the solution was not visually uniform at this time. In addition, the relative evaporation rate of the (C) high volatile solvent needs to be larger than the relative evaporation rate of the (D) low volatile solvent mentioned later. Here, the "relative evaporation rate" means the relative value of the evaporation rate based on the time taken for butyl acetate to evaporate 90 mass%, and the detailed description is described in TECHNIQUES OF CHEMISTRY VOL. 2 ORGANIC SOLVENTS Physical Properties and methods of purification 4th ed. (Interscience Publishers, Inc. 1986 page 62). Moreover, it is preferable that (C) high volatile solvent is low in dispersion stability with respect to the said (A) tin containing indium oxide particle (particle of (A) component). (C) Since a high volatile solvent has a relative evaporation rate larger than (D) and (B) has high solubility to an ethylenically unsaturated group containing fluorine-containing polymer, the curable resin composition of this invention is apply | coated to a base material, and a solvent ( In the process of evaporating C) and (D), the particle | grains of (A) component can be localized.

The solvent which can be used as the (C) high-volatile solvent in the present invention is a solvent having a relative evaporation rate of approximately 1.7 or more, specifically methyl ethyl ketone (MEK; relative evaporation rate 3.8), isopropanol (IPA; relative evaporation rate 1.7 ), Methyl isobutyl ketone (MIBK; relative evaporation rate 1.6), acetone, methyl propyl ketone and the like.

(D) A solvent (low volatility solvent) which is high in the dispersion stability of (A) tin-containing indium oxide particle, and is compatible with the solvent of (C).

The (D) low-volatile solvent contained in curable resin composition of this invention is a solvent with high dispersion stability of the said (A) tin containing indium oxide particle (particle of (A) component). Here, that the dispersion stability of the particle | grains of (A) component is high means that the glass plate is immersed in the isopropanol dispersion liquid of the particle | grains of (A) component, the particle | grains of (A) component adhere to a glass wall, and the particle | grains of the (A) component When the attached glass plate is immersed in each solvent, it is said that the particle | grains of (A) component are disperse | distributed uniformly visually in the said solvent. Low dispersion stability means that it is not uniformly disperse | distributed visually at this time. Moreover, it is preferable that the (D) low-volatile solvent is low in the solubility of the said (B) ethylenically unsaturated group containing fluorine-containing polymer.

Solvents that can be used as the (D) low-volatile solvent in the present invention include methanol (relative evaporation rate 2.1), isopropanol (IPA; relative evaporation rate 1.7), n-butanol (n-BuOH; relative evaporation rate 0.5), tert -Butanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethyl cellosolve, propyl cellosolve, butyl cellosolve, propylene glycol monoethyl ether acetate, and the like. From the viewpoint of improving the optical properties (haze, reflectance) and surface resistance of the resulting cured film, the (D) low-volatile solvent particularly preferably contains propylene glycol monomethyl ether (PGME).

The (C) high volatile solvent and / or (D) low volatile solvent used by this invention can use the solvent normally used for manufacture of the said (B) ethylenically unsaturated group containing fluorine-containing polymer as it is.

The (C) high volatile solvent and (D) low volatile solvent used by this invention need to be compatible. Compatibility is sufficient if the compatibility of the (C) high volatile solvent and (D) low volatile solvent is not separated in the specific structure of the composition of this invention.

Here, whether the selected solvent corresponds to either (C) high volatile solvent or (D) low volatile solvent used in the present invention is relatively determined among a plurality of selected solvent types, so that the relative evaporation rate is Isopropanol which is 1.7 may be used as (C) a high volatile solvent, and may be used as (D) a low volatile solvent.

The total amount of the solvent (C) and the solvent (D) is usually 300 to 5000 parts by mass, preferably 300 to 4000 parts by mass, relative to 100 parts by mass of the component other than the solvents (C) and (D) in the curable resin composition. More preferably, 300-3000 mass parts is used. The compounding ratio of a solvent (C) and a solvent (D) can be arbitrarily selected in the range of 1: 99-99: 1.

(E) a polyfunctional (meth) acrylate compound containing two or more (meth) acryloyl groups and / or a fluorine-containing (meth) acrylate compound containing one or more (meth) acryloyl groups (hereinafter May be collectively referred to as a "curable compound."

The polyfunctional (meth) acrylate compound (E-1) containing two or more (meth) acryloyl groups is used in order to improve the scratch resistance of the hardened | cured material obtained by hardening | curing curable resin composition, and the antireflection film using the same. Here, "a polyfunctional (meth) acrylate compound containing two or more (meth) acryloyl groups" means the compound containing two or more acryloyl groups, or the compound containing two or more methacryloyl groups. it means.

The fluorine-containing (meth) acrylate compound (E-2) containing one or more (meth) acryloyl groups is used in order to reduce the refractive index of curable resin composition.

The compound (E-1) is not particularly limited as long as it is a compound containing two or more (meth) acryloyl groups in the molecule. Examples thereof include neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and pentaerythritol tetra (meth). ) Acrylate, dipentaerythritol tetra (meth) acrylate, alkyl modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol penta (meth) acrylic Rate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, `` U-15HA '' (brand name, Shinnakamura Kagaku 1 type single, such as "HDP-M20" (brand name, Negami Kogyo Co., Ltd. make), or 2 or more types of these are mentioned. In addition, among these, neopentyl glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and caprolactone modified Dipentaerythritol hexa (meth) acrylate, "U-15HA", and "HDP-M20" (brand name, Negami Kogyo Co., Ltd. product) are especially preferable.

The compound (E-2) is not particularly limited as long as it is a fluorine-containing (meth) acrylate compound containing one or more (meth) acryloyl groups. As such an example, single 1 type, such as a perfluoro octyl ethyl (meth) acrylate, an octafluoro pentyl (meth) acrylate, a trifluoroethyl (meth) acrylate, or a combination of 2 or more of these is mentioned. .

Although content in particular of component (E) in curable resin composition of this invention is not restrict | limited, Usually, it is 5-80 mass% with respect to 100 mass% of composition total amounts except the organic solvent. The reason is that the scratch resistance of the cured coating film of the curable resin composition may not be obtained when the addition amount is less than 5 mass%. On the other hand, when the addition amount exceeds 80 mass%, the refractive index of the cured coating film of the curable resin composition is It is because it may become high and sufficient antireflection effect may not be acquired. Moreover, for this reason, it is more preferable to make the addition amount of a component (E) into 5 to 70 mass%, and it is still more preferable to set it as the value within the range of 5 to 50 mass%.

(F) radical photopolymerization initiator

In the curable resin composition of this invention, the (F) radical photopolymerization initiator (radiation (photo) polymerization initiator) which generate | occur | produces an active radical species by radiation (light) irradiation can be mix | blended as needed.

The radiation (photo) polymerization initiator is not particularly limited as long as it is decomposed by light irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenonebenzyl ketal, 1-hydroxycyclohexylphenyl ketone, 2 , 2-dimethoxy-1,2-diphenylethan-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone , 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propylether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy- 2-methylpropane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethyl thioxanthone, 2-isopropyl thioxanthone, 2-chlorothioke Santone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Butanone-1,4- (2-hydroxye Phenyl) (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl Phosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), and the like.

As a commercial item of a radiation (photo) polymerization initiator, the brand name of the Shiva specialty chemicals company make, for example: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, Tarocure 1116, 1173, BASF make, brand name: Lucillin TPO, UCB make, trade name: Uvecryl P36, Pratetsu, Ranvelte, make: trade name Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KT046, KIP75 / B, etc. are mentioned.

As for the compounding quantity of the radical photopolymerization initiator (F) used as needed in this invention, it is preferable to mix | blend 0.01-10 mass%, making the whole composition amount except the organic solvent 100 mass%, and 0.1-10 mass% Is more preferable. If it is less than 0.01 mass%, the hardness when it is made into hardened | cured material may become inadequate, and when it exceeds 10 mass%, it may not be hardened to the inside (lower layer) when it is made into hardened | cured material.

(G) other ingredients

In the curable composition of this invention, as long as the effect of this invention is not impaired, a photosensitizer, a polymerization inhibitor, a polymerization start adjuvant, a leveling agent, a wettability improving agent, surfactant, a plasticizer, a ultraviolet absorber, antioxidant, an electrification charge An inhibitor, an inorganic filler, a pigment, dye, solvents other than solvent (C) and (D), etc. can be mix | blended suitably.

2. Manufacturing method of curable resin composition

The composition of this invention can be manufactured as follows.

Highly soluble solvent of tin-containing indium oxide particle dispersion (component (A)), ethylenically unsaturated group-containing fluoropolymer (component (B)), ethylenically unsaturated group-containing fluoropolymer ((C) solvent), and tin-containing oxidation Dispersion stability of indium particles is high and is compatible with the solvent of (C) ((D) solvent), if necessary, polyfunctional (meth) acrylate (component (E)), radiation (photo) polymerization initiator (( F) component) and the like are placed in a reaction vessel with a stirrer and stirred at 35 ° C to 45 ° C for 2 hours to prepare a curable resin composition of the present invention.

When the solvent is substituted with the solvent (α) used for the first particle dispersion and a different solvent (β), 1.0 times the solvent (β) is added to the mass of the solvent (α) of the particle dispersion under the same conditions. Stir. Then, this composition liquid is concentrated under reduced pressure to the mass which becomes 50% of solid content concentration using the rotary evaporator, and the composition of this invention is manufactured.

3. Coating (Coating) Method of Curable Resin Composition

Curable resin composition of this invention is suitable for the use of an anti-reflective film and a coating material, As a base material which is an object of reflection prevention or a coating, it is plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, for example). , Epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene-based resin, etc.), metal, wood, paper, glass, slate and the like. The shape of these substrates may be plate-like, film-like or three-dimensional shaped bodies, and the coating method may be a conventional coating method such as dip coating, spray coating, flow coating, shower coating, roll coating, spin coating, brush coating, or the like. Can be mentioned. The thickness of the coating film by these coatings is 0.1-400 micrometers normally after drying and hardening, Preferably it is 1-200 micrometers.

4. Curing method of curable resin composition

Curable resin composition of this invention can be hardened by radiation (light). The source thereof is not particularly limited as long as it can be cured in a short time after coating the composition. For example, as a source of infrared rays, a lamp, a resistance heating plate, a laser, and the like can be cited. Examples of the source include daylight, lamps, fluorescent lamps, lasers, and the like. Mercury lamps, halogen lamps, lasers, and the like may be used as the source of ultraviolet rays, and heat generated from commercially available tungsten filaments as a source of electron beams. The electron system, the cold cathode system which generate | occur | produces by passing a high voltage pulse through metal, and the secondary electron system which uses the secondary electron which generate | occur | produces by collision of ionized gaseous molecule and a metal electrode are mentioned. As the source of alpha rays, beta rays, and gamma rays, for example, fission materials such as ⁶⁰ Co may be mentioned. In the case of gamma rays, a vacuum tube may be used to impinge the accelerated electrons to the anode. These radiations can be irradiated alone or in combination of two or more thereof over a period of time.

When using an active energy ray, it is preferable to make an exposure amount into the value within the range of 0.01-10 J / cm <^2> . The reason is that the exposure amount is 0.01 J / cm ² It is because hardening defect may generate | occur | produce if it is less than the case, and hardening time may become excessively long when an exposure amount exceeds 10 J / cm < ² >. Further, it is more preferable For these reasons, the exposure dose is more preferably in the range of 0.1 to 5 J / cm ^2, and in the range of 0.3 to 3 J / cm ^2.

It is necessary to perform hardening reaction of curable resin composition of this invention under anaerobic conditions, such as nitrogen. This is because radical polymerization is inhibited by oxygen, resulting in insufficient curing reaction.

II. Cured film

The cured film of this invention is obtained by hardening | curing the curable resin composition of the said invention, It has a multilayer structure of two or more layers, It is characterized by the above-mentioned. In particular, the (A) tin-containing indium oxide particles (particles of the component (A)) include at least one layer having a high density, and one or more layers substantially free of the particles of the component (A). It is preferable to have a layer structure of two or more layers.

The cured film of this invention can be obtained by coating the said curable resin composition on various base materials, for example, a plastic base material, and hardening it. Specifically, it is possible to obtain a coating molded product by coating the composition, drying the volatile component at 0 to 200 ° C., and then performing a curing treatment with the above-described radiation. In this case, the preferable irradiation light amount of ultraviolet-ray is 0.01-10 J / cm <^2> , More preferably, it is 0.1-2 J / cm <^2> . Moreover, irradiation conditions of a preferable electron beam are 10-300 KV of pressurized voltages, 0.02-0.30 mA / cm <^{2> of} electron densities, and 1-10 Mrad of electron beam irradiation amounts.

After apply | coating curable resin composition, in the process of evaporating and drying the solvent (C) and solvent (D) in a composition, the particle | grains of (A) component apply | coated to the base side (near boundary with an adjacent layer) or its It is localized on the other side. Therefore, since the particle | grains of (A) component exist in high density near one interface of a cured film, and the particle | grains of (A) component do not exist substantially in the vicinity of the other interface of a cured film, the resin layer of low refractive index Is formed. Therefore, the cured film which has a layer structure of two or more layers substantially is obtained by hardening | curing one coating film which consists of curable resin composition. Each layer formed separately can be confirmed by observing the cross section of the obtained film | membrane with an electron microscope, for example. The layer in which the particles of the component (A) are present at a high density is a concept indicating a portion where the particles of the component (A) are aggregated, and is a layer substantially composed of the particles of the component (A) as a main component. B) A component etc. may coexist. On the other hand, the layer in which the particle | grains of (A) component do not exist substantially is a concept which shows the part which the particle | grains of (A) component do not exist, but the particle of (A) component does not fall within the range which does not impair the effect of this invention. It may be included a bit. This layer is a layer comprised substantially from components other than particle | grains of (A) component, such as hardened | cured material of (B) component and (E) component. The cured film of this invention has a 2-layered structure in which the layer in which the particle | grains of (A) component existed at high density, and the layer in which the particle | grains of (A) component substantially do not exist substantially each formed the continuous layer was formed. When a polyethylene terephthalate (PET) resin (including a PET resin having an easy adhesion layer) is used as the substrate, a layer which is usually a substrate, a layer in which particles of component (A) are present at a high density, and (A) Layers in which substantially no particles of the component are present are formed adjacent to each other in this order.

Here, the layer structure of two or more layers means two or more layers including both "a layer in which particles of component (A) are present at high density" and "a layer in which particles of component (A) are substantially free". It may contain, and may consist only of two or more "layers in which a tin-containing indium oxide particle exists in high density."

The (B) ethylenically unsaturated group-containing fluorine-containing polymer in the curable resin composition of the present invention has a lower refractive index than a thermosetting resin (for example, a melamine compound) and has preferable optical properties as a low refractive index layer of an antireflection film. As the (A) tin-containing indium oxide particles, by using an IPA dispersion of tin-containing indium oxide particles having high transparency and excellent conductivity, an antireflection film having more excellent optical characteristics and antistatic properties can be formed.

While the cured film of this invention is high hardness, it has a characteristic which can form the coating film (film | film | coat) excellent in abrasion resistance and adhesiveness of adjacent layers, such as a base material and a low refractive index layer, and a base material. Moreover, since heat is not used for hardening reaction and does not accompany the hydrolysis reaction which arises in a thermosetting reaction, the cured film obtained is excellent in moisture heat resistance. Therefore, the cured film of this invention is used especially suitably for anti-reflective films, such as a film type liquid crystal element, a touch panel, and a plastic optical component.

The degree of change in the refractive index can be adjusted by the content of the component (A), the content of the (B) ethylenically unsaturated group-containing fluorine-containing polymer, the composition, the content of the (E) component (curable compound), and the like.

In addition, the refractive index in the low refractive index part of a cured film is 1.20-1.55, for example, and the refractive index in the high refractive index part is 1.50-2.20.

III. Laminate

The laminated body whose cured film which has a layer structure of two or more layers obtained from curable resin composition of this invention is a part of laminated structure can be obtained. Any two or more adjacent layers other than the base material layer which comprises a laminated body can be manufactured as a cured film of curable resin composition of this invention.

For example, when the substrate is a transparent substrate, the laminate has an excellent antireflection film by providing a low refractive index layer in the outermost layer (the layer furthest from the substrate). The laminated body can be used for optical components, such as a lens and a selective permeable membrane filter, in addition to an antireflection film.

The specific layer structure of an antireflection film is not specifically limited. A typical antireflection film is provided with an antireflection function by laminating at least a high refractive index film and a low refractive index film on the substrate in this order. In addition, a part of the laminated constitution of the laminate may include a hard coating layer, an antistatic layer, and the like. Since the cured film obtained by hardening | curing curable resin composition of this invention can form a high refractive index layer and a low refractive index layer on a base material by one process, the manufacturing process can be simplified.

The cured film of this invention consists of two layers, a high refractive index layer and a low refractive index layer normally, and can form a laminated body suitable as an antireflection film by forming this on a base material. An antireflection film which is a typical example of such a laminate is shown in FIG. 1. The high refractive index layer 14 and the low refractive index layer 16 are formed by providing the hard-coat layer 12 on the base material 10, apply | coating and hardening curable resin composition of this invention on it.

The anti-reflection film may further have other layers, for example, a so-called wide band having a relatively uniform reflectance characteristic for light of a wide wavelength range by providing a plurality of combinations of a high refractive index film and a low refractive index film. The antireflection film may be made, or an antistatic layer may be provided.

Although there is no restriction | limiting in particular as a base material, When using as an anti-reflective film, For example, the above-mentioned plastics (PET, polycarbonate, polymethylmethacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose) (TAC) resin, ABS resin, AS resin, norbornene-type resin, etc.) are mentioned.

The cured product of the present invention obtained by applying the curable resin composition of the present invention on a substrate and UV curing is excellent in scratch resistance (steel wool resistance) and haze, and has high hardness.

Since the laminated body of this invention is excellent in scratch resistance and haze, and excellent in heat-and-moisture resistance, it is especially preferably used as an anti-reflective film, such as a film type liquid crystal element, a touch panel, a plastic optical component.

EXAMPLE

EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in more detail, the scope of the present invention is not limited to description of these Examples. In addition, in the Example, unless otherwise indicated, the compounding quantity of each component "part" means a mass part and "%" means the mass%.

Preparation Example 1: Preparation of hydroxyl-containing fluorine-containing polymer (b-1)

After fully replacing the autoclave made of stainless steel with an internal volume 1.5 L stirrer with nitrogen gas, 800 g of ethyl acetate, 1, vinyloxy-3,3,4,4,5,5,6,6,7 "VPS-1001" as 165.5 g of 7,7,8,8,9,9,10,10,10-heptadecafluorodecane, 16.2 g of ethyl vinyl ether, 49.5 g of hydroxyethyl vinyl ether, and azo group-containing polydimethylsiloxane. (Made by Wako Pure Chemical Industries, Ltd.) 12.0 g and 2.0 g of lauroyl peroxide were added, and after cooling to dryness-methanol to -50 degreeC, oxygen in a system was removed again by nitrogen gas.

Then, 202.6 g of hexafluoropropylene was added to start the temperature increase. The reaction was continued under stirring at 70 ° C., and water cooled after 20 hours to terminate the reaction. After reaching room temperature, the unreacted monomer was taken out, the autoclave was opened, and the polymer solution of 22% of solid content concentration was obtained. The obtained polymer solution was thrown into methanol, and the polymer was deposited, washed with methanol, and vacuum dried at 50 deg. C to obtain 264 g of fluorine-containing polymer (b-1).

Preparation Example 2 Preparation of Ethylenic Unsaturation-Containing Fluorine-Containing Polymer (F Polymer 1)

In a 1 liter volumetric flask equipped with an electronic stirrer, a glass cooling tube and a thermometer, 63.00 g of the hydroxyl group-containing fluorine-containing polymer (b-1) obtained in Production Example 1 and 2,6-di-t as a polymerization inhibitor 0.01 g of butylmethylphenol and 442 g of MIBK were added and stirring was carried out until the hydroxyl group-containing fluorine-containing polymer (b-1) was dissolved in MIBK at 20 ° C, and the solution became transparent and uniform. Subsequently, 15.01 g of 2-acryloyloxy ethyl isocyanate is added to the system, stirred until the solution becomes uniform, and then 0.16 g of dibutyltin dilaurate is added to start the reaction, and the temperature of the system is increased. Was maintained at 55 to 65 ° C and stirring was continued for 5 hours to obtain a MIBK solution of an ethylenically unsaturated group-containing fluorine-containing polymer (F polymer 1). After weighing 2 g of this solution to the aluminum dish, it dried and weighed for 5 minutes on the 150 degreeC hotplate, and calculated | required solid content, and it was 15%.

The polystyrene reduced number average molecular weight by gel permeation chromatography of the obtained F polymer 1 was 29,600, and the fluorine content was 49 mass%.

Example 1

Preparation of Curable Resin Composition 1

260 g of ITO particle sol (NID-20, an ITO dispersion manufactured by Fuji Chemical Corporation (isopropyl alcohol (IPA) solution), 52.0 g as particles), an ethylenically unsaturated group-containing fluorine-containing polymer obtained in Production Example 2 (F polymer 1 ) 215.5 g (32.3 g as ethylenically unsaturated group-containing fluoropolymer), dipentaerythritol pentaacrylate (SR-399E, manufactured by Nippon Kayaku Co., Ltd.) 17.1 g, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -1-butanone (Irgacure 369, Shiva Specialty Chemicals make, radical photopolymerization initiator) 2.56 g, methyl ethyl ketone 206 g, methyl isobutyl ketone 186 g, isopropanol 23 g, normal 45 g of butanol and 45 g of methyl amyl ketone were added and stirred. Solid content concentration of the obtained curable resin composition was 10.4%. The solvent ratio which mix | blended is shown in Table 1.

In addition, three types of curable resin composition samples were prepared using three types of ITO dispersions with different lots.

Examples 2-4

Preparation of Curable Resin Compositions 2 to 4

Except having mix | blended each solid component in the ratio shown in Table 1, it carried out similarly to Example 1, and obtained curable resin compositions 2-6. At this time, the solvent was mix | blended so that it might become the same solvent ratio as Table 1 similar to Example 1. In addition, about curable resin compositions 2-4, each of three types of curable resin composition samples was manufactured using three types of ITO dispersions from which a lot differs.

In addition, three cured film samples were produced, respectively, using curable resin compositions 1-4 (each of 3 types of samples) manufactured in the said Examples 1-4, and the characteristic of the cured film was evaluated. The manufacturing method of a cured film is as follows.

Silica particle sol (methyl ethyl ketone silica sol, MEK-ST manufactured by Nissan Chemical Industries, Ltd., number average particle diameter 0.022 µm, silica concentration 30%) 98.6 g, 1 g of 1-hydroxycyclohexylphenyl ketone, Irga Cure 907 (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, manufactured by Ciba Specialty Chemicals) 1.2 g, dipentaerythritol hexaacrylate (DPHA ) 33.2 g and 7 g of cyclohexanone were mixed and stirred to obtain a composition for a silica particle-containing hard coating layer. This silica particle-containing hard coating layer composition was coated on a triacetyl cellulose film (manufactured by Fuji Shashin Film Co., Ltd., film thickness of 80 μm) using a wire bar coater (# 12), and then dried at 80 ° C. in an oven for 2 minutes. I was. Subsequently, a hard coat layer was formed by irradiating ultraviolet rays under light irradiation conditions of 0.3 J / cm ² using a high pressure mercury lamp under air. It was 5 micrometers when the film thickness of the hard-coat layer was measured with the stylus type film thickness meter.

On the obtained hard coat layer, the curable resin composition obtained by the said Examples 1-4 and Comparative Examples 1 and 2 was coated using the wire bar coater (# 3), and it dried at 80 degreeC in oven for 2 minutes. Subsequently, under a nitrogen atmosphere, ultraviolet rays were irradiated under a light irradiation condition of 0.9 J / cm ² using a high pressure mercury lamp to form a cured film layer having a thickness of 0.2 μm.

Evaluation of Curing Film

(1) layer separation

The cross section of the obtained cured film was observed under a microscope, and it was evaluated whether it separated into two layers. Evaluation criteria are as follows. Typical examples of the following evaluation criteria are shown in FIG. 2.

(Circle): It is divided into two layers (The cured film is divided into the layer (high refractive index layer) in which the ITO particle of a base material exists in high density, and the layer (low refractive index layer) substantially free of ITO particle on the air side. .

(Triangle | delta): Although it isolate | separates two layers, since the separation interface is not smooth, the part which does not separate two layers locally arises.

×: not separated into two layers.

In addition, the layer separability of the composition of a comparative example is called "(circle) -x" and "(triangle | delta) -x" because there may be layer separation and layer separation depending on the lot of the used ITO particle dispersion liquid, and a stable result is not obtained. Notation.

(2) haze

Turbidity (haze value) in the obtained laminated body was measured according to JIS K7105 using a color haze meter (manufactured by Suga Seiki Co., Ltd.).

(3) Surface Resistance (Ω / □)

The surface resistance (Ω / square) of the obtained cured film was measured using the high resistance meter (HP4330 by Hewlett-Packard Co., Ltd.) at the main electrode diameter 26mm (phi), and the applied voltage 100V.

(4) reflectance

The reflectance of the obtained antireflective laminate was wavelength 340 to 700 nm by a spectral reflectance measuring device (magnetic spectrophotometer U-3410, manufactured by Hitachi Seisakusho Co., Ltd.) incorporating a large sample chamber integrating sphere apparatus 150-09090. It evaluated by measuring in the range of. Specifically, the reflectance of the antireflection laminate (antireflection film) at each wavelength was measured based on the reflectance in the aluminum vapor deposition film, and the reflectance of light at a wavelength of 550 nm was determined among them. .

(5) steel wool resistant

The steel wool tolerance test of the cured film was implemented by the method shown next. That is, a steel wool (Bonstar N0.0000, manufactured by Nippon Steel Wool Co., Ltd.) is attached to a Hakjin type friction fastness tester (AB-301, Tester Sangyo Co., Ltd.), and the surface of the cured film is 1000 g. Was repeated 10 times, and the presence or absence of the scratches on the surface of the cured film was visually confirmed by the following criteria.

(Circle): Peeling of a cured film and generation | occurrence | production of a scratch are hardly confirmed.

(Triangle | delta): Fine scratches are recognized by a cured film.

X: Peeling generate | occur | produces in a part of cured film, or a string-shaped flaw arises on the surface of a cured film.

Abbreviated-name of Table 1, etc. show the following.

NID-20: Fuji Chemicals ITO dispersion (IPA: 20 mass% dispersion)

JX-1002ITV: Shokubai Kasei Kagaku Kogyo ITO dispersion (IPA: 20 mass% dispersion)

SR-399E: dipentaerythritol pentaacrylate: manufactured by Nippon Kayaku

NK oligo U-6HA: six-functional urethane acrylate; Shin-Nakamura Kagaku high school production

NK oligo U-15HA: 15 functional urethane acrylate; Shin-Nakamura Kagaku high school production

Irgacure 369: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone; Shiva, specialty, chemicals production

MEK: methyl ethyl ketone

MIBK: methyl isobutyl ketone

IPA: Isopropanol

MAK: methyl amyl ketone

n-BuOH: n-butanol

PGME: propylene glycol monomethyl ether

Preparation Example 3: Preparation of hydroxyl-containing fluorine-containing polymer (b-2)

After fully replacing the autoclave made of stainless steel with an internal volume 1.5 L stirrer with nitrogen gas, 500 g of ethyl acetate, 43.2 g of perfluoro (propyl vinyl ether), 41.2 g of ethyl vinyl ether, and hydroxyethyl vinyl ether As 21.5 g, nonionic reactive emulsifier, "Adeka Riaso NE-30" (made by Asahi Denka Kogyo Co., Ltd.) 40.5 g, azo-group containing polydimethylsiloxane "VPS-1001" (made by Wako Pure Chemical Industries, Ltd.) 6.0 g and lauroyl peroxide 1.25 g were added, cooled to -50 ° C with dry ice-methanol, and then oxygen in the system was removed again with nitrogen gas.

Then, 97.4 g of hexafluoropropylene was added to start the temperature increase. The pressure when the temperature in the autoclave reached 60 ° C. was 5.3 × 10 ⁵ pa. Thereafter, the reaction was continued under stirring at 70 ° C. for 20 hours, and the autoclave was water-cooled to stop the reaction when the pressure was lowered to 1.7 × 10 ⁵ pa. After reaching room temperature, the unreacted monomer was taken out, the autoclave was opened, and the polymer solution of 26.4% of solid content concentration was obtained. The obtained polymer solution was thrown into methanol to precipitate a polymer, and then washed with methanol and dried in vacuo at 50 ° C to obtain 220 g of a hydroxyl group-containing fluorine-containing polymer (b-2).

Preparation Example 4: Preparation of Ethylenic Unsaturation-Containing Fluorine-Containing Polymer (F Polymer 2)

In a 1 liter volumetric flask equipped with an electronic stirrer, a glass cooling tube and a thermometer, 50.0 g of the hydroxyl group-containing fluorine-containing polymer (b-2) obtained in Production Example 3 and 2,6-di-t as a polymerization inhibitor 0.01 g of butylmethylphenol and 374 g of MIBK were added, and agitation was performed until the hydroxyl group-containing fluorine-containing polymer (b-2) was dissolved in MIBK at 20 ° C, and the solution became transparent and uniform. Subsequently, 16.0 g of 2-acryloyloxy ethyl isocyanate is added to the system, stirred until the solution becomes uniform, and then 0.1 g of dibutyltin dilaurate is added to start the reaction, and the temperature of the system is started. Was maintained at 55 to 65 ° C and stirring was continued for 5 hours to obtain a MIBK solution of an ethylenically unsaturated group-containing fluorine-containing polymer (F polymer 2). After weighing 2 g of this solution to the aluminum dish, it dried and weighed for 5 minutes on the 150 degreeC hotplate, and calculated | required solid content, and it was 15.0%.

The polystyrene reduced number average molecular weight by gel permeation chromatography of the obtained F polymer 2 was 43,000, and the fluorine content was 35 mass%.

Example 5

Preparation of Curable Resin Composition 5

Ethylene unsaturated group-containing fluorine-containing polymer (F polymer 2) obtained in 250 g of ITO particle sol (NID-20, ITO dispersion made by Fuji Chemical (isopropyl alcohol (IPA) solution), 50.0 g as particles), and Production Example 4 ) 207.2 g (31.08 g as ethylenically unsaturated group-containing fluoropolymer), dipentaerythritol pentaacrylate (SR-399E, manufactured by Nippon Kayaku Co.) 16.46 g, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -1-butanone (Irgacure 369, Ciba Specialty Chemicals Co., Ltd., radical photopolymerization initiator) 2.46 g, methyl ethyl ketone 178 g, methyl isobutyl ketone 118 g, normal butanol 168 g It was added and stirred. Solid content concentration of the obtained curable resin composition was 10.6%. The blended solvent ratio is shown in Table 3.

Examples 6-10

Preparation of Curable Resin Compositions 6 to 10

Except having mix | blended each solid component in the ratio shown in Table 2, it carried out similarly to Example 5, and obtained curable resin compositions 6-10. At this time, the solvent was mix | blended so that it might become the same solvent ratio as Table 3 similar to Example 5.

Moreover, the cured film was manufactured using curable resin composition 5-10 manufactured in the said Examples 5-10, and the characteristic of the cured film was evaluated. The manufacturing method of a cured film is as follows.

Silica particle sol (methyl ethyl ketone silica sol, MEK-ST manufactured by Nissan Chemical Industries, Ltd., number average particle diameter 0.022 µm, silica concentration 30%) 98.6 g, 1 g of 1-hydroxycyclohexylphenyl ketone, Irga Cure 907 (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, manufactured by Ciba Specialty Chemicals) 1.2 g, dipentaerythritol hexaacrylate (DPHA ) 33.2 g and 7 g of cyclohexanone were mixed and stirred to obtain a composition for a silica particle-containing hard coating layer. This silica particle-containing hard coating layer was coated on a triacetyl cellulose film (LOFO, film thickness of 80 μm) using a wire bar coater (# 12), and then dried at 8.0 ° C. in an oven for 1 minute. Subsequently, a hard coat layer was formed by irradiating ultraviolet rays under light irradiation conditions of 0.6 J / cm ² using a high pressure mercury lamp under air. It was 5 micrometers when the film thickness of the hard coat layer was measured by the stylus type film thickness meter.

On the obtained hard coat layer, after coating the curable resin composition obtained in the said Examples 5-10 using the wire bar coater (# 3), it dried at 80 degreeC in oven for 1 minute. Subsequently, under a nitrogen atmosphere, ultraviolet rays were irradiated under a light irradiation condition of 0.9 J / cm ² using a high pressure mercury lamp to form a cured film layer having a thickness of 0.2 μm.

Evaluation of Curing Film

(1) layer separation

The cross section of the obtained cured film was observed under a microscope, and it was evaluated whether it separated into two layers. Evaluation criteria are as follows.

(Circle): It is isolate | separated into two layers (the middle refractive index layer or the hard-coat layer side is a layer (high refractive index layer) which tin-containing indium oxide particle exists in high density, and the layer which does not substantially exist tin-containing indium oxide particle on it ( Low refractive index layer).

×: not separated into two layers.

(2) haze

The turbidity (haze value) in the obtained laminated body was measured using the haze measuring system, and the following references | standards evaluated.

(Circle): Haze value is 1% or less.

(Triangle | delta): A haze value exceeds 1% and is 3% or less.

X: Haze value exceeded 3%.

(3) Surface Resistance (Ω / □)

The surface resistance ((ohm / square)) of the obtained cured film was measured using the high resistance meter (HP4330 by Hewlett-Packard Co., Ltd.) at the main electrode diameter of 26 mm (phi) and the applied voltage of 100V, and the following references | standards evaluated.

○: The resistance value is 1 × 10 ¹¹ Ω / □ or less.

(Triangle | delta): A resistance value exceeds 1x10 <^11> ohm / square, and is 1x10 <^{13> (} ohm) / square or less.

X: Resistance exceeded 1x10 ¹³ ohms / square.

(4) antireflection

The antireflection property of the obtained antireflection laminate is wavelength 340 to a spectroscopic reflectance measuring device (magnetic spectrophotometer U-3410, manufactured by Hitachi Seisakusho Co., Ltd.) incorporating a large sample chamber integrating sphere apparatus 150-09090. The reflectance was measured and evaluated in the range of 700 nm. Specifically, the reflectance of the antireflective laminate (antireflection film) at each wavelength is measured with the reflectance in the aluminum vapor deposition film as a reference (100%), and among them, from the reflectance of light at a wavelength of 550 nm, Antireflection was evaluated based on the following criteria.

○: The reflectance is 1% or less.

(Triangle | delta): Reflectance exceeds 1% and is 2% or less.

X: reflectance exceeds 2%.

(5) steel wool resistant

The steel wool tolerance test of the cured film was implemented by the method shown next. That is, a steel wool (Bonstar N0.0000, manufactured by Nippon Steel Wool Co., Ltd.) is attached to the Hakjin type friction fastness tester (AB-301, Tester Sangyo Co., Ltd.), and the surface of the cured film is 500 g. Was repeated 10 times, and the presence or absence of scratches on the surface of the cured film was visually confirmed by the following criteria.

(Circle): Peeling of a cured film and generation | occurrence | production of a scratch are hardly confirmed.

(Triangle | delta): Fine scratches are recognized by a cured film.

X: Peeling generate | occur | produces in a part of cured film, or a string-shaped flaw arises on the surface of a cured film.

Abbreviated-name etc. in Table 2 show the following.

NID-20: Fuji Chemicals ITO dispersion (IPA: 20% dispersion)

SR-399E: dipentaerythritol pentaacrylate; Nippon Kayaku Manufacturing

NK oligo U-6HA: urethane acrylate; Shin-Nakamura Kagaku high school production

Irgacure 369: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone; Shiva, specialty, chemicals production

From the result of Table 1 and Table 2, it turned out that curable resin composition of this invention is excellent in layer separation property and antireflection property. In particular, it was found that Examples 1 to 4 using the ethylenically unsaturated group-containing fluorine-containing polymer having a high fluorine content had low reflectance and excellent scratch resistance.

Curable resin composition of this invention can form the cured film which has a multilayer structure of two or more layers on a base material from one coating film.

Curable resin composition of this invention and its hardened | cured material are, for example, a plastic optical component, a touch panel, a film-type liquid crystal element, a plastic container, the flooring material as a building interior material, a wall material, an artificial marble, etc. Protective coatings; Anti-reflection films such as a film type liquid crystal element, a touch panel and a plastic optical component; Adhesive of various base materials, sealing material: As a binder of printing ink, etc., it can use especially suitably as an anti-reflective film.

Claims (12)

(A) tin-containing indium oxide particles, (B) an ethylenically unsaturated group-containing fluorine-containing polymer, (C) (B) Highly soluble solvent of ethylenically unsaturated group containing fluorine-containing polymer, and (D) Solvent which is high in the dispersion stability of (A) tin-containing indium oxide particle, and is compatible with the solvent of (C) And the relative evaporation rate of the solvent of (C) is higher than the relative evaporation rate of the solvent of (D). The curable resin composition according to claim 1, wherein the (A) tin-containing indium oxide particles are derived from an isopropanol dispersion sol of tin-containing indium oxide. The fluorine-containing polymer according to claim 1, wherein the (B) ethylenically unsaturated group-containing fluorine-containing polymer Hydroxyl group-containing fluorine-containing polymer, Compound containing functional group and ethylenically unsaturated group which can react with hydroxyl group It is obtained by reacting with curable resin composition characterized by the above-mentioned. The hydroxy group-containing fluorine-containing polymer according to claim 3, wherein the hydroxyl group-containing fluorine-containing polymer is 100% by mass of (a) 5 to 90% by mass of a structural unit represented by the following formula (1), (b) Curable resin composition containing 0.3-90 mass% of structural units represented, and 1-65 mass% of structural units represented by following General formula (3). <Formula 1>

[In Formula 1, R ¹ represents a group represented by a fluorine atom, a fluoroalkyl group, or -OR ² (wherein R ² represents an alkyl group or a fluoroalkyl group.) <Formula 2>

In Formula 2, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group,-(CH ₂ ) _x -OR ⁵ or -OCOR ⁵ (wherein R ⁵ represents an alkyl group or a fluoroalkyl group, x is Represents a group represented by 0 or 1), a carboxyl group or an alkoxycarbonyl group] <Formula 3>

In the formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents-(CH ₂ ) _v -OR ²⁷ or -OCOR ²⁷ (wherein R ²⁷ represents a hydrogen atom, a hydroxyalkyl group or a glycidyl group) , v represents a number from 0 to 2). 4. When the hydroxyl group-containing fluorine-containing polymer is 100% by mass, the 0.1 to 10% by mass of the structural unit represented by the following formula (4) derived from the azo group-containing polysiloxane compound (d) Curable resin composition containing further. <Formula 4>

[In Formula 4, R <^8> and R <^9> may be same or different and represents a hydrogen atom, an alkyl group, a halogenated alkyl group, or an aryl group. The curable resin composition according to claim 3, wherein the functional group capable of reacting with the hydroxyl group is selected from the group consisting of an isocyanate group, a carboxyl group, an acid halide group, and an acid anhydride group. The curable resin composition according to claim 1, wherein the ethylenically unsaturated group-containing fluorine-containing polymer contains 40% by mass or more of fluorine. The solvent according to claim 1, wherein the solvent of (C) is a solvent having low dispersion stability of (A) tin-containing indium oxide particles, The solvent of (D) is a solvent with low solubility of the (B) ethylenically unsaturated group containing fluoropolymer, Curable resin composition characterized by the above-mentioned. (E) A polyfunctional (meth) acrylate compound containing at least two (meth) acryloyl groups and / or a fluorine-containing (meth) containing at least one (meth) acryloyl group. ) An acrylate compound further contains a curable resin composition. The curable resin composition according to claim 1, further comprising (F) a radical photopolymerization initiator. It is obtained by hardening | curing curable resin composition in any one of Claims 1-10, and has a multilayered structure of two or more layers, The cured film characterized by the above-mentioned. 12. The method of claim 11, wherein the (A) tin-containing indium oxide particles include at least one layer having a high density, and (A) tin-containing indium oxide particles having at least one layer substantially free of two layers. Cured film which has a layer structure more than a layer.

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