JP4887937B2 - Curable resin composition and cured film comprising the same - Google Patents

Description

  The present invention relates to a curable resin composition and a cured film comprising the same, and in particular, 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, is formed from a single coating film. The present invention relates to a curable resin composition and a cured film comprising the same.

  In various display panels such as liquid crystal display panels, cold cathode ray tube panels, plasma displays, etc., in order to prevent reflection of external light and improve image quality, it has low refractive index, scratch resistance, coatability, and durability. There is a need for an antireflection film including a low refractive index layer made of an excellent cured product. These display panels are often wiped with gauze impregnated with ethanol or the like in order to remove attached fingerprints, dust, and the like, and are required to have scratch resistance. In particular, in a liquid crystal display panel, the antireflection film is provided on the liquid crystal unit in a state of being bonded to a polarizing plate. In addition, for example, triacetyl cellulose is used as the base material. However, in an antireflection film using such a base material, an alkali is usually used in order to increase the adhesiveness when being bonded to the polarizing plate. It is necessary to saponify with an aqueous solution. Therefore, in the use of a liquid crystal display panel, an antireflection film excellent in alkali resistance is particularly required in terms of durability.

  As a material for a low refractive index layer of an antireflection film, for example, a fluororesin-based paint containing a hydroxyl group-containing fluoropolymer is known and disclosed in Patent Document 1, Patent Document 2, Patent Document 3, and the like. However, in such a fluororesin-based paint, it is necessary to heat and crosslink a hydroxyl group-containing fluoropolymer and a curing agent such as melamine resin under an acid catalyst in order to cure the coating film. Depending on the conditions, there are problems that the curing time becomes excessively long and the types of base materials that can be used are limited. Moreover, although the obtained coating film was excellent in the weather resistance, there was a problem that it was poor in scratch resistance and durability.

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

JP 57-34107 A JP 59-189108 A JP 60-67518 A Japanese Patent Publication No. 6-35559

These conventional anti-reflective coatings made of fluorine-based materials require the formation of a low-refractive-index layer made of a fluorine-based material on the high-refractive index layer provided on the substrate. It was necessary to provide the process separately.
Further, the scratch resistance of the low refractive index layer as the surface layer was not sufficient.
The present invention has been made in the background of the above situation, and its object is to provide a curable resin composition that can be cured by ultraviolet rays that can efficiently produce a low refractive index layer and a high refractive index layer. There is to do. Another object of the present invention is to provide a cured film having lower reflectivity, higher transparency, greater adhesion to the substrate, excellent scratch resistance, and excellent environmental resistance. It is to provide.

  In order to achieve the above object, the present inventors conducted intensive research, blended tin-containing indium oxide particles with a high fluorine content ethylenically unsaturated group-containing fluorine-containing polymer that is cured by ultraviolet irradiation, and When a composition in which two kinds of solvents having specific physical properties are combined is applied to a substrate and the solvent is evaporated, the layer containing the tin-containing indium oxide particles or the ITO particles exist in a high density. It has been found that the layer is separated into two or more layers, that is, a layer in which the tin-containing indium oxide particles are hardly present. Furthermore, the cured film obtained by irradiating with ultraviolet rays was found to be excellent in scratch resistance and transparency, and further excellent in weather resistance, and the present invention was completed.

That is, this invention provides the following curable resin composition and the cured film formed by hardening it.
[1] The following ingredients:
(A) Tin-containing indium oxide particles (B) Ethylenically unsaturated group-containing fluoropolymer containing 40% by mass or more of fluorine (C) (B) High solubility of ethylenically unsaturated group-containing fluoropolymer Solvent (D) (A) The dispersion stability of the tin-containing indium oxide particles is high, the solvent contains a solvent compatible with the solvent (C), and the relative evaporation rate of the solvent (C) is (D The curable resin composition is characterized by being larger than the relative evaporation rate of the solvent.
[2] The curable resin composition according to the above [1], wherein the (A) tin-containing indium oxide particles are derived from an isopropanol-dispersed sol of tin-containing indium oxide.
[3] The ethylenically unsaturated group-containing fluorine-containing polymer containing (B) 40% by mass or more of fluorine,
A hydroxyl group-containing fluoropolymer,
A compound containing a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated group;
The curable resin composition according to the above [1] or [2], which is obtained by reacting
[4] When the hydroxyl group-containing fluoropolymer is 100% by mass of the whole fluoropolymer, the following structural units (a) 5 to 90% by mass, (b) 0.3 to 90% by mass and (c ) The curable resin composition according to the above [3], comprising 1 to 65% by mass.
(A) Structural unit represented by the following formula (1) (b) Structural unit represented by the following formula (2) (c) Structural unit represented by the following formula (3)
[In formula (1), R ¹ represents a fluorine atom, a fluoroalkyl group or a group represented by —OR ² (R ² represents an alkyl group or a fluoroalkyl group)]
[In the formula (2), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, and a group represented by — (CH ₂ ) _x —OR ⁵ or —OCOR ⁵ (R ⁵ represents an alkyl group or a fluoroalkyl group). A group, x represents a number of 0 or 1), a carboxyl group or an alkoxycarbonyl group]
[In the formula (3), R ⁶ is a hydrogen atom or a methyl group, R ⁷ is a group represented by — (CH ₂ ) _v —OR ²⁷ or —OCOR ²⁷ (R ²⁷ is a hydrogen atom, a hydroxyalkyl group or glycidyl And v represents a number from 0 to 2)]
[5] When the hydroxyl group-containing fluoropolymer is 100 mass% of the whole fluoropolymer, the following structural unit (d) 0.1 to 10 mass% derived from the azo group-containing polysiloxane compound is further added. The curable resin composition according to the above [3] or [4].
(D) Structural unit represented by the following general formula (4)
[In General Formula (4), R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group]
[6] The functional group capable of reacting with the hydroxyl group is any one of the above [3] to [5], which is a group selected from the group consisting of an isocyanate group, a carboxyl group, an acid halide group, and an acid anhydride group. Curable resin composition.
[7] 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 in which the solubility of the (B) ethylenically unsaturated group-containing fluoropolymer is low, and the curable resin composition according to any one of the above [1] to [6] object.
[8] Furthermore, component (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 The curable resin composition according to any one of the above [1] to [7], comprising:
[9] The curable resin composition according to any one of the above [1] to [8], further comprising a component (F) a radical photopolymerization initiator.
[10] A cured film obtained by curing the curable resin composition according to any one of [1] to [9], and having a multilayer structure of two or more layers.
[11] Two or more layers consisting of (A) one or more layers in which tin-containing indium oxide particles are present at high density and one or less layers in which (A) tin-containing indium oxide particles are substantially absent The cured film as described in [10] above, which has a structure.

  The curable resin composition of the present invention can form a cured film having a multilayer structure of any two or more layers, such as a low refractive index layer and a high refractive index layer, from a single coating film. The manufacturing process of the cured film which has can be simplified.

  Since the curable resin composition of the present invention does not undergo a curing reaction due to heat involving hydrolysis, it can provide a cured film excellent in environmental resistance (moisture heat resistance and the like).

  The curable resin composition of the present invention can be advantageously used for the formation of optical materials such as an antireflection film and a selective transmission film filter, and also requires weather resistance by utilizing its high fluorine content. It can be suitably used as a coating material, a weather-resistant film material, a coating material, and the like for the substrate to be formed. Moreover, since the cured film has excellent adhesion to the substrate, has high scratch resistance, has antistatic performance, and imparts a good antireflection effect, it is extremely useful as an antireflection film. By applying it to a display device, the visibility can be improved.

Furthermore, the reflectance of the obtained laminated body can be improved by raising the fluorine content of the ethylenically unsaturated group-containing fluoropolymer.
In addition, by not introducing a reactive surfactant into the fluorine-containing polymer containing an ethylenically unsaturated group, fluctuations in the layer separation characteristics (layer separation, Can be improved).

  Hereinafter, the curable resin composition of the present invention, the cured film thereof, and the laminate will be specifically described.

I. Curable resin composition The curable resin composition of the present invention comprises (A) tin-containing indium oxide particles, (B) an ethylenically unsaturated group-containing fluoropolymer, and (C) (B) an ethylenically unsaturated group. A solvent (fast volatile solvent) in which the fluorine-containing polymer is highly soluble, (D) a solvent having high dispersion stability of the (A) tin-containing indium oxide particles and compatible with the solvent (C) ( A slow volatile solvent).

1. Each component of the 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 a cured film obtained by curing the curable resin composition of the present invention highly refractive.

The tin-containing indium oxide particles (A) used in the present invention are a dispersion of isopropanol (hereinafter sometimes referred to as “IPA”) or propylene glycol monomethyl ether (hereinafter sometimes referred to as “PGME”). Is preferred. The solvent dispersion of tin-containing indium oxide particles (A) can be used alone or in combination of two or more having different particle concentrations.
As a commercial item of the IPA dispersion liquid of tin-containing indium oxide particles (A), for example, JX1002-ITV (manufactured by Catalytic Chemical Industry Co., Ltd., IPA: 20% by mass dispersion liquid), JX1003-ITV (Catalytic Chemical Industry Co., Ltd.) , PGME: 20% by mass dispersion), NID-20 (Fuji Chemical Co., Ltd., IPA: 20% by mass dispersion), and the like.

  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, and particularly preferably 0.001 μm to 0.1 μm, as measured by electron microscopy. preferable. When the number average particle diameter exceeds 2 μm, the transparency when cured is reduced, and the surface state when coated is liable to be deteriorated. Various surfactants and amines may be added to improve the dispersibility of the particles. When the particle shape is a rod shape (refers to a shape having an aspect ratio of more than 1 and 10 or less), the minor axis is defined as the particle diameter.

The shape of the tin-containing indium oxide particles (A) is spherical, hollow, porous, rod-like (refers to a shape having an aspect ratio of more than 1 and not more than 10), plate-like, fibrous, or indefinite shape, preferably Is spherical.
The form of the tin-containing indium oxide particles (A) can be used in a state of being dispersed in a dry powder, water or an organic solvent. In particular, the use of a dispersion of tin-containing indium oxide particles is preferred in applications where the cured product requires excellent transparency.

  The amount (inclusive) of tin-containing indium oxide particles (component (A)) in the curable resin composition is within the range of 10 to 90% by mass, with the total amount of the composition excluding the organic solvent being 100% by mass. Is more preferable, and it is more preferable that it is the range of 20-80 mass%, and it is more preferable that it is the range of 30-70 mass%. If it is less than 10% by mass, the hardness of the cured film may be insufficient, or a layer having a high refractive index may not be obtained. If it exceeds 90% by mass, the film formability may be insufficient. The amount of tin-containing indium oxide particles (component (A)) means solid content, and when the tin-containing indium oxide particles (component (A)) are used in the form of a dispersion, Does not include the amount of dispersion medium.

(D) Ethylenically unsaturated group-containing fluoropolymer containing 40% by mass or more of fluorine The ethylenically unsaturated group-containing fluoropolymer used in the present invention is a hydroxyl group-containing fluoropolymer and a reaction with a hydroxyl group. It is obtained by reacting a compound containing a possible functional group and an ethylenically unsaturated group. Here, the compound containing a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated group is a compound containing one isocyanate group and at least one ethylenically unsaturated group, or an ethylenically unsaturated group. Examples thereof include saturated group-containing carboxylic acid compounds or derivatives thereof.
The fluorine-containing polymer containing an ethylenically unsaturated group used in the present invention usually has a fluorine content of 40% by mass or more, and preferably 45% by mass or more. When the fluorine content is 40% by mass or more, a cured film having a lower refractive index can be obtained. The fluorine content can be calculated from the composition obtained by analyzing the composition of the polymer by ¹³ C-NMR.

(1) Hydroxyl group-containing fluoropolymer The hydroxyl group-containing fluoropolymer comprises the following structural units (a) 5 to 90% by mass, (b) 0.3 to 90% by mass, and (c) 1 to 65% by mass. It is preferable that
(A) A structural unit represented by the following general formula (1).
(B) A structural unit represented by the following general formula (2).
(C) A structural unit represented by the following general formula (3).
By comprising in this way, the coating film excellent in low refractive index property, scratch resistance, coating property, and durability can be obtained.

[In General Formula (1), R ¹ represents a fluorine atom, a fluoroalkyl group, or a group represented by —OR ² (R ² represents an alkyl group or a fluoroalkyl group)]

[In General Formula (2), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, and a group represented by — (CH ₂ ) _x —OR ⁵ or —OCOR ⁵ (R ⁵ represents an alkyl group or a fluoro group) An alkyl group, x represents a number of 0 or 1), a carboxyl group, or an alkoxycarbonyl group]

[In General Formula (3), R ⁶ is a hydrogen atom or a methyl group, R ⁷ is a group represented by — (CH ₂ ) _v —OR ²⁷ or —OCOR ²⁷ (R ²⁷ is a hydrogen atom, a hydroxyalkyl group or A glycidyl group, v is a number from 0 to 2)]

(1) Structural unit (a)
In the general formula (1), examples of the fluoroalkyl group represented by R ¹ and R ² include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorocyclohexyl group. A C1-C6 fluoroalkyl group is mentioned. The alkyl group R ^2, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an alkyl group having 1 to 6 carbon atoms such as a cyclohexyl group.

The structural unit (a) can be introduced by using a fluorine-containing vinyl monomer as a polymerization component. Such a 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 fluororefines such as tetrafluoroethylene, hexafluoropropylene and 3,3,3-trifluoropropylene; alkyl perfluorovinyl ethers or alkoxyalkyl perfluorovinyl ethers; perfluoro (methyl vinyl ether), perfluoro Perfluoro (alkyl vinyl ethers) such as (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether); perfluoro (alkoxyalkyl vinyl ether) such as perfluoro (propoxypropyl vinyl ether) ) A single species or a combination of two or more species.
Among these, hexafluoropropylene and perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether) are more preferable.

In addition, it is preferable that the content rate of a structural unit (a) shall be 5-90 mass% when the whole quantity of a hydroxyl-containing fluoropolymer is 100 mass%. This is because when the content is less than 5% by mass, the fluorine content of the fluoropolymer is low, and it is difficult to develop a low refractive index, which is an optical characteristic of the fluorine-containing material intended by the present invention. On the other hand, if the content exceeds 90% by mass, the solubility of the hydroxyl group-containing fluoropolymer in organic solvent, transparency, or adhesion to the substrate may be reduced. Because.
For such reasons, the content of the structural unit (a) is more preferably 10 to 70% by mass, and preferably 15 to 60% by mass with respect to the total amount of the hydroxyl group-containing fluoropolymer. Is more preferable.

(2) Structural unit (b)
In the general 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 a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, and a lauryl group. Examples of the alkoxycarbonyl group ⁴ include a methoxycarbonyl group and an ethoxycarbonyl group. Examples of the fluoroalkyl group of R ⁵ include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorobutyl group, and a perfluorobutyl group. Fluorohexyl group, 2- (trifluoromethyl) ethyl group, 2- (perfluoroethyl) ethyl group, 2- (perfluoropropyl) ethyl group, 2- (perfluorobutyl) ethyl group, 2- (perfluoropentyl) ) Ethyl group, 2- (perfluorohexyl) ethyl group, 2- (perfluorooctyl) ethyl Group, 2- (perfluorononyl) ethyl group, 2- (perfluoro decyl) ethyl group, and the like.

  The structural unit (b) can be introduced by using the above-mentioned vinyl monomer having a substituent as a polymerization component. Examples of such vinyl monomers include 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-hexyl vinyl ether, n -Alkyl vinyl ethers such as octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether or cycloalkyl vinyl ethers; allyl ethers such as ethyl allyl ether, butyl allyl ether; vinyl acetate, vinyl propionate, vinyl butyrate, pivalin Carboxylic acid vinyl ester such as vinyl acid vinyl, vinyl caproate, vinyl vinyl versatate, vinyl stearate Tellurium; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- ( (Meth) acrylic acid esters such as n-propoxy) ethyl (meth) acrylate; unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid; and the following structural formula Things.

(In the formula, R ²⁸ represents a hydrogen atom or a methyl group, and w represents a number of 0 to 2.)
These can be used singly or in combination of two or more.

In addition, it is preferable that the content rate of a structural unit (b) shall be 0.3-90 mass% when the whole quantity of a hydroxyl-containing fluoropolymer is 100 mass%. The reason for this is that when the content is less than 0.3% by mass, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced. On the other hand, when the content exceeds 90% by mass. This is because optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluoropolymer may be deteriorated.
For these reasons, the content of the structural unit (b) is more preferably 0.4 to 70% by mass with respect to the total amount of the hydroxyl group-containing fluoropolymer, and 0.5 to 60 is preferable. It is more preferable to set it as the mass%.

(3) Structural unit (c)
In the general formula ^(3), the hydroxyalkyl group of ^{R 27,} 2-hydroxyethyl group, 2-hydroxypropyl, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 5-hydroxypentyl Group, 6-hydroxyhexyl group and the like.

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-hydroxypentyl vinyl ether, Examples include hydroxyl group-containing vinyl ethers such as 6-hydroxyhexyl vinyl ether, hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether, allyl alcohol, and the like.
Moreover, as a hydroxyl-containing vinyl monomer, in addition to the above, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone (meth) acrylate, polypropylene Glycol (meth) acrylate or the like can be used.
Moreover, in this invention, since a hydroxyl group is produced | generated by hydrolysis, it is considered that a glycidyl group also contains a hydroxyl group. As a monomer containing a glycidyl group, glycidyl (meth) acrylate can be used.

In addition, it is preferable that the content rate of a structural unit (c) shall be 1-65 mass% when the whole quantity of a hydroxyl-containing fluoropolymer is 100 mass%. The reason for this is that when the content is less than 1.0% by mass, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced. On the other hand, when the content exceeds 65% by mass. This is because optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluoropolymer may be deteriorated.
For such reasons, the content of the structural unit (c) is more preferably 1 to 45% by mass, and more preferably 1 to 30% by mass with respect to the total amount of the hydroxyl group-containing fluoropolymer. Is more preferable.

(4) Structural unit (d) and structural unit (e)
The hydroxyl group-containing fluoropolymer preferably contains 0.1 to 10% by mass of the following structural unit (d) derived from an azo group-containing polysiloxane compound.
(D) A structural unit represented by the following general formula (4).

[In General Formula (4), R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group, or an aryl group]
By including the structural unit (d), the scratch resistance is improved.

In the ethylenically unsaturated group-containing fluoropolymer of the present invention, the structural unit (d) is preferably included as a part of the following structural unit (e).
(E) A structural unit represented by the general formula (6).

[In General Formula (6), R ^{11 to} R ¹⁴ may be the same or different and each represents a hydrogen atom, an alkyl group, or a cyano group, and R ^{15 to} R ¹⁸ may be the same or different, A hydrogen atom or an alkyl group, a halogenated alkyl group, or an aryl group is shown, p and q are numbers 1 to 6, s and t are numbers 0 to 6, and y is a number 1 to 200. ]

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

In the general formula (4), the alkyl group of R ⁸ or R ^{9 is} an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, or a propyl group, and the halogenated alkyl group is a trifluoromethyl group, Examples of the fluoroalkyl group having 1 to 4 carbon atoms such as a fluoroethyl group, a perfluoropropyl group, and a perfluorobutyl group, and examples of the aryl group include a phenyl group, a benzyl group, and a naphthyl group.

  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). Examples of such azo group-containing polysiloxane compounds include compounds represented by the following general formula (7).

[In General Formula (7), R ^{11 to} R ¹⁴ , R ^{15 to} R ¹⁸ , p, q, s, t, and y are the same as those in General Formula (6), and z is a number from 1 to 20. It is. ]

When the compound represented by the general formula (7) is used, the structural unit (d) is included in the hydroxyl group-containing fluoropolymer as a part of the structural unit (e). In this case, in the general formula (7), examples of the alkyl group represented by R ^{11 to} R ¹⁴ include alkyl groups having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, and a cyclohexyl group. Examples of the alkyl group of ^{15 to} R ¹⁸ include an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group.

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

[In general formula (8), y and z are the same as the said general formula (7). ]

In addition, it is preferable that the content rate of a structural unit (d) shall be 0.1-10 mass% when the whole quantity of a hydroxyl-containing fluoropolymer is 100 mass%. The reason for this is that when the content is less than 0.1% by mass, the surface slipperiness of the cured coating film is lowered, and the scratch resistance of the coating film may be lowered. If it exceeds 10% by mass, the transparency of the hydroxyl group-containing fluorine-containing polymer is inferior, and when used as a coating material, repelling and the like are likely to occur during coating.
For these reasons, the content of the structural unit (d) is more preferably 0.1 to 5% by mass with respect to the total amount of the hydroxyl group-containing fluoropolymer, It is more preferable to set it as the mass%. For the same reason, the content of the structural unit (e) is desirably determined so that the content of the structural unit (d) contained therein is in the above range.

(5) Structural unit (f)
Furthermore, the said hydroxyl-containing fluoropolymer may also contain 0.1-30 mass% of the following structural units (f) when the whole quantity of a hydroxyl-containing fluoropolymer is 100 mass%.
(F) A structural unit represented by the following general formula (5).

[In general formula (5), R ¹⁰ represents a group having an emulsifying action]

By including the structural unit (f), the coating property is improved.
However, when the (B) ethylenically unsaturated group-containing fluoropolymer contains the structural unit (f), the coating layer formed by coating the curable resin composition of the present invention on a substrate or the like is (A Uncertain characteristics (layer separability) of separation into one or more layers in which tin-containing indium oxide particles are present at high density and (A) one or less layers in which tin-containing indium oxide particles are substantially absent. Therefore, the introduction of the structural unit (f) is not preferable when reliable layer separation is expected.

Hereinafter, the structural unit (f) will be described.
In the general formula (5), the group having an emulsifying action of R ¹⁰ has both a hydrophobic group and a hydrophilic group, and the hydrophilic group has a polyether structure such as polyethylene oxide and polypropylene oxide. Is preferred.

  Examples of the group having such an emulsifying action include a group represented by the following general formula (9).

[In General Formula (9), n is a number from 1 to 20, m is a number from 0 to 4, and u is 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 general formula (10), n, m, and u are the same as those in general formula (9) above]

In addition, it is preferable that the content rate of a structural unit (f) shall be 0.1-30 mass% when the whole quantity of a hydroxyl-containing fluoropolymer is 100 mass%. The reason is that when the content is 0.1% by mass or more, the solubility of the hydroxyl group-containing fluoropolymer in the solvent is improved. On the other hand, if the content is within 30% by mass, the curable resin composition This is because the adhesiveness of the film does not increase excessively, handling becomes easy, and moisture resistance does not decrease even when used as a coating material.
For such reasons, the content of the structural unit (f) is more preferably 0.1 to 25% by mass, and 1 to 20% by mass with respect to the total amount of the hydroxyl group-containing fluoropolymer. More preferably.

(6) Molecular Weight The hydroxyl group-containing fluoropolymer has a polystyrene-reduced number average molecular weight of 5,000 as measured by gel permeation chromatography (hereinafter referred to as “GPC”) using tetrahydrofuran (hereinafter referred to as “THF”) as a solvent. It is preferably ~ 500,000. The reason for this is that when the number average molecular weight is less than 5,000, the mechanical strength of the hydroxyl group-containing fluoropolymer may be lowered. On the other hand, when the number average molecular weight exceeds 500,000, it will be described later. This is because the viscosity of the curable resin composition becomes high and thin film coating may be difficult.
For these reasons, the number average molecular weight in terms of polystyrene of the hydroxyl group-containing fluoropolymer is more preferably 10,000 to 300,000, and even more preferably 10,000 to 100,000.

(2) Compound containing one isocyanate group and at least one ethylenically unsaturated group As a compound containing one isocyanate group and at least one ethylenically unsaturated group, The compound is not particularly limited as long as it is a compound containing one isocyanate group and at least one ethylenically unsaturated group.
In addition, when two or more isocyanate groups are contained, there is a possibility of causing gelation when reacting with a hydroxyl group-containing fluoropolymer.
Moreover, since the curable resin composition mentioned later can be hardened more easily as said ethylenically unsaturated group, the compound which has a (meth) acryloyl group is more preferable.
As such a compound, 2- (meth) acryloyloxyethyl isocyanate and 2- (meth) acryloyloxypropyl isocyanate may be used singly or in combination of two or more.

Such a compound can also be synthesized by reacting diisocyanate and a hydroxyl group-containing (meth) acrylate.
In this case, examples of diisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate. -To, 1,5-naphthalenediisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane di- Isocyanate, 3,3′-dimethylphenylene diisocyanate, 4,4′-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate) 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanatoethyl) Fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-bis (isocyanate) Methyl) cyclohexane, tetramethylxylylene diisocyanate, 2,5 (or 2,6) -bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, or a combination of two or more. It is done.
Among these, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylenebis (4-cyclohexylisocyanate), and 1,3-bis (isocyanatomethyl) cyclohexane are particularly preferable.

Examples of hydroxyl group-containing (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone (meth) acrylate, polypropylene glycol (meta ) Acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, isocyanuric acid EO-modified di (meth) acrylate, or a combination of two or more Can be mentioned.
Among these, 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are particularly preferable.
In addition, as a commercial item of a hydroxyl-containing polyfunctional (meth) acrylate, for example, Osaka Organic Chemical Co., Ltd. product name HEA, Nippon Kayaku Co., Ltd. product name KAYARAD DPHA, PET-30, Toagosei Co., Ltd. Product name Aronix M-215, M-233, M-305, M-400 and the like can be obtained.

  When synthesizing from diisocyanate and a hydroxyl group-containing polyfunctional (meth) acrylate, the amount of the hydroxyl group-containing polyfunctional (meth) acrylate added is preferably 1 to 1.2 mol with respect to 1 mol of diisocyanate.

  Examples of the method for synthesizing such a compound include a method in which diisocyanate and a hydroxyl group-containing (meth) acrylate are collectively charged and reacted, a method in which diisocyanate is dropped into a hydroxyl group-containing (meth) acrylate, and a reaction method.

(3) Ethylenically unsaturated group-containing carboxylic acid compound or derivative thereof As the ethylenically unsaturated group-containing carboxylic acid compound or derivative thereof, a compound having an ethylenically unsaturated group and carboxylic acid in the molecule, or an acid halide thereof, The compound is not particularly limited as long as it is a compound that forms an ester with a hydroxyl group-containing fluoropolymer, such as an acid anhydride.
Moreover, since the curable resin composition can be more easily cured as the ethylenically unsaturated group, a compound having a (meth) acryloyl group is more preferable.
Examples of such a compound include (meth) acrylic acid, (meth) acrylic acid chloride, (meth) acrylic acid bromide, and anhydrous (meth) acrylic acid.

(4) Reaction molar ratio The ethylenically unsaturated group-containing fluorine-containing polymer of the present invention includes the above-described compound containing one isocyanate group and at least one ethylenically unsaturated group, and a hydroxyl group-containing fluorine-containing polymer. It is preferable that the polymer is reacted at a molar ratio of isocyanate group / hydroxyl group of 0.1 to 1.9. The reason for this is that if the molar ratio is less than 0.1, the scratch resistance and durability may be reduced. On the other hand, if the molar ratio exceeds 1.9, the coating film of the curable resin composition may be deteriorated. This is because the scratch resistance after immersion in an alkaline aqueous solution may be lowered.
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 and the hydroxyl group-containing fluorine-containing polymer are mixed with an ethylenically unsaturated group-containing carboxylic acid compound or derivative thereof / hydroxyl molar ratio of 0.1 to 0.1. It is preferable to make it react in the ratio of 1.9. However, when the carboxylic acid derivative is an acid anhydride, one molecule can react with two hydroxyl groups, so the molar ratio of acid anhydride / hydroxyl group of the ethylenically unsaturated group-containing carboxylic acid compound is A ratio of 0.05 to 0.95 is preferable.

The addition amount of the ethylenically unsaturated group-containing fluoropolymer (B) in the curable resin composition of the present invention is not particularly limited, but is usually 1 with respect to the total amount of the composition other than the organic solvent. -80 mass%. The reason for this is that when the addition amount is less than 1% by mass, the refractive index of the cured coating film of the curable resin composition increases, and a sufficient antireflection effect may not be obtained. This is because if the amount exceeds 80% by mass, the scratch resistance of the cured coating film of the curable resin composition may not be obtained.
For this reason, the amount of component (E) added is more preferably 2 to 70% by mass, and even more preferably 3 to 60% by mass.

(C) (B) Solvent having high solubility of ethylenically unsaturated group-containing fluoropolymer (fast volatile solvent)
The (C) fast volatile solvent contained in the curable resin composition of the present invention is a solvent in which the (B) ethylenically unsaturated group-containing fluoropolymer is highly soluble. Here, that the solubility of the ethylenically unsaturated group-containing fluoropolymer is high means that (B) the ethylenically unsaturated group-containing fluoropolymer is added to each solvent so that the amount becomes 50% by mass. When stirring for a time, it means that the solution becomes visually uniform. The low solubility means that the solution is not visually uniform at this time. The relative evaporation rate of the (C) fast volatile solvent needs to be larger than the relative evaporation rate of the later-described (D) slow volatile solvent. Here, “relative evaporation rate” refers to the relative value of the evaporation rate based on the time required for 90% by mass of butyl acetate to evaporate. For details, see TECHNIQUES OF CHEMISTRY VOL. 2 ORGANIC SOLVENTS Physical Properties and methods of purification 4th ed. (Interscience Publishers, Inc. 1986 page 62). The (C) fast volatile solvent preferably has low dispersion stability with respect to the (A) tin-containing indium oxide particles (particles of the component (A)). (C) The fast volatile solvent has a relative evaporation rate larger than (D), and (B) a high solubility in the ethylenically unsaturated group-containing fluoropolymer, the curable resin composition of the present invention, In the process of applying to the substrate and evaporating the solvents (C) and (D), the particles of the component (A) can be unevenly distributed.

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

(D) (A) Solvent having a high dispersion stability of tin-containing indium oxide particles and compatible with the solvent (C) (slow volatile solvent)
The (D) slow volatile solvent contained in the curable resin composition of the present invention is a solvent having high dispersion stability of the (A) tin-containing indium oxide particles (particles of the component (A)). Here, the dispersion stability of the particles of the component (A) is high when the glass plate is immersed in an isopropanol dispersion of the particles of the component (A), and the particles of the component (A) are adhered to the glass wall. When the glass plate to which the particles of the component A) are adhered is immersed in each solvent, the particles of the component (A) are uniformly dispersed visually in the solvent. Low dispersion stability means that it is not uniformly dispersed visually. Moreover, it is preferable that (D) slow volatile solvent has low solubility of the said (B) ethylenically unsaturated group containing fluoropolymer.

  As the solvent that can be used as the (D) slow volatile solvent in the present invention, methanol (relative evaporation rate 2.1), isopropanol (IPA; 1.7), n-butanol (n-BuOH; 0.5), Examples thereof include 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. In view of improving optical properties (haze, reflectance) and surface resistance of the resulting cured film, it is preferable that (D) the slow volatile solvent contains propylene glycol monomethyl ether (PGME).

As the (C) fast volatile solvent and / or (D) slow volatile solvent used in the present invention, the solvent used for the production of the (B) ethylenically unsaturated group-containing fluoropolymer can be used as it is.
The (C) fast volatile solvent and (D) slow volatile solvent used in the present invention must be compatible. The compatibility is sufficient if the specific composition of the composition of the present invention has such compatibility that (C) the fast volatile solvent and (D) the slow volatile solvent are not separated.
Here, whether the selected solvent corresponds to (C) fast volatile solvent or (D) slow volatile solvent used in the present invention is relatively determined among a plurality of selected solvent types. Therefore, isopropanol having a relative evaporation rate of 1.7 may be used as (C) a fast volatile solvent or (D) a slow volatile solvent.

  The total amount of the solvent (C) and the solvent (D) is usually 300 to 5000 parts by mass, preferably 300 to 100 parts by mass with respect to 100 parts by mass of the components other than the solvent (C) and (D) in the curable resin composition. 4000 parts by mass, more preferably 300 to 3000 parts by mass is used. The mixing ratio of the solvent (C) and the solvent (D) can be arbitrarily selected in the range of 1:99 to 99: 1.

(E) a polyfunctional (meth) acrylate compound containing at least two (meth) acryloyl groups and / or a fluorine-containing (meth) acrylate compound containing at least one (meth) acryloyl group And may be collectively referred to as “curable compounds”)
The polyfunctional (meth) acrylate compound (E-1) containing at least two or more (meth) acryloyl groups is a cured product obtained by curing a curable resin composition, and an antireflection film using the cured product. Used to increase scratch resistance.
The fluorine-containing (meth) acrylate compound (E-2) containing at least one (meth) acryloyl group is used to lower the refractive index of the curable resin composition.

  The compound (E-1) is not particularly limited as long as it is a compound containing at least two (meth) acryloyl groups in the molecule. Examples of such include neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone Modified dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, “U-15HA” Trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.), "HDP-M20" and the like are alone or in a combination of two or more of such (trade name, Negami Chemical Industrial Co., Ltd.). Of 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”, “HDP-M20” (trade name, manufactured by Negami Industrial Co., Ltd.) is particularly preferable.

  The compound (E-2) is not particularly limited as long as it is a fluorine-containing (meth) acrylate compound containing at least one (meth) acryloyl group. As such an example, one kind of perfluorooctylethyl (meth) acrylate, octafluoropentyl (meth) acrylate, trifluoroethyl (meth) acrylate, or a combination of two or more kinds can be given.

  The content of the component (E) in the curable resin composition of the present invention is not particularly limited, but is usually 5 to 80% by mass with respect to 100% by mass of the total composition excluding the organic solvent. is there. The reason for this is that when the addition amount is less than 5% by mass, the scratch resistance of the cured coating film of the curable resin composition may not be obtained. On the other hand, when the addition amount exceeds 80% by mass, This is because the refractive index of the cured coating film of the curable resin composition becomes high and a sufficient antireflection effect may not be obtained. For these reasons, the amount of component (E) added is more preferably 5 to 70% by mass, and even more preferably 5 to 50% by mass.

(F) Photoradical polymerization initiator In the curable resin composition of the present invention, if necessary, active radical species are generated by radiation (light) irradiation. (F) Photoradical polymerization initiator (radiation (photo) polymerization. Initiator) can be blended.

  The radiation (photo) polymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2 , 2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy Roxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2 , 4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine 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, for example, Ciba Specialty Chemicals Co., Ltd. trade name: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG24-61, Darocur 1116, 1173, manufactured by BASF, Inc. Product name: Lucillin TPO, manufactured by UCB, Inc. Product name: Uvekril P36, manufactured by Fratteri Lamberti, Inc. Product names: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B and the like.

  The blending amount of the radical photopolymerization initiator (F) used as necessary in the present invention is preferably 0.01 to 10% by mass, based on 100% by mass of the total composition excluding the organic solvent. 1-10 mass% is further more preferable. If it is less than 0.01% by mass, the hardness when it is a cured product may be insufficient. If it exceeds 10% by mass, it may not be cured to the inside (lower layer) when it is a cured product.

(G) Other components In the curable composition of the present invention, as long as the effects of the present invention are not impaired, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, and wettability improvement are performed as necessary. An agent, a surfactant, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, an inorganic filler, a pigment, a dye, a solvent other than the solvents (C) and (D), and the like can be appropriately blended.

2. Manufacturing method of curable resin composition The composition of this invention can be manufactured as follows.
Tin-containing indium oxide particle dispersion (component (A)), ethylenically unsaturated group-containing fluoropolymer (component (B)), solvent having high solubility of ethylenically unsaturated group-containing fluoropolymer ((C) solvent ) And a solvent having high dispersion stability of tin-containing indium oxide particles and being compatible with the solvent (C) (solvent (D)), and if necessary, a polyfunctional (meth) acrylate (component (E) ), Radiation (photo) polymerization initiator (component (F)) and the like are placed in a reaction vessel equipped with a stirrer and stirred at 35 ° C. to 45 ° C. for 2 hours to obtain the curable resin composition of the present invention.
When replacing the solvent with a different type of solvent (β) from the solvent (α) used in the initial particle dispersion, the solvent (β) is 1.0 times the mass of the solvent (α) in the particle dispersion. And stirring under the same conditions. Next, this composition solution is concentrated under reduced pressure to a mass that gives a solid concentration of 50% using a rotary evaporator to obtain the composition of the present invention.

3. Method for Applying (Coating) Curable Resin Composition The curable resin composition of the present invention is suitable for use as an antireflection film or a coating material. As a base material to be subjected to antireflection or coating, for example, plastic ( Polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass, slate, and the like. The shape of these substrates may be a plate, film or three-dimensional molded body, and the coating method is a normal coating method such as dipping coating, spray coating, flow coating, shower coating, roll coating, spin coating, brush coating, etc. Can be mentioned. The thickness of the coating film by these coatings is usually 0.1 to 400 μm after drying and curing, and preferably 1 to 200 μm.

4). Curing method of curable resin composition The curable resin composition of the present invention can be cured by radiation (light). The radiation source is not particularly limited as long as the composition can be cured in a short time after coating. For example, as an infrared radiation source, a lamp, a resistance heating plate, a laser, or the like, or visible light is used. As a radiation source, sunlight, a lamp, a fluorescent lamp, a laser, etc. are generated from a commercially available tungsten filament as an ultraviolet ray source, a mercury lamp, a halide lamp, a laser, etc., and as an electron beam source. Examples include a method using thermal electrons, a cold cathode method in which a metal is generated through a high voltage pulse, and a secondary electron method in which secondary electrons generated by collision between ionized gaseous molecules and a metal electrode are used. Examples of the source of alpha rays, beta rays, and gamma rays include fission materials such as ⁶⁰ Co. For gamma rays, a vacuum tube that collides accelerated electrons with the anode can be used. These radiations can be irradiated alone or in combination of two or more at a certain time.

When an active energy ray is used, the exposure dose is preferably set to a value within the range of 0.01 to 10 J / cm ² . The reason for this is that when the exposure amount is less than 0.01 J / cm ² , curing failure may occur. On the other hand, when the exposure amount exceeds 10 J / cm ² , the curing time may become excessively long. Because there is. For this reason, the exposure dose is more preferably set to a value in the range of 0.1 to 5 J / cm ² , and more preferably set to a value in the range of 0.3 to 3 J / cm ^2. .

  The curing reaction of the curable resin composition of the present invention needs to be performed under anaerobic conditions such as nitrogen. The reason is that radical polymerization is inhibited by oxygen, resulting in insufficient curing reaction.

II. Cured film The cured film of the present invention is obtained by curing the curable resin composition of the present invention, and has a multilayer structure of two or more layers. In particular, the (A) tin-containing indium oxide particles (particles of the component (A)) are one or more layers present at a high density, and one or less layers are substantially free of the particles of the component (A). It preferably has a layer structure of two or more layers.

The cured film of the present invention can be obtained by coating the curable resin composition on various substrates, for example, a plastic substrate and curing it. Specifically, after coating the composition and preferably drying the volatile component at 0 to 200 ° C., it can be obtained as a coated molded body by performing the above-described curing treatment with radiation. In such a case, the preferable irradiation amount of ultraviolet rays is 0.01 to 10 J / cm ² , more preferably 0.1 to ² J / cm ² . Moreover, as for the irradiation conditions of a preferable electron beam, a pressurization voltage is 10-300 KV, an electron density is 0.02-0.30 mA / cm < ² >, and an electron beam irradiation amount is 1-10 Mrad.

  In the process where the solvent (C) and the solvent (D) in the composition are evaporated and dried after coating the curable resin composition, the particles of the component (A) are coated on the coating base side (near the boundary with the adjacent layer) or It is unevenly distributed on the opposite side. Therefore, the particles of the component (A) are present in high density near one interface of the cured film, and the particles of the component (A) are substantially absent near the other interface of the cured film. The resin layer is formed. Therefore, a cured film having a layer structure of two or more layers can be obtained by curing one coating film made of the curable resin composition. Each layer formed by separation can be confirmed, for example, by observing a cross section of the obtained film with an electron microscope. 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 substantially composed of the particles of the component (A) as a main component. Although it is a layer, the component (B) may coexist in the layer. On the other hand, the layer in which the particles of the component (A) are substantially absent is a concept indicating a portion where the particles of the component (A) are not present, but the particles of the component (A) are within the range not impairing the effects of the present invention. May be included slightly. This layer is a layer substantially composed of components other than the particles of component (A) such as a cured product of component (B) and component (E). In many cases, the cured film of the present invention has a two-layer structure in which a layer in which particles of the component (A) are present in high density and a layer in which the particles of the component (A) are substantially absent are formed in succession. Have. When a polyethylene terephthalate (PET) resin (including a PET resin having an easy-adhesion layer) or the like is used for the base material, usually, a layer that is a base material, a layer in which particles of the component (A) are present at a high density, A layer substantially free of component particles is formed adjacent in this order.

  Here, the layer structure of two or more layers includes both “a layer in which (A) component particles are present in high density” and “a layer in which (A) component particles are substantially absent”. It may be composed of the above layers, or may be composed of only two or more “layers in which tin-containing indium oxide particles are present at high density”.

  The (B) ethylenically unsaturated group-containing fluoropolymer in the curable resin composition of the present invention has a refractive index lower than that of a thermosetting resin (for example, a melamine compound), and the low refractive index of the antireflection film. The layer has preferable optical properties. And (A) Antireflection which has the further excellent optical characteristic and antistatic property by using the IPA dispersion liquid of the tin containing indium oxide particle which is highly transparent and excellent in electroconductivity as a tin containing indium oxide particle A film can be formed.

  The cured film of the present invention is characterized by high hardness and capable of forming a coating film (film) excellent in scratch resistance and adhesion to the base material and adjacent layers such as the base material and the low refractive index layer. is doing. Moreover, since heat is not used for the curing reaction, it does not involve a hydrolysis reaction caused by the thermosetting reaction, and thus the obtained cured film has excellent heat and moisture resistance. Therefore, the cured film of the present invention is particularly suitably used for an antireflection film for film type liquid crystal elements, touch panels, plastic optical components and the like.

The degree of change in refractive index depends on the content of (A) component, (B) the content and composition of the ethylenically unsaturated group-containing fluoropolymer, and the content and type of (E) component (curable compound). Etc. can be adjusted.
Moreover, 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 a high refractive index part is 1.50-2.20.

III. Laminate A laminate can be obtained by using a cured film having a layer structure of two or more layers obtained from the curable resin composition of the present invention as a part of the laminate structure. Any two or more adjacent layers other than the base material layer constituting the laminate can be produced as a cured film of the curable resin composition of the present invention.
For example, when the substrate is a transparent substrate, the laminate is an excellent antireflection film by providing a low refractive index layer on the outermost layer (the layer farthest from the substrate). In addition to the antireflection film, the laminate can be used for optical parts such as a lens and a selective transmission film filter.
The specific layer configuration of the antireflection film is not particularly limited. Usually, at least a high refractive index film and a low refractive index film are laminated in this order on a base material so as to have an antireflection function. In addition to this, a hard coat layer, an antistatic layer, and the like can be included in a part of the layer structure of the laminate. Since the cured film obtained by curing the curable resin composition of the present invention can form a high refractive index layer and a low refractive index layer on a substrate in one step, the manufacturing process can be simplified. it can.

  The cured film of the present invention usually comprises two layers of a high refractive index layer and a low refractive index layer, and by forming this on a substrate, a laminate suitable as an antireflection film can be formed. An antireflection film as a typical example of such a laminate is shown in FIG. The high refractive index layer 14 and the low refractive index layer 16 are formed by providing the hard coat layer 12 on the substrate 10 and applying and curing the curable resin composition of the present invention thereon.

  The antireflection film may further include layers other than these. For example, a plurality of combinations of a high refractive index film and a low refractive index film are provided to provide a relatively uniform reflectance with respect to light in a wide wavelength range. A so-called wideband antireflection film having characteristics may be used, and an antistatic layer may be provided.

  Although there is no restriction | limiting in particular as a base material, When using as an antireflection film, for example, the above-mentioned plastics (PET, polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose (TAC) ) Resin, ABS resin, AS resin, norbornene resin, and the like.

  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), haze, and high hardness.

  Since the laminate is excellent in scratch resistance and haze and is excellent in moisture and heat resistance, it is particularly suitably used as an antireflection film for film-type liquid crystal elements, touch panels, plastic optical components and the like.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated further in detail, the scope of the present invention is not limited to description of these Examples. In the examples, unless otherwise specified, the amount of each component means “parts” by mass and “%” means mass%.

Production Example 1: Production of hydroxyl group-containing fluoropolymer (b-1) A stainless steel autoclave with an internal volume of 1.5 L equipped with a magnetic stirrer was sufficiently replaced with nitrogen gas, and then 800 g of ethyl acetate, 1-vinyloxy-3, 3, 4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecane 165.5 g, ethyl vinyl ether 16.2 g, hydroxyethyl vinyl ether 49.5 g Then, 12.0 g of “VPS-1001” (manufactured by Wako Pure Chemical Industries, Ltd.) and 2.0 g of lauroyl peroxide were added as azo group-containing polydimethylsiloxane, cooled to −50 ° C. with dry ice-methanol, and then again nitrogen. The oxygen in the system was removed with gas.
Next, 202.6 g of hexafluoropropylene was added, and the temperature increase was started. The reaction was continued under stirring at 70 ° C., and after 20 hours, the reaction was stopped by cooling with water. After reaching room temperature, the unreacted monomer was released and the autoclave was opened to obtain a polymer solution having a solid content concentration of 22%. The obtained polymer solution was poured into methanol to precipitate a polymer, which was then washed with methanol and vacuum dried at 50 ° C. to obtain 264 g of a fluoropolymer (b-1).

Production Example 2 Production of Ethylenically Unsaturated Group-Containing Fluoropolymer (F Polymer 1) A 1-liter separable flask equipped with a magnetic stirrer, a glass condenser and a thermometer was obtained in Production Example 1. 63.00 g of the hydroxyl group-containing fluoropolymer (b-1), 0.01 g of 2,6-di-tert-butylmethylphenol and 442 g of MIBK as a polymerization inhibitor were charged, and the hydroxyl group-containing fluoropolymer (b -1) was dissolved in MIBK and stirred until the solution became clear and uniform. Then, 15.01 g of 2-acryloyloxyethyl isocyanate was added to this system and stirred until the solution became homogeneous, then 0.16 g of dibutyltin dilaurate was added to start the reaction, and the temperature of the system was changed to 55 to 55. The MIBK solution of the ethylenically unsaturated group-containing fluoropolymer (F polymer 1) was obtained by maintaining at 65 ° C. and continuing stirring for 5 hours. 2 g of this solution was weighed in an aluminum dish, dried on a hot plate at 150 ° C. for 5 minutes, and weighed to determine the solid content, which was 15%.
The obtained F polymer 1 had a polystyrene-reduced number average molecular weight of 29,600 by gel permeation chromatography and a fluorine content of 49% by mass.

Production Example 3 Production of Hydroxyl Group-Containing Fluoropolymer (b-2) A stainless steel autoclave with an internal volume of 1.5 L with a magnetic stirrer was sufficiently substituted with nitrogen gas, and then 500 g of ethyl acetate and perfluoro (propyl vinyl ether) 43. 2 g, 41.2 g of ethyl vinyl ether, 21.5 g of hydroxyethyl vinyl ether, 40.5 g of “ADEKA rear soap NE-30” (manufactured by Asahi Denka Kogyo Co., Ltd.) as a nonionic reactive emulsifier, and “VPS as an azo group-containing polydimethylsiloxane” −1001 ”(manufactured by Wako Pure Chemical Industries, Ltd.) and 1.25 g of lauroyl peroxide were added, and after cooling to −50 ° C. with dry ice-methanol, oxygen in the system was removed again with nitrogen gas.
Next, 97.4 g of hexafluoropropylene was added, and the temperature increase was started. The pressure when the temperature in the autoclave reached 60 ° C. was 5.3 × 10 ⁵ Pa. Thereafter, the reaction was continued with stirring at 70 ° C. for 20 hours. When the pressure dropped to 1.7 × 10 ⁵ Pa, the autoclave was cooled with water to stop the reaction. After reaching room temperature, unreacted monomers were released and the autoclave was opened to obtain a polymer solution having a solid content concentration of 26.4%. The obtained polymer solution was poured into methanol to precipitate a polymer, which was then washed with methanol and vacuum dried at 50 ° C. to obtain 220 g of a hydroxyl group-containing fluoropolymer (b-2).

Production Example 4: Production of Ethylenically Unsaturated Group-Containing Fluoropolymer (F Polymer 2) Obtained in Production Example 3 into a 1-liter separable flask equipped with a magnetic stirrer, a glass cooling tube and a thermometer. 50.0 g of the hydroxyl group-containing fluoropolymer (b-2), 0.01 g of 2,6-di-t-butylmethylphenol and 374 g of MIBK as a polymerization inhibitor were charged, and the hydroxyl group-containing fluoropolymer (b -2) was dissolved in MIBK and stirred until the solution became clear and uniform. Next, 16.0 g of 2-acryloyloxyethyl isocyanate was added to this system and stirred until the solution became homogeneous, then 0.1 g of dibutyltin dilaurate was added to start the reaction, and the temperature of the system was changed to 55 to 55. The MIBK solution of the ethylenically unsaturated group-containing fluoropolymer (F polymer 2) was obtained by maintaining the temperature at 65 ° C. and continuing stirring for 5 hours. 2 g of this solution was weighed in an aluminum dish, dried on a hot plate at 150 ° C. for 5 minutes, and weighed to determine the solid content, which was 15.0%.
The obtained F polymer 2 had a polystyrene-reduced number average molecular weight of 43,000 by gel permeation chromatography and a fluorine content of 35% by mass.

Example 1
Preparation of curable resin composition 1 260 g of ITO particle sol (NID-20, Fuji Chemical ITO dispersion (isopropyl alcohol (IPA) solution, 52.0 g as particles)), ethylenic unsaturation obtained in Production Example 2 215.5 g of a group-containing fluoropolymer (F polymer 1) (32.3 g as an ethylenically unsaturated group-containing fluoropolymer), 17.1 g of dipentaerythritol pentaacrylate (SR-399E, Nippon Kayaku Co., Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone (Irgacure 369, manufactured by Ciba Specialty Chemicals, photo radical polymerization initiator) 2.56 g, methyl ethyl ketone 206 g, methyl isobutyl ketone 186 g, isopropanol 23 g, normal butanol 45 g, methylamino Luketone 45g was added and stirred. The solid content concentration of the obtained curable resin composition was 10.4%. The blended solvent ratio is shown in Table 1.
Three curable resin composition samples were prepared using three types of ITO dispersions in different lots.

Examples 2 to 4 and Comparative Examples 1 and 2
Preparation of Curable Resin Compositions 2-6 Curable resin compositions 2-6 were obtained in the same manner as in Example 1 except that each solid component was blended in the ratio shown in Table 1. At this time, the solvent was blended so as to have the same solvent ratio as in Table 1 as in Example 1. Moreover, also about the curable resin compositions 2-6, each 3 types of curable resin composition samples were produced using three types of ITO dispersion liquids from different lots.

In addition, using the curable resin compositions 1 to 6 manufactured in Examples 1 to 4 and Comparative Examples 1 and 2 (each using three types of samples), three cured film samples were produced, and cured films were obtained. The characteristics were 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-hydroxycyclohexyl phenyl ketone 2.1 g, IRGACURE 907 (2-methyl -1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (produced by Ciba Specialty Chemicals) 1.2 g, dipentaerythritol hexaacrylate (DPHA) 33.2 g, and cyclohexanone 7 g were mixed and stirred. A composition for a hard coat layer containing silica particles was obtained. The silica particle-containing hard coat layer composition was applied to a triacetyl cellulose film (manufactured by Fuji Photo Film Co., Ltd., film thickness 80 μm) using a wire bar coater (# 12), and then in an oven at 80 ° C. For 2 minutes. 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 in the 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, using a wire bar coater (# 3), the curable resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were applied, and then in an oven. Dry at 80 ° C. for 2 minutes. Subsequently, a cured film layer having a thickness of 0.2 μm was formed by irradiating ultraviolet rays under a light irradiation condition of 0.9 J / cm ² using a high-pressure mercury lamp in a nitrogen atmosphere.

<Evaluation of cured film>
(1) Layer separation property The cross section of the obtained cured film was observed with a microscope, and it was evaluated whether or not it was separated into two layers. The evaluation criteria are as follows. A typical example of the following evaluation criteria is shown in FIG.
○: separated into two layers (the cured film is a layer in which the ITO particles on the substrate side are present at high density (high refractive index layer) and a layer in which the ITO particles on the air side are not substantially present (low refraction) Rate layer)).
(Triangle | delta): Although two-layer separation is carried out, since the separation interface is not smooth, the part which does not carry out two-layer separation locally has arisen.
X: Not separated into two layers.
In addition, the layer separation property of the composition of the comparative example, depending on the lot of the ITO particle dispersion used, there are those that separate layers and those that do not separate layers, and stable results cannot be obtained. ”And“ Δ˜ × ”.

(2) Haze The turbidity (Haze value) in the obtained laminate was measured using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.) according to JIS K7105.

(3) Surface resistance (Ω / □)
The surface resistance (Ω / □) of the obtained cured film was measured using a high resistance meter (HP4330, manufactured by Hewlett-Packard Company) at a main electrode diameter of 26 mmΦ and an applied voltage of 100V.

(4) Reflectance The reflectance of the obtained anti-reflection laminate was measured using a spectral reflectance measuring device (a self-recording spectrophotometer U-3410 incorporating a large sample chamber integrating sphere attachment device 150-09090, Hitachi, Ltd.). The reflectance was measured and evaluated in the wavelength range of 340 to 700 nm. Specifically, the reflectance of the antireflection laminate (antireflection film) at each wavelength is measured using the reflectance of the aluminum deposited film as a reference (100%), and the reflectance of light at a wavelength of 550 nm is obtained. It was.

(5) Steel wool resistance The steel wool resistance test of the cured film was carried out by the following method. That is, steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) was attached to a Gakushin friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film was loaded with 1000 g. Under the above conditions, rubbing was repeated 10 times, and the presence or absence of scratches on the surface of the cured film was visually confirmed according to the following criteria.
◯: Almost no peeling or scratching of the cured film is observed.
(Triangle | delta): A thin crack is recognized by the cured film.
X: Peeling occurred in a part of the cured film, or streak scratches occurred on the surface of the cured film.

Abbreviations and the like in Table 1 indicate the following.
NID-20: Fuji Chemical ITO dispersion (IPA: 20 mass% dispersion)
JX-1002ITV: ITO dispersion manufactured by Catalyst Kasei Kogyo (IPA: 20% by mass dispersion)
SR-399E: Dipentaerythritol pentaacrylate; Nippon Kayaku NK Oligo U-6HA: Hexafunctional urethane acrylate; Shin Nakamura Chemical Industry NK Oligo U-15HA: 15 functional urethane acrylate; -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone; manufactured by Ciba Specialty Chemicals MEK: methyl ethyl ketone MIBK: methyl isobutyl ketone IPA: isopropanol MAK: methyl amyl ketone n-BuOH: n- Butanol PGME: Propylene glycol monomethyl ether

  From the results of Table 1, it can be seen that in the examples using the fluorine-containing polymer containing an ethylenically unsaturated group having a high fluorine content, the layer separation is good, the reflectance is low, and the scratch resistance is excellent. .

The curable resin composition of the present invention can form a cured film having a multilayer structure of two or more layers on a substrate from one coating film.
The curable resin composition of the present invention and the cured product thereof are scratched (scratched) such as plastic optical parts, touch panels, film-type liquid crystal elements, plastic containers, floor materials as building interior materials, wall materials, artificial marble, etc. Protective coating materials for prevention and contamination prevention; antireflection films for film-type liquid crystal elements, touch panels, plastic optical components, etc .; adhesives and sealing materials for various substrates; binder materials for printing inks, especially as antireflection films It can be used suitably.

It is a figure which shows the typical example of the anti-reflective film containing the cured film formed from the curable resin composition of this invention. It is an electron microscope image which shows the typical example of the evaluation criteria of layer separation. It is an electron microscope image which shows the typical example (cured film of Example 4) of the cured film cross section of this invention which is carrying out 2 layer separation.

Explanation of symbols

1: Antireflection film laminate 10: Base material 12: Hard coat layer 14: High refractive index layer 16: Low refractive index layer

Claims (11)

The following ingredients:
(A) Tin-containing indium oxide particles (B) Ethylenically unsaturated group-containing fluorine-containing polymer containing 40% by mass or more of fluorine (C) 1 selected from methyl ethyl ketone, isopropanol, methyl isobutyl ketone, acetone and methyl propyl ketone The above fast volatile solvents (D) From methanol, n-butanol , tert-butanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethyl cellosolve, propyl cellosolve, butyl cellosolve and propylene glycol monoethyl ether acetate Including a selected slow volatile solvent , and the relative evaporation rate of the solvent of (C) is greater than the relative evaporation rate of the solvent of (D),
The content of the (A) tin-containing indium oxide particles is 10 to 90% by mass with respect to 100% by mass of the total composition excluding the organic solvent, and the (B) ethylenically unsaturated group-containing fluoropolymer. Content is 1-80 mass% with respect to 100 mass% of composition whole quantity except an organic solvent, The total amount of the solvent of said (C) and the solvent of (D) is the solvent of (C), and (D) Curing characterized in that it is 300 to 5000 parts by mass with respect to 100 parts by mass of the total amount of components other than the solvent of (C), and the mixing ratio of the solvent (C) and the solvent (D) is 1:99 to 99: 1. Resin composition.   The curable resin composition according to claim 1, wherein the (A) tin-containing indium oxide particles are derived from an isopropanol-dispersed sol of tin-containing indium oxide. (B) an ethylenically unsaturated group-containing fluorine-containing polymer containing 40% by mass or more of fluorine,
A hydroxyl group-containing fluoropolymer,
A compound containing a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated group;
The curable resin composition according to claim 1, which is obtained by reacting. When the hydroxyl group-containing fluoropolymer is 100% by mass of the whole fluoropolymer, the following structural units (a) 5 to 90% by mass, (b) 0.3 to 90% by mass, and (c) 1 to The curable resin composition according to claim 3, comprising 65% by mass.
(A) Structural unit represented by the following formula (1) (b) Structural unit represented by the following formula (2) (c) Structural unit represented by the following formula (3)
[In formula (1), R ¹ represents a fluorine atom, a fluoroalkyl group or a group represented by —OR ² (R ² represents an alkyl group or a fluoroalkyl group)]
[In the formula (2), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, and a group represented by — (CH ₂ ) _x —OR ⁵ or —OCOR ⁵ (R ⁵ represents an alkyl group or a fluoroalkyl group. A group, x represents a number of 0 or 1), a carboxyl group or an alkoxycarbonyl group]
[In the formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a group represented by — (CH ₂ ) _v —OR ²⁷ or —OCOR ²⁷ (R ²⁷ represents a hydrogen atom, a hydroxyalkyl group or a glycidyl group. And v represents a number from 0 to 2)] The hydroxyl group-containing fluoropolymer further comprises the following structural unit (d) 0.1 to 10 mass% derived from an azo group-containing polysiloxane compound when the entire fluoropolymer is 100 mass%. The curable resin composition according to 3 or 4.
(D) Structural unit represented by the following general formula (4)
[In General Formula (4), R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group]   The curable resin composition according to any one of claims 3 to 5, wherein the functional group capable of reacting with the hydroxyl group is a group selected from the group consisting of an isocyanate group, a carboxyl group, an acid halide group, and an acid anhydride group. object.   The solvent (C) is a solvent having low dispersion stability of (A) tin-containing indium oxide particles, and the solvent (D) is a solvent having low solubility of (B) an ethylenically unsaturated group-containing fluoropolymer. It is a curable resin composition of any one of Claims 1-6 characterized by the above-mentioned. Furthermore, component (E) contains 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. ,
The content of the said component (E) is 5-80 mass% with respect to 100 mass% of composition whole quantity except an organic solvent, The curable resin of any one of Claims 1-7 characterized by the above-mentioned. Composition. In addition, component (F) includes a radical photopolymerization initiator,
Hardening of any one of Claims 1-8 whose content of the said component (F) is 0.01-10 mass% with respect to 100 mass% of composition whole quantity except an organic solvent. Resin composition.   A cured film obtained by curing the curable resin composition according to claim 1 and having a multilayer structure of two or more layers. The (A) one or more layers in which the tin-containing indium oxide particles are present at a high density and the (A) one or less layers in which the tin-containing indium oxide particles are substantially absent have a layer structure of two or more layers. The cured film according to claim 10.