JP2005089536A - Curable resin composition and antireflection coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition and an antireflection coating excellent in scratch resistance, coatability and durability. <P>SOLUTION: The curable resin composition comprises (A) a fluorine-containing polymer having an ethylenically unsaturated group; (B) a multifunctional (meth)acrylate compound having at least two or more (meth)acryloyl groups and/or a fluorine-containing (meth)acrylate compound having at least one or more (meth)acryloyl groups; and (C) particles composed mainly of silica. A cured product obtained by curing the curable resin composition is used in an antireflection coating 10 as a low-refractive-index layer 18. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a curable resin composition and an antireflection film. More specifically, a curable resin composition containing an ethylenically unsaturated group-containing fluorine-containing polymer and capable of obtaining a cured product having excellent scratch resistance, coating property, and durability when cured, and The present invention relates to an antireflection film including a low refractive index layer made of such a cured product.

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.
In these display panels, the surface is often wiped with gauze impregnated with ethanol or the like in order to remove attached fingerprints, dust, and the like, and scratch resistance is required.
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 (for example, Patent Documents 1 to 3).
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-mentioned problems, 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 are converted into an isocyanate group. A coating composition containing an unsaturated group-containing fluorine-containing vinyl polymer obtained by reacting at a ratio of number / hydroxyl number of 0.01 to 1.0 has been proposed (for example, Patent Document 4). .

JP 57-34107 A JP 59-189108 A JP 60-67518 A JP 61-296073 A

However, in the above publication, when preparing the unsaturated group-containing fluorine-containing vinyl polymer, an isocyanate group-containing unsaturated compound in an amount sufficient to react all the hydroxyl groups of the hydroxyl group-containing fluorine-containing polymer is not used, Actively left unreacted hydroxyl groups in the polymer.
Therefore, a coating composition containing such a polymer can be cured at a low temperature in a short time, but is further cured using a curing agent such as a melamine resin in order to react the remaining hydroxyl groups. There was a need. Furthermore, the coating film obtained by the said gazette had the subject that it could not be said that coating property and abrasion resistance were sufficient.

  Accordingly, an object of the present invention is to provide a curable resin composition and an antireflection film excellent in scratch resistance, coating property and durability.

According to the present invention, the following curable resin composition and antireflection film are provided.
[1] The following components (A), (B) and (C):
(A) an ethylenically unsaturated group-containing fluoropolymer,
(B) 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,
(C) particles mainly composed of silica,
A curable resin composition comprising:

[2] The (A) ethylenically unsaturated group-containing fluoropolymer is
A compound containing one isocyanate group and at least one ethylenically unsaturated group;
A hydroxyl group-containing fluoropolymer,
The curable resin according to [1], which is an ethylenically unsaturated group-containing fluorine-containing polymer obtained by reacting an isocyanate group / hydroxyl group at a ratio of 1.1 to 1.9. Composition.

［式（１）中、Ｒ¹はフッ素原子、フルオロアルキル基又は−ＯＲ²で表される基（Ｒ²はアルキル基又はフルオロアルキル基を示す）を示す］

［式（２）中、Ｒ³は水素原子又はメチル基を、Ｒ⁴はアルキル基、−(ＣＨ₂)_x−ＯＲ⁵若しくは−ＯＣＯＲ⁵で表される基（Ｒ⁵はアルキル基又はグリシジル基を、ｘは０又は１の数を示す）、カルボキシル基又はアルコキシカルボニル基を示す］

［式（３）中、Ｒ⁶は水素原子又はメチル基を、Ｒ⁷は水素原子又はヒドロキシアルキル基を、ｖは０又は１の数を示す］ [3] The hydroxyl group-containing fluoropolymer comprises the following structural units (a) 20 to 70 mol%, (b) 10 to 70 mol% and (c) 5 to 70 mol%, and
The curable resin composition according to [2], wherein the polystyrene-reduced number average molecular weight measured by gel permeation chromatography is 5,000 to 500,000.
(A) A structural unit represented by the following formula (1).
(B) A structural unit represented by the following formula (2).
(C) A 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 glycidyl group. , X represents a number of 0 or 1, and represents a carboxyl group or an alkoxycarbonyl group]

[In formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a hydroxyalkyl group, and v represents a number of 0 or 1]

[4] The particles according to any one of [1] to [3], wherein (C) silica-based particles are surface-treated with an organic compound containing a polymerizable unsaturated group. Curable resin composition.

[5] The curable resin composition according to any one of [1] to [4], wherein the particle (C) having silica as a main component is a hollow particle or a porous particle.

[6] An antireflection film having a low refractive index layer made of a cured product obtained by curing the curable resin composition according to any one of [1] to [5].

  According to the curable resin composition and the antireflection film of the present invention, excellent scratch resistance, coating property, and durability can be obtained.

  Embodiments of the curable resin composition and the antireflection film of the present invention will be described below.

1. Curable resin composition The curable resin composition of this invention may contain the following component (A)-(F). Among these components, (A) to (C) are essential components, and (D) to (F) are optional components that can be appropriately contained.
(A) an ethylenically unsaturated group-containing fluoropolymer (B) a polyfunctional (meth) acrylate compound containing at least two (meth) acryloyl groups and / or at least one (meth) acryloyl group Containing fluorine-containing (meth) acrylate compound (C) Silica-based particles (D) Active energy ray irradiation or heat generation of active species (E) Organic solvent (F) Other additives These The components will be described below.

(A) Ethylenically unsaturated group-containing fluorine-containing polymer The ethylenically unsaturated group-containing fluorine-containing polymer is a compound containing one isocyanate group and at least one ethylenically unsaturated group, and a hydroxyl group-containing polymer. It is obtained by reacting a fluoropolymer with an isocyanate group / hydroxyl molar ratio of 1.1 to 1.9.

(1) A 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.
As examples of the diisocyanate, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), and 1,3-bis (isocyanate methyl) cyclohexane are preferable.

As examples of the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are 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.

(2) Hydroxyl group-containing fluoropolymer The hydroxyl group-containing fluoropolymer preferably comprises the following structural units (a), (b) and (c).
(A) A structural unit represented by the following formula (1).
(B) A structural unit represented by the following formula (2).
(C) A structural unit represented by the following formula (3).

［式（１）中、Ｒ¹はフッ素原子、フルオロアルキル基又は−ＯＲ²で表される基（Ｒ²はアルキル基又はフルオロアルキル基を示す）を示す］

[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)]

［式（２）中、Ｒ³は水素原子又はメチル基を、Ｒ⁴はアルキル基、−(ＣＨ₂)_x−ＯＲ⁵若しくは−ＯＣＯＲ⁵で表される基（Ｒ⁵はアルキル基又はグリシジル基を、ｘは０又は１の数を示す）、カルボキシル基又はアルコキシカルボニル基を示す］

[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 glycidyl group. , X represents a number of 0 or 1, and represents a carboxyl group or an alkoxycarbonyl group]

［式（３）中、Ｒ⁶は水素原子又はメチル基を、Ｒ⁷は水素原子又はヒドロキシアルキル基を、ｖは０又は１の数を示す］

[In formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a hydroxyalkyl group, and v represents a number of 0 or 1]

(I) Structural unit (a)
In the above 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, a perfluorocyclohexyl group, and the like. 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), (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether); Perfluoro (alkoxyalkyl vinyl ether) s such as perfluoro (propoxypropyl vinyl ether) These may be used alone or in combination of two or more.
Among these, hexafluoropropylene and perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether) are more preferable, and it is more preferable to use these in combination.

In addition, the content rate of a structural unit (a) is 20-70 mol% when the whole quantity of a hydroxyl-containing fluoropolymer is 100 mol%. The reason for this is that when the content is less than 20 mol%, it is sometimes difficult to develop a low refractive index, which is the characteristic of the optically fluorine-containing material intended by the present application. This is because when the ratio exceeds 70 mol%, the solubility of the hydroxyl group-containing fluoropolymer in an organic solvent, transparency, or adhesion to a substrate may be lowered.
For these reasons, the content of the structural unit (a) is more preferably 25 to 65 mol%, and more preferably 30 to 60 mol%, based on the total amount of the hydroxyl group-containing fluoropolymer. Is more preferable.

(Ii) 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. Examples of the group include a methoxycarbonyl group and an ethoxycarbonyl group.

  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 or cycloalkyl vinyl ethers such as octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether; 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; (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and other unsaturated carboxylic acids, etc. The combination of is mentioned.

In addition, the content rate of a structural unit (b) is 10-70 mol% when the whole quantity of a hydroxyl-containing fluoropolymer is 100 mol%. This is because if the content is less than 10 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced. On the other hand, if the content exceeds 70 mol%, the hydroxyl group This is because optical properties such as transparency and low reflectivity of the fluorinated polymer may be deteriorated.
For such reasons, the content of the structural unit (b) is more preferably 20 to 60 mol%, and more preferably 30 to 60 mol%, based on the total amount of the hydroxyl group-containing fluoropolymer. Is more preferable.

(Iii) Structural unit (c)
In the formula (3), as the hydroxyalkyl group of R ⁷ , 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 5-hydroxypentyl group , 6-hydroxyhexyl group.

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.

In addition, it is preferable that the content rate of a structural unit (c) shall be 5-70 mol% when the whole quantity of a hydroxyl-containing fluoropolymer is 100 mol%. This is because if the content is less than 5 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced. On the other hand, if the content exceeds 70 mol%, the hydroxyl group This is because optical properties such as transparency and low reflectivity of the fluorinated polymer may be deteriorated.
For such reasons, the content of the structural unit (c) is more preferably 5 to 40 mol%, and more preferably 5 to 30 mol%, based on the total amount of the hydroxyl group-containing fluoropolymer. Is more preferable.

(Iv) Structural unit (d) and structural unit (e)
The hydroxyl group-containing fluoropolymer preferably further comprises the following structural unit (d).

［式（４）中、Ｒ⁸及びＲ⁹は、同一でも異なっていてもよく、水素原子、アルキル基、ハロゲン化アルキル基又はアリール基を示す］ (D) A structural unit represented by the following formula (4).

[In 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]

In the 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 or perfluoro group. C1-C4 fluoroalkyl groups, such as an ethyl group, a perfluoropropyl group, a perfluorobutyl group, etc., A phenyl group, a benzyl group, a naphthyl group etc. are each mentioned as an aryl group.

  The structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the formula (4). Examples of such azo group-containing polysiloxane compounds include compounds represented by the following formula (5).

［式（５）中、Ｒ¹⁰〜Ｒ¹³は、同一でも異なっていてもよく、水素原子、アルキル基又はシアノ基を示し、Ｒ¹⁴〜Ｒ¹⁷は、同一でも異なっていてもよく、水素原子又はアルキル基を示し、ｐ、ｑは１〜６の数、ｓ、ｔは０〜６の数、ｙは１〜２００の数、ｚは１〜２０の数を示す。］

[In the formula (5), R ^{10 to} R ¹³ may be the same or different and each represents a hydrogen atom, an alkyl group or a cyano group, and R ^{14 to} R ¹⁷ may be the same or different and represent a hydrogen atom. Alternatively, it represents an alkyl group, p and q are numbers 1 to 6, s and t are numbers 0 to 6, y is a number 1 to 200, and z is a number 1 to 20. ]

  When the compound represented by the formula (5) is used, the structural unit (d) is included in the hydroxyl group-containing fluoropolymer as a part of the structural unit (e).

［式（６）中、Ｒ¹⁰〜Ｒ¹³、Ｒ¹⁴〜Ｒ¹⁷、ｐ、ｑ、ｓ、ｔ及びｙは、上記式（５）と同じである。］ (E) A structural unit represented by the following formula (6).

[In the formula (6), R ^{10 to} R ¹³ , R ^{14 to} R ¹⁷ , p, q, s, t, and y are the same as in the above formula (5). ]

In the formulas (5) and (6), examples of the alkyl group represented by R ^{10 to} R ¹³ 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 ^{14 to} R ¹⁷ 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 above formula (5) is particularly preferably a compound represented by the following formula (7).

［式（７）中、ｙ及びｚは、上記式（５）と同じである。］

[In Formula (7), y and z are the same as the said Formula (5). ]

In addition, it is preferable that the content rate of a structural unit (d) shall be 0.1-10 mol% when the whole quantity of a hydroxyl-containing fluoropolymer is 100 mol%. The reason for this is that when the content is less than 0.1 mol%, the surface slipperiness of the cured coating film is lowered, and the scratch resistance of the coating film may be lowered. If the amount exceeds 10 mol%, the transparency of the hydroxyl group-containing fluoropolymer 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 mol% with respect to the total amount of the hydroxyl group-containing fluoropolymer, More preferably, it is mol%. 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.

(V) Structural unit (f)
It is also preferred that the hydroxyl group-containing fluoropolymer further comprises the following structural unit (f).

［式（８）中、Ｒ¹⁸は乳化作用を有する基を示す］ (F) A structural unit represented by the following formula (8).

[In formula (8), R ¹⁸ represents a group having an emulsifying action]

In the formula (8), the group having an emulsifying action of R ¹⁸ includes a group having both a hydrophobic group and a hydrophilic group, and the hydrophilic group having a polyether structure such as polyethylene oxide and polypropylene oxide. preferable.

［式（９）中、ｎは１〜２０の数、ｍは０〜４の数、ｕは３〜５０の数を示す］ Examples of the group having such an emulsifying action include a group represented by the following formula (9).

[In 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 formula (10).

［式（１０）中、ｎ、ｍ及びｕは、上記式（９）と同様である］

[In Formula (10), n, m, and u are the same as those in Formula (9) above]

In addition, it is preferable that the content rate of a structural unit (f) shall be 0.1-5 mol% when the whole quantity of a hydroxyl-containing fluoropolymer is 100 mol%. This is because, when the content is 0.1 mol% or more, the solubility of the hydroxyl group-containing fluoropolymer in the solvent is improved. On the other hand, if the content is within 5 mol%, 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 3 mol% based on the total amount of the hydroxyl group-containing fluoropolymer, and 0.2 to 3 More preferably, it is mol%.

(Vi) Molecular Weight The hydroxyl group-containing fluoropolymer preferably has a polystyrene-equivalent number average molecular weight of 5,000 to 500,000 measured by gel permeation chromatography using tetrahydrofuran as a solvent. 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.

(3) Reaction molar ratio The ethylenically unsaturated group-containing fluoropolymer is the above-described compound containing one isocyanate group and at least one ethylenically unsaturated group, and a hydroxyl group-containing fluoropolymer. Is obtained at a molar ratio of isocyanate group / hydroxyl group of 1.1 to 1.9. The reason for this is that if the molar ratio is less than 1.1, 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 1.1 to 1.5, and more preferably 1.2 to 1.5.

The amount of component (A) added is not particularly limited, but is usually 3 to 90% by weight based on the total amount of the composition other than the organic solvent. The reason for this is that when the addition amount is less than 3% by weight, the refractive index of the cured coating film of the curable resin composition becomes high, and a sufficient antireflection effect may not be obtained. This is because if the amount exceeds 90% by weight, the scratch resistance of the cured coating film of the curable resin composition may not be obtained.
For this reason, the amount of component (A) added is more preferably 5 to 80% by weight, and even more preferably 10 to 60% by weight.

(B) a polyfunctional (meth) acrylate compound containing at least two (meth) acryloyl groups and / or a fluorine-containing (meth) acrylate compound (1) containing at least one (meth) acryloyl group Polyfunctional (meth) acrylate compound containing two or more (meth) acryloyl groups At least two or more (meth) acryloyl group-containing polyfunctional (meth) acrylate compounds are obtained by curing a curable resin composition. It is used for enhancing the scratch resistance of the obtained cured product and the antireflection film using the same.

The compound 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” Product name, include alone or in a combination of two or more of Shin-Nakamura Chemical Co., Ltd.), and the like.
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 is particularly preferred.

(2) Fluorine-containing (meth) acrylate compound containing at least one (meth) acryloyl group At least one fluorine-containing (meth) acrylate compound containing (meth) acryloyl group is a curable resin composition. It is used to lower the refractive index of.

  The compound 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 amount of component (B) added is not particularly limited, but is usually 5 to 90% by weight with respect to the total amount of the composition other than the organic solvent. The reason for this is that when the addition amount is less than 5% by weight, the scratch resistance of the cured coating film of the curable resin composition may not be obtained, whereas when the addition amount exceeds 90% by weight, 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 (B) added is more preferably 10 to 80% by weight, and even more preferably 15 to 60% by weight.

(C) Particles mainly composed of silica (1) Particles mainly composed of silica The curable resin composition of the present invention has scratch resistance of the cured product of the curable resin composition, particularly steel wool resistance. In order to improve, particles containing silica as a main component are blended. As the particles containing silica as a main component, known particles can be used, and as long as the shape is spherical, not only ordinary colloidal silica but also hollow particles, porous particles, and core / shell type particles. From the viewpoint of reducing the refractive index of the composition, hollow particles and porous particles are preferable, and hollow particles are particularly preferable. Moreover, not only spherical shape but an indeterminate shape particle | grains may be sufficient. Colloidal silica having a number average particle size determined by a dynamic light scattering method of 1 to 100 nm, a solid content of 10 to 40% by weight, and a pH of 2.0 to 6.5 is preferable.

The dispersion medium is preferably water or an organic solvent. Examples of organic solvents include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol, and ethylene glycol monopropyl ether; ketones such as meethyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethyl Examples include amides such as formamide, dimethylacetamide, and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate, and γ-butyrolactone; and organic solvents such as ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in combination of two or more as a dispersion medium.
As a commercial product of particles mainly composed of silica, for example, Snowtex O (manufactured by Nissan Chemical Industries, Ltd.) (number average particle diameter determined by dynamic light scattering method 7 nm, solid content 20% by weight, pH 2.7) ), Snowtex OL (number average particle diameter determined by dynamic light scattering method: 15 nm, solid content: 20% by weight, pH 2.5), and the like.

Moreover, what carried out surface treatments, such as chemical modification, on the colloidal silica surface can be used, for example, a hydrolyzable silicon compound having one or more alkyl groups in the molecule or one containing a hydrolyzate thereof. Can be reacted. Such hydrolyzable silicon compounds include trimethylmethoxysilane, tributylmethoxysilane, dimethyldimethoxysilane, dibutyldimethoxysilane, methyltrimethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, 1,1. , 1-trimethoxy-2,2,2-trimethyl-disilane, hexamethyl-1,3-disiloxane, 1,1,1-trimethoxy-3,3,3-trimethyl-1,3-disiloxane, α-trimethylsilyl -Ω-dimethylmethoxysilyl-polydimethylsiloxane, α-trimethylsilyl-ω-trimethoxysilyl-polydimethylsiloxane hexamethyl-1,3-disilazane, and the like. A hydrolyzable silicon compound having one or more reactive groups in the molecule can also be used. Hydrolyzable silicon compounds having one or more reactive groups in the molecule are, for example, urea propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl having NH ₂ groups as reactive groups. Trimethoxysilane or the like having an OH group, bis (2-hydroxyethyl) -3aminotripropylmethoxysilane or the like having an isocyanate group, 3-isocyanatopropyltrimethoxysilane or the like having a thiocyanate group 3 As thiocyanate propyltrimethoxysilane and the like having an epoxy group (3-glycidoxypropyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like having a thiol group 3 -Mercaptopropyltrimethoxy Sisilane etc. can be mentioned. A preferred compound is 3-mercaptopropyltrimethoxysilane.

  The particles containing silica as a main component are preferably those which have been surface-treated with an organic compound containing a polymerizable unsaturated group (hereinafter sometimes referred to as “specific organic compound”). By such surface treatment, the scratch resistance of the cured product obtained by curing the composition of the present invention is hardly deteriorated even after being immersed in an alkaline aqueous solution.

(2) Specific organic compound The specific organic compound used in the present invention is a polymerizable compound containing a polymerizable unsaturated group in the molecule. This compound is a compound further containing a group represented by the following formula (11) in the molecule, and a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis. preferable.

［式（１１）中、ＸはＮＨ、Ｏ（酸素原子）又はＳ（イオウ原子）を示し、ＹはＯ又はＳを示す。］

[In the formula (11), X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]

(I) Polymerizable unsaturated group The polymerizable unsaturated group contained in the specific organic compound is not particularly limited. For example, acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, A cinnamoyl group, a maleate group, and an acrylamide group can be mentioned as preferred examples.
This polymerizable unsaturated group is a structural unit that undergoes addition polymerization with active radical species.

(Ii) Group represented by Formula (11) The specific organic compound preferably further includes a group represented by Formula (11) in the molecule. Specific examples of the group [—X—C (═Y) —NH—] represented by the formula (11) include [—O—C (═O) —NH—], [—O—C (═S). ) —NH—], [—S—C (═O) —NH—], [—NH—C (═O) —NH—], [—NH—C (═S) —NH—], and [ -S-C (= S) -NH-]. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of thermal stability, [—O—C (═O) —NH—] group, [—O—C (═S) —NH—] group and [—S—C (═O) — It is preferable to use in combination with at least one of the NH— groups.
The group [—X—C (═Y) —NH—] represented by the formula (11) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical strength and group when cured. It is considered that it gives properties such as adhesion to the material and heat resistance.

(Iii) A silanol group or a group that generates a silanol group by hydrolysis The specific organic compound is a compound having a silanol group in the molecule (hereinafter sometimes referred to as “silanol group-containing compound”) or by hydrolysis. A compound that generates a silanol group (hereinafter sometimes referred to as a “silanol group-generating compound”) is preferable. Examples of such a silanol group-forming compound include compounds having an alkoxy group, aryloxy group, acetoxy group, amino group, halogen atom, etc. on the silicon atom, but an alkoxy group or aryloxy group on the silicon atom. In other words, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.
The silanol group-generating site of the silanol group or the silanol group-generating compound is a structural unit that binds to the oxide particles by a condensation reaction or a condensation reaction that occurs following hydrolysis.

(Iv) Preferred Embodiment Specific examples of the specific organic compound include compounds represented by the following formula (12).

R ¹⁹ and R ²⁰ may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and a represents a number of 1, 2 or 3.
Examples of R ¹⁹ and R ²⁰ include methyl, ethyl, propyl, butyl, octyl, phenyl, xylyl groups and the like.

Examples of the group represented by [(R ¹⁹ O) _a R ²⁰ _3-a Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, a dimethylmethoxysilyl group, and the like. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.

R ²¹ is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms and may contain a chain, branched or cyclic structure. Examples of such an organic group include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, and dodecamethylene. Among these, preferred examples are methylene, propylene, cyclohexylene, phenylene and the like.

R ²² is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500. For example, chain polyalkylene groups such as hexamethylene, octamethylene, dodecamethylene; alicyclic or polycyclic divalent organic groups such as cyclohexylene and norbornylene; divalent groups such as phenylene, naphthylene, biphenylene and polyphenylene Aromatic group; and these alkyl group-substituted and aryl group-substituted products. Further, these divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and include a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, and a group represented by the formula (11). Can also be included.

R ²³ is a (b + 1) -valent organic group, preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.

  Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species. For example, acryloyl (oxy) group, methacryloyl (oxy) group, vinyl (oxy) group, propenyl (oxy) group, butadienyl (oxy) group, styryl (oxy) group, ethynyl (oxy) group, cinnamoyl (oxy) group , Maleate group, acrylamide group, methacrylamide group and the like. Among these, an acryloyl (oxy) group and a methacryloyl (oxy) group are preferable. Further, b is preferably a positive integer of 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5.

  For the synthesis of the specific organic compound used in the present invention, for example, a method described in JP-A-9-100111 can be used. That is, (i) it can be carried out by an addition reaction of a mercaptoalkoxysilane, a polyisocyanate compound, and an active hydrogen group-containing polymerizable unsaturated compound. (B) The reaction can be carried out by a direct reaction between a compound having an alkoxysilyl group and an isocyanate group in the molecule and an active hydrogen-containing polymerizable unsaturated compound. Furthermore, (c) it can also be directly synthesized by an addition reaction of a compound having a polymerizable unsaturated group and an isocyanate group in the molecule with mercaptoalkoxysilane or aminosilane.

In order to synthesize the compound represented by the formula (12), (a) is preferably used among these methods. More specifically, for example,
Method (a): First, a mercaptoalkoxysilane and a polyisocyanate compound are reacted to form an intermediate containing an alkoxysilyl group, [—S—C (═O) —NH—] group and an isocyanate group in the molecule. Next, an active hydrogen-containing polymerizable unsaturated compound is reacted with the isocyanate remaining in the intermediate, and this unsaturated compound is bonded via a [—O—C (═O) —NH—] group. How to
Method (b): First, a polyisocyanate compound and an active hydrogen-containing polymerizable unsaturated compound are reacted to form a polymerizable unsaturated group, [—O—C (═O) —NH—] group, and isocyanate in the molecule. Forming an intermediate containing a group, reacting this with a mercaptoalkoxysilane, and bonding the mercaptoalkoxysilane via a [—S—C (═O) —NH—] group,
Etc. Further, among them, the method (a) is preferable in that there is no decrease in polymerizable unsaturated groups due to the Michael addition reaction.

  In the synthesis of the compound represented by the formula (12), examples of the alkoxysilane capable of forming a [—S—C (═O) —NH—] group by reaction with an isocyanate group include an alkoxysilyl group. And compounds having at least one mercapto group in the molecule. Examples of such mercaptoalkoxysilane include mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropyldimethoxymethylsilane, mercaptopropylmethoxydimethylsilane, mercaptopropyltriphenoxy silane, mercapto Mention may be made of propyltributoxysilane. Among these, mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane are preferable. Moreover, an addition product of an amino-substituted alkoxysilane and an epoxy group-substituted mercaptan and an addition product of an epoxysilane and an α, ω-dimercapto compound can also be used.

  The polyisocyanate compound used when synthesizing the specific organic compound can be selected from polyisocyanate compounds composed of chain saturated hydrocarbons, cyclic saturated hydrocarbons, and aromatic hydrocarbons.

  Examples of such polyisocyanate compounds include, for example, 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, methylene bis (4- (Cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanate) Ethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-bis (Isocyanatemethyl) cyclohexane, tetramethylxylylene diisocyanate, 2,5 (or 6) -bis (isocyanatemethyl) -bicyclo [2.2.1] heptane, and the like. Among these, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylenebis (4-cyclohexylisocyanate), 1,3-bis (isocyanatomethyl) cyclohexane and the like are preferable. These can be used singly or in combination of two or more.

  In the synthesis of a specific organic compound, as an example of an active hydrogen-containing polymerizable unsaturated compound that can be bonded to the polyisocyanate compound via an [—O—C (═O) —NH—] group by an addition reaction, Examples of compounds having at least one active hydrogen atom capable of forming a [—O—C (═O) —NH—] group by addition reaction with an isocyanate group and at least one polymerizable unsaturated group Can do.

Examples of these active hydrogen-containing polymerizable unsaturated compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- Hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythr Litholtri (meth) acrylate, dipentaerythritol penta Data) acrylate - door, and the like can be given. Moreover, the compound obtained by addition reaction with glycidyl group containing compounds, such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth) acrylate, and (meth) acrylic acid can be used. Among these compounds, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate and the like are preferable.
These compounds can be used individually by 1 type or in mixture of 2 or more types.

(3) Surface treatment method of particles mainly composed of silica with a specific organic compound (hereinafter also referred to as particles) The surface treatment method of particles with a specific organic compound is not particularly limited. It is also possible to manufacture by mixing, heating and stirring. The reaction is preferably carried out in the presence of water in order to efficiently combine the silanol group-forming site of the specific organic compound with the particles. However, when the specific organic compound has a silanol group, there is no need for water. Therefore, the surface treatment can be performed by a method including an operation of mixing at least the particles and the specific organic compound.

  The reaction amount of the particles and the specific organic compound is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, particularly preferably 1% by weight, with the total of the particles and the specific organic compound being 100% by weight. That's it. If it is less than 0.01% by weight, the dispersibility of the particles in the composition is not sufficient, and the transparency and scratch resistance of the resulting cured product may not be sufficient.

Hereinafter, the surface treatment method will be described in more detail using the alkoxysilyl group-containing compound (alkoxysilane compound) represented by the formula (12) as an example of the specific organic compound.
The amount of water consumed by hydrolysis of the alkoxysilane compound during the surface treatment may be an amount that allows at least one alkoxy group on silicon in one molecule to be hydrolyzed. Preferably, the amount of water added or present during hydrolysis is at least one third of the number of moles of all alkoxy groups on the silicon, more preferably one half of the number of moles of all alkoxy groups. It is less than 3 times. The product obtained by mixing the alkoxysilane compound and the particles in a completely moisture-free condition is a product in which the alkoxysilane compound is physically adsorbed on the particle surface, and particles composed of such components are not included. In the hardened | cured material of the composition to contain, the effect of expression of high hardness and abrasion resistance is low.

  At the time of surface treatment, after subjecting the alkoxysilane compound to a separate hydrolysis operation, this is mixed with powder particles or solvent dispersion sol of particles, followed by heating and stirring operations; hydrolysis of the alkoxysilane compound; Can be selected in the presence of particles; or a method in which particles are surface-treated in the presence of other components such as a polymerization initiator. In this, the method of hydrolyzing the said alkoxysilane compound in presence of particle | grains is preferable. During the surface treatment, the temperature is preferably 0 ° C. or higher and 150 ° C. or lower, more preferably 20 ° C. or higher and 100 ° C. or lower. The processing time is usually in the range of 5 minutes to 24 hours.

In the case of using a powdery powder during the surface treatment, an organic solvent may be added for the purpose of smoothly and uniformly performing the reaction with the alkoxysilane compound. Examples of such organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone. Esters such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone it can. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.
The amount of these solvents added is not particularly limited as long as it meets the purpose of carrying out the reaction smoothly and uniformly.

  When a solvent-dispersed sol is used as the particles, it can be produced by mixing at least a solvent-dispersed sol and a specific organic compound. Here, an organic solvent which is uniformly compatible with water may be added for the purpose of ensuring the uniformity at the initial stage of the reaction and allowing the reaction to proceed smoothly.

In addition, an acid, a salt or a base may be added as a catalyst to promote the reaction during the surface treatment.
Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, toluenesulfonic acid, phthalic acid, malonic acid, formic acid, acetic acid, and succinic acid; methacrylic acid, acrylic acid, and itacone An unsaturated organic acid such as an acid, as a salt, for example, an ammonium salt such as tetramethylammonium hydrochloride or tetrabutylammonium hydrochloride, and as a base, for example, aqueous ammonia, diethylamine, triethylamine, dibutylamine, Primary, secondary or tertiary aliphatic amines such as cyclohexylamine, aromatic amines such as pyridine, quaternary ammonium hydroxides such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide Etc.
Among these, preferred examples of the acid include organic acids and unsaturated organic acids, and the base includes tertiary amine or quaternary ammonium hydroxide. The amount of these acids, salts or bases added is preferably 0.001 to 1.0 part by weight, more preferably 0.01 to 0.1 part by weight, based on 100 parts by weight of the alkoxysilane compound. It is.

In order to accelerate the reaction, it is also preferable to add a dehydrating agent.
As the dehydrating agent, inorganic compounds such as zeolite, anhydrous silica, and anhydrous alumina, and organic compounds such as methyl orthoformate, ethyl orthoformate, tetraethoxymethane, and tetrabutoxymethane can be used. Of these, organic compounds are preferable, and orthoesters such as methyl orthoformate and ethyl orthoformate are more preferable.
The amount of the alkoxysilane compound bonded to the particles is usually a thermogravimetric analysis from 110 ° C. to 800 ° C. in air as a constant value of weight loss% when the dry powder is completely burned in air. It can ask for.

  (C) The compounding quantity in the resin composition of the particle | grains which have silica as a main component is normally 1-90weight% with respect to composition whole quantity except an organic solvent, 5-80 weight% is preferable, 10-70 is preferable. % By weight is more preferable, and 20 to 60% by weight is particularly preferable. If it is less than 5% by weight, the hardness of the cured product may be insufficient, and if it exceeds 90% by weight, it may not be cured (not form a film). The amount of particles means solid content, and when the particles are used in the form of a solvent-dispersed sol, the amount of the solvent does not include the amount of solvent.

(D) Compound that generates active species by irradiation of active energy rays or heat A compound that generates active species by irradiation of active energy rays or heat is used to cure the curable resin composition.

(1) Compounds that generate active species upon irradiation with active energy rays Compounds that generate active species upon irradiation with active energy rays (hereinafter referred to as “photopolymerization initiators”) include light that generates radicals as active species. A radical generator etc. are mentioned.
The active energy ray is defined as an energy ray capable of decomposing a compound that generates active species to generate active species. Examples of such active energy rays include optical energy rays such as visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, and γ rays. However, it is preferable to use ultraviolet rays from the viewpoint of having a certain energy level, a high curing speed, and a relatively inexpensive irradiation apparatus, and a small size.

(I) Kind Examples of the photo radical generator include acetophenone, acetophenone benzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, carbazole, xanthone, 4- Chlorobenzophenone, 4,4′-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3′-dimethyl-4-methoxybenzophenone, thioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1- (4-dodecyl) Phenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, triphenylamine, 2,4,6 -Trimethylbenzoyldiphenylphosphine oxide 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, Michler ketone, 3-methylacetophenone, 3, 3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone (BTTB), 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl) -1-butanone, 4 Examples thereof include -benzoyl-4'-methyldiphenyl sulfide, benzyl, or a combination of BTTB and xanthene, thioxanthene, coumarin, ketocoumarin, and other dye sensitizers.

  Among these photopolymerization initiators, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4,6- Trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2 -Phenylmethyl) -1-butanone and the like are preferable, and 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (Dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl ) -1-butanone, and the like.

(Ii) Addition amount The addition amount of the photopolymerization initiator is not particularly limited, but is preferably 0.01 to 20% by weight based on the total amount of the composition other than the organic solvent. This is because when the amount added is less than 0.01% by weight, the curing reaction becomes insufficient, and the scratch resistance and the scratch resistance after immersion in an alkaline aqueous solution may decrease. On the other hand, when the addition amount of the photopolymerization initiator exceeds 20% by weight, the refractive index of the cured product increases and the antireflection effect may be lowered.
For this reason, the amount of the photopolymerization initiator added is more preferably 0.05 to 15% by weight, more preferably 0.1 to 15% by weight, based on the total amount of the composition other than the organic solvent. More preferably.

(2) Compound that generates active species by heat Examples of the compound that generates active species by heat (hereinafter referred to as “thermal polymerization initiator”) include a thermal radical generator that generates radicals as the active species.

(I) Type Examples of thermal radical generators include benzoyl peroxide, tert-butyl-oxybenzoate, azobisisobutyronitrile, acetyl peroxide, lauryl peroxide, tert-butyl peracetate, cumyl peroxide, tert -One kind of butyl peroxide, tert-butyl hydroperoxide, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc. Single or 2 or more types of combinations can be mentioned.

(Ii) Addition amount The addition amount of the thermal polymerization initiator is not particularly limited, but is preferably 0.01 to 20% by weight based on the total amount of the composition other than the organic solvent. This is because when the amount added is less than 0.01% by weight, the curing reaction becomes insufficient, and the scratch resistance and the scratch resistance after immersion in an alkaline aqueous solution may decrease. On the other hand, when the addition amount of the photopolymerization initiator exceeds 20% by weight, the refractive index of the cured product increases and the antireflection effect may be lowered.
For these reasons, it is more preferable that the amount of the thermal polymerization initiator added is 0.05 to 15% by weight with respect to the total amount of the composition other than the organic solvent, and it is within the range of 0.1 to 15% by weight. More preferably, the value of

(E) Organic solvent It is preferable to add an organic solvent to the curable resin composition. Thus, by adding an organic solvent, a thin antireflection film can be formed uniformly. Examples of such an organic solvent include one kind or a combination of two or more kinds such as methyl isobutyl ketone, methyl ethyl ketone, methanol, ethanol, t-butanol, and isopropanol.

  The addition amount of the organic solvent is not particularly limited, but is preferably 100 to 100,000 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated group-containing fluoropolymer. This is because when the addition amount is less than 100 parts by weight, it may be difficult to adjust the viscosity of the curable resin composition. On the other hand, when the addition amount exceeds 100,000 parts by weight, the curable resin composition may be difficult to adjust. This is because the storage stability of the composition may decrease, or the viscosity may decrease excessively, making handling difficult.

(F) Additive In the curable resin composition, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, and a surfactant, as long as the object and effect of the present invention are not impaired. It is also preferable to further contain additives such as plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, silane coupling agents, inorganic fillers other than the component (C), pigments, and dyes.

Next, the preparation method and curing conditions of the curable resin composition of the present invention will be described.
The curable resin composition of the present invention comprises the (A) ethylenically unsaturated group-containing fluoropolymer, the (B) component and the (C) component, or, if necessary, the (D) component, (E). It can prepare by adding an organic solvent and (F) additive, respectively, and mixing under room temperature or a heating condition. Specifically, it can be prepared using a mixer such as a mixer, a kneader, a ball mill, or a three roll. However, when mixing under heating conditions, it is preferable to carry out at or below the decomposition start temperature of the thermal polymerization initiator.

The curing conditions of the curable resin composition are not particularly limited, but for example, when an active energy ray is used, the exposure amount is preferably set to a value within the range of 0.01 to 10 J / cm ² .
This is because when the exposure dose is less than 0.01 J / cm ² , curing failure may occur. On the other hand, when the exposure dose exceeds 10 J / cm ² , the curing time may become excessively long. Because there is.
For these reasons, 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. .

Moreover, when making a curable resin composition heat and harden | cure, it is preferable to heat for 1 to 180 minutes at the temperature within the range of 30-200 degreeC. By heating in this way, an antireflection film having excellent scratch resistance can be obtained more efficiently without damaging the substrate and the like.
For these reasons, it is more preferable to heat at a temperature in the range of 50 to 180 ° C. for 2 to 120 minutes, and further to heat at a temperature in the range of 80 to 150 ° C. for 5 to 60 minutes. preferable.

2. Antireflective film The antireflective film of this invention contains the low-refractive-index layer which consists of hardened | cured material which hardened the said curable resin composition. Furthermore, the antireflection film of the present invention can contain a high refractive index layer, a hard coat layer, and / or a substrate under the low refractive index layer.
FIG. 1 shows such an antireflection film 10. As shown in FIG. 1, a hard coat layer 14, a high refractive index layer 16, and a low refractive index layer 18 are laminated on a substrate 12.
At this time, the high refractive index layer 16 may be formed directly on the substrate 12 without providing the hard coat layer 14.
Further, an intermediate refractive index layer (not shown) may be further provided between the high refractive index layer 16 and the low refractive index layer 18 or between the high refractive index layer 16 and the hard coat layer 14.

(1) Low refractive index layer A low refractive index layer is comprised from the hardened | cured material obtained by hardening | curing the curable resin composition of this invention. Since the configuration and the like of the curable resin composition are as described above, a specific description thereof will be omitted, and the refractive index and thickness of the low refractive index layer will be described below.

The refractive index of the cured product obtained by curing the curable resin composition (the refractive index of Na-D line, measurement temperature 25 ° C.), that is, the refractive index of the low refractive index film is preferably 1.45 or less. . The reason for this is that when the refractive index of the low refractive index film exceeds 1.45, the antireflection effect may be significantly reduced when combined with a high refractive index film.
Therefore, the refractive index of the low refractive index film is more preferably 1.44 or less, and further preferably 1.43 or less.
In the case where a plurality of low refractive index films are provided, it is sufficient that at least one of the low refractive index films has a refractive index value within the above-mentioned range. Therefore, the other low refractive index films exceed 1.45. It may be a value.

Moreover, when providing a low refractive index layer, since the more excellent antireflection effect is acquired, it is preferable to make the refractive index difference between high refractive index layers into 0.05 or more values. The reason for this is that when the refractive index difference between the low refractive index layer and the high refractive index layer is less than 0.05, a synergistic effect in these antireflective film layers cannot be obtained. This is because there is a case in which the lowering may occur.
Therefore, it is more preferable to set the refractive index difference between the low refractive index layer and the high refractive index layer to a value within the range of 0.1 to 0.5, and within the range of 0.15 to 0.5. More preferably, it is a value.

The thickness of the low refractive index layer is not particularly limited, but is preferably 50 to 300 nm, for example. The reason for this is that when the thickness of the low refractive index layer is less than 50 nm, the adhesion to the high refractive index film as the base may be reduced. On the other hand, when the thickness exceeds 300 nm, optical interference occurs. This is because the antireflection effect may be reduced.
Therefore, the thickness of the low refractive index layer is more preferably 50 to 250 nm, and further preferably 60 to 200 nm.
In order to obtain higher antireflection properties, when a plurality of low refractive index layers are provided to form a multilayer structure, the total thickness may be 50 to 300 nm.

(2) High refractive index layer Although it does not restrict | limit especially as a curable composition for forming a high refractive index layer, As a film formation component, epoxy-type resin, phenol-type resin, melamine-type resin, It is preferable to include one kind or a combination of two or more kinds of alkyd resins, cyanate resins, acrylic resins, polyester resins, urethane resins, siloxane resins and the like. If these resins are used, a strong thin film can be formed as the high refractive index layer, and as a result, the scratch resistance of the antireflection film can be remarkably improved.
However, the refractive index of these resins alone is usually 1.45 to 1.62, which may not be sufficient to obtain high antireflection performance. Therefore, it is more preferable to blend high refractive index inorganic particles, for example, metal oxide particles. Moreover, as a hardening form, although the curable composition which can be thermosetting, ultraviolet curing, and electron beam curing can be used, the ultraviolet curable composition with favorable productivity is used more suitably.

The thickness of the high refractive index layer is not particularly limited, but is preferably 50 to 30,000 nm, for example. The reason for this is that when the thickness of the high refractive index layer is less than 50 nm, the antireflection effect and adhesion to the substrate may be reduced when combined with the low refractive index layer, while the thickness is If the thickness exceeds 30,000 nm, optical interference may occur, and the antireflection effect may be reduced.
Therefore, the thickness of the high refractive index layer is more preferably 50 to 1,000 nm, and further preferably 60 to 500 nm.
In order to obtain higher antireflection properties, when a plurality of high refractive index layers are provided to form a multilayer structure, the total thickness may be set to 50 to 30,000 nm.
In addition, when providing a hard-coat layer between a high refractive index layer and a base material, the thickness of a high refractive index layer can be 50-300 nm.

(3) Hard coat layer The constituent material of the hard coat layer used in the antireflection film of the present invention is not particularly limited. Examples of such a material include one kind of siloxane resin, acrylic resin, melamine resin, epoxy resin, or a combination of two or more kinds.

  Moreover, although it does not restrict | limit especially also about the thickness of a hard-coat layer, it is preferable to set it as 1-50 micrometers, and it is more preferable to set it as 5-10 micrometers. The reason for this is that when the thickness of the hard coat layer is less than 1 μm, the adhesion of the antireflection film to the substrate may not be improved. On the other hand, when the thickness exceeds 50 μm, it is uniform. This is because it may be difficult to form.

(4) Substrate The type of the substrate used for the antireflection film of the present invention is not particularly limited. For example, glass, polycarbonate resin, polyester resin, acrylic resin, triacetyl cellulose resin (TAC) The base material which consists of etc. can be mentioned. By using an antireflection film containing these base materials, excellent reflection can be achieved in a wide range of application areas of antireflection films such as camera lens parts, television (CRT) screen display parts, and color filters in liquid crystal display devices. The prevention effect can be obtained.

  Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to the description of these examples.

(Production Example 1)
Synthesis of Hydroxyl-Containing Fluoropolymer 1 A stainless steel autoclave with an internal volume of 2.0 liters equipped with a magnetic stirrer was sufficiently replaced with nitrogen gas, and then 400 g of ethyl acetate, 53.2 g of perfluoro (propyl vinyl ether), 36.1 g of ethyl vinyl ether. , Hydroxyethyl vinyl ether 44.0 g, lauroyl peroxide 1.00 g, azo group-containing polydimethylsiloxane represented by the above formula (7) (VPS1001 (trade name), manufactured by Wako Pure Chemical Industries, Ltd.) 6.0 g and After charging 20.0 g of nonionic reactive emulsifier (NE-30 (trade name), manufactured by Asahi Denka Kogyo Co., Ltd.) and cooling to −50 ° C. with dry ice-methanol, the oxygen in the system was again purged with nitrogen gas. Removed.

Next, 120.0 g of hexafluoropropylene was charged, 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 put into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 220 g of a hydroxyl group-containing fluoropolymer. This is designated as a hydroxyl group-containing fluoropolymer 1. Table 1 shows the monomers and solvents used.
It attached to the obtained hydroxyl-containing fluoropolymer 1, and measured the polystyrene conversion number average molecular weight by gel permeation chromatography and the fluorine content by the alizarin complexone method, respectively. Further, ¹ H-NMR, ¹³ C-NMR both results of NMR analysis, elemental analysis and fluorine content to determine the percentage of each monomer component constituting the hydroxyl group-containing fluoropolymer 1. The results are shown in Table 2.

VPS1001 is an azo group-containing polydimethylsiloxane represented by the above formula (7) having a number average molecular weight of 70 to 90,000 and a polysiloxane moiety having a molecular weight of about 10,000. NE-30 is a nonionic reactive emulsifier wherein n is 9, m is 1 and u is 30 in the above formula (10).
Furthermore, in Table 2, the correspondence between the monomer and the structural unit is as follows.
Monomer Structural unit Hexafluoropropylene (a)
Perfluoro (propyl vinyl ether) (a)
Ethyl vinyl ether (b)
Hydroxyethyl vinyl ether (c)
NE-30 (f)
Polydimethylsiloxane skeleton (d)

(Production Example 2)
Synthesis of hydroxyl group-containing fluoropolymer 2 A hydroxyl group-containing fluoropolymer was synthesized in the same manner as in Production Example 1, except that the amounts of ethyl vinyl ether and hydroxyethyl vinyl ether used were changed as shown in Table 1. This is designated as a hydroxyl group-containing fluoropolymer 2. The ratio of each monomer component is shown in Table 2.

(Production Example 3)
Synthesis of ethylenically unsaturated group-containing fluorine-containing polymer (A-1) Hydroxyl-containing fluorine-containing polymer obtained in Production Example 1 in a 1-liter separable flask equipped with an electromagnetic stirrer, a glass condenser, and a thermometer Polymer 1 was charged with 50.0 g, 0.016 g of 2,6-di-t-butylmethylphenol and 370 g of methyl isobutyl ketone (MIBK) as a polymerization inhibitor, and hydroxyl group-containing fluoropolymer 1 was converted to MIBK at 20 ° C. Stir until dissolved and the solution is clear and uniform.
Next, 15.1 g of 2-methacryloyloxyethyl 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. The MIBK solution of the ethylenically unsaturated group-containing fluoropolymer (A-1) 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 15.2% by weight. The compounds used, solvent and solid content are shown in Table 3.

(Production Example 4)
Synthesis of Ethylenically Unsaturated Group-Containing Fluoropolymer (A-2) As shown in Table 3, in Production Example 3, the type of hydroxyl-containing fluoropolymer, 2-methacryloyloxyethyl isocyanate, MIBK, and isocyanate group A MIBK solution of an ethylenically unsaturated group-containing fluoropolymer (A-2) was obtained in the same manner as in Production Example 3 except that the molar ratio of / hydroxyl was changed.

(Production Example 5)
Preparation of silica-based particles (C-1) Solid content 20% by weight, pH 2.7, specific surface area by BET method 226 m ² / g, on silica particles determined by methyl red adsorption method Water-dispersed colloidal silica having a silanol concentration of 4.1 × 10 ⁻⁵ mol / g, a metal content in a solvent determined by atomic absorption spectrometry of 4.6 ppm as Na, 0.013 ppm as Ca, and 0.011 ppm as K ( 30 kg of Nissan Chemical Industries, Ltd., trade name: Snowtex-O) is placed in a tank, heated to 50 ° C., circulating flow rate 50 liters / minute, pressure 1 kg / cm ² , ultrafiltration membrane module ((stock) ) Tritec) and alumina ultrafiltration membrane (Nippon Choshi Co., Ltd., trade name: ceramic UF element, specifications: 4 mmΦ, 19 holes, length 1 m, fractional molecular weight = 150,000, membrane area = 0. 4m ²⁾ was concentrated using. After 0.5 hour, 10 kg of the filtrate was discharged, and the solid content became 30% by weight. The average permeation flow rate (unit area of ultrafiltration membrane, membrane permeation weight per unit time) before the start of concentration was 90 kg / m ² / hour, and 55 kg / m ² / hour at the end of concentration. The number average particle size determined by the dynamic light scattering method was 11 nm, which did not change before and after concentration.

After completion of the above-mentioned steps, 14 kg of methanol is added, concentration is performed using the ultrafiltration membrane module and the ultrafiltration membrane at a temperature of 50 ° C., a circulation flow rate of 50 liters / minute, and a pressure of 1 kg / cm ² , and 14 kg of filtrate is obtained. By repeating the discharging operation 6 times, methanol-dispersed colloidal silica having a solid content of 30% by weight, a water content determined by the Karl Fischer method of 1.5% by weight, and a number average particle size determined by the dynamic light scattering method of 11 nm. 20 kg was prepared. The average permeation flow rate of 6 times was 60 kg / m ² / hour, and the required time was 6 hours. The specific surface area of the obtained methanol-dispersed colloidal silica by the BET method was 237 m ² / g, and the silanol concentration on the silica particles determined by the methyl red adsorption method was 3.5 × 10 ⁻⁵ mol / g.

0.6 kg of trimethylmethoxysilane (manufactured by Toray Dow Corning Co., Ltd.) was added to 20 kg of the methanol-dispersed colloidal silica thus prepared, and the mixture was heated and stirred at 60 ° C. for 3 hours. The number average particle size determined by the dynamic light scattering method was 11 nm, and no change was observed before the treatment. The specific surface area of the obtained methanol-dispersed hydrophobized colloidal silica by BET method was 240 m ² / g, and the silanol concentration on the silica particles determined by methyl red adsorption method was 2.1 × 10 ⁻⁵ mol / g.

After completion of the above-mentioned steps, the operation of adding 14 kg of methyl ethyl ketone, concentrating using the ultrafiltration membrane at a temperature of 50 ° C., a circulation flow rate of 50 liters / minute, and a pressure of 1 kg / cm ² , and discharging 14 kg of filtrate five times Repeatedly, the solid content was 30% by weight, the water content determined by the Karl Fischer method was 0.3% by weight, the methanol content determined by gas chromatography (GC) was 3.2% by weight, and the dynamic light scattering method was used. Further, 20 kg of MEK-dispersed hydrophobized colloidal silica having a number average particle diameter of 11 nm was prepared. The average permeation flow rate for 5 times was 70 kg / m ² / hour, and the required time was 4 hours. The specific surface area of the obtained MEK-dispersed colloidal silica by the BET method was 230 m ² / g, and the silanol concentration on the silica particles determined by the methyl red adsorption method was 1.8 × 10 ⁻⁵ mol / g. The metal content of MEK-dispersed hydrophobized colloidal silica obtained by atomic absorption spectroscopy was extremely small, with 0.05 ppm for Na and 0.001 ppm for Ca and K. The MEK-dispersed colloidal silica obtained as described above is defined as (C-1).

(Production Example 6)
Synthesis of specific organic compound (S1) A solution of 7.8 parts mercaptopropyltrimethoxysilane and 0.2 part dibutyltin dilaurate in dry air was stirred at 50 ° C for 1 hour with 20.6 parts isophorone diisocyanate. After dropping, the mixture was stirred at 60 ° C. for 3 hours. 71.4 parts of pentaerythritol triacrylate was added dropwise thereto at 30 ° C. over 1 hour, and then the mixture was heated and stirred at 60 ° C. for 3 hours to obtain the specific organic compound (S1).
In the infrared absorption spectrum of the product, the absorption peak of 2550 Kaiser characteristic of the mercapto group and the absorption peak of 2260 Kaiser characteristic of the isocyanate group disappeared. Characteristic 1720 Kaiser peak and acryloyl group characteristic of carbonyl in —O—C (═O) —NH—] and [—S—C (═O) —NH—] groups A peak of Kaiser was observed, and an acryloyl group, a [—S—C (═O) —NH—] group, and a [—O—C (═O) —NH—] group as polymerizable unsaturated groups were observed. It was shown that a specific organic compound having both was produced.

(Production Example 7)
Preparation of particles containing silica as main component (C-2) 8.7 parts of specific organic compound (S1) synthesized in Production Example 6 under a nitrogen stream, methyl ethyl ketone silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK) -ST (number average particle diameter 0.022 μm, silica concentration 30%)) 91.3 parts (solid content 27.4 parts), isopropanol 0.2 parts and ion-exchanged water 0.1 parts, After stirring for 3 hours, 1.4 parts of methyl orthoformate was added, and further heated and stirred at the same temperature for 1 hour to obtain a colorless and transparent particle (C-2) dispersion (dispersion a). 2 g of dispersion a was weighed in an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour and weighed to determine the solid content, which was 35% by weight.

(Production Example 8)
Preparation of Particles Containing Silica as Main Component (C-3) A mixture of 100 g of silica sol having an average particle diameter of 5 nm and a SiO ₂ concentration of 20% by weight and 1900 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor was 10.5, and 9000 g of a 1.17 wt% sodium silicate aqueous solution as SiO ₂ and 9000 g of a 0.83 wt% sodium aluminate aqueous solution as Al ₂ O ₃ were simultaneously added to the mother liquor. . Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition, and hardly changed thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO ₂ .Al ₂ O ₃ core particle dispersion with a solid concentration of 20 wt%.
1,700 g of pure water is added to 500 g of this core particle dispersion and heated to 98 ° C., and while maintaining this temperature, a silicic acid solution (SiO ₂₎ obtained by dealkalizing a sodium silicate aqueous solution with a cation exchange resin. A dispersion of core particles having a silica outer shell formed by adding 3,000 g (concentration: 3.5 wt%) was obtained.
Next, 1,125 g of pure water was added to 500 g of a dispersion of core particles formed with a silica shell having a solid content concentration of 13 wt% by washing with an ultrafiltration membrane, and concentrated hydrochloric acid (35.5%) was further added. The solution was dropped to pH 1.0, and dealumination was performed. Subsequently, the aluminum salt dissolved in the ultrafiltration membrane was separated while adding 10 liters of pH 3 hydrochloric acid aqueous solution and 5 liters of pure water, and then the solvent was replaced with ethanol using the ultrafiltration membrane, so that the solid content concentration was 20 wt. A dispersion b of hollow silica-based particles (C-3) consisting of% silica outer shell was prepared.

  The average particle diameter and refractive index of the silica-based particles (C-3) were 40 nm and 1.33, respectively. Here, the average particle diameter was measured by a dynamic light scattering method.

(Production Example 9)
Preparation of particles containing silica as main component (C-4) Under a nitrogen stream, 8.7 parts of specific organic compound (S1) synthesized in Production Example 6 and 137 parts of C-3 (solid content: 27.4 parts), After stirring a mixture of 0.2 parts of isopropanol and 0.1 parts of ion-exchanged water at 80 ° C. for 3 hours, 1.4 parts of orthoformate methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to be colorless. A transparent particle (C-4) dispersion (dispersion c) was obtained. 2 g of dispersion c was weighed in an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour, and weighed to determine the solid content, which was 25% by weight.

(Production Example 10)
Preparation of composition for hard coat layer containing zirconia 8.2 parts of specific organic compound (S1) synthesized in Production Example 6, 91.8 parts of toluene zirconia sol (number average particle diameter 0.01 μm, zirconia concentration 30%), methyl ethyl ketone 41.2 parts and ion-exchanged water 0.1 part mixture were stirred at 60 ° C. for 4 hours, 1.3 parts of orthoformate methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to disperse the particles. A liquid (dispersion d) was obtained. 2 g of this dispersion d was weighed in an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour, and weighed to determine the solid content, which was 25% by weight.

  In a container shielded from ultraviolet rays in a dry air stream, 312 parts of the produced dispersion d, 12.0 parts of dipentaerythritol hexaacrylate, 9.0 parts of pentaerythritol triacrylate, 2-methyl-1- A composition for a hard coat layer having a uniform solution was obtained by stirring 1.0 part of [4- (methylthio) phenyl] -2-morpholinopropan-1-one at 50 ° C. for 2 hours. 2 g of this composition was weighed into an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour, and weighed to determine the solid content, which was 30% by weight.

(Production Example 11)
Preparation of substrate for coating curable resin composition For zirconia-containing hard coat layer prepared in Production Example 10 on the easy-adhesion treated surface of single-sided easy-adhesive polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd., film thickness 188 μm) The composition was applied using a wire bar coater (# 7) and dried in an oven at 80 ° C. for 1 minute to form a coating film. Next, ultraviolet rays were irradiated under a light irradiation condition of 0.9 mJ / cm ² using a high-pressure mercury lamp in the air to prepare a substrate for coating a curable resin composition. When the film thickness of the hard coat layer on this substrate was measured with a stylus type surface shape measuring instrument, it was 3 μm.

(Example 1)
As shown in Table 4, 329 g of MIBK solution of the ethylenically unsaturated group-containing fluoropolymer (A-1) obtained in Production Example 3 (50 g as A-1), “at least two (meth) or more (meta) 25 g of dipentaerythritol pentaacrylate (DPPA, manufactured by Sartomer) as a polyfunctional (meth) acrylate compound containing an acryloyl group ”, 23 g of particles (C-1) mainly obtained from Production Example 5; 2 g of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907, manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, MIBK1161 g (MIBK of A-1 above) Combine 1440 g of MIBK added as the solvent of the solution and 868 g of tert-butyl alcohol. They were charged into a separable glass flask, to give a 1 hour stirring uniform curable resin composition at 23 ° C.. Further, the solid content was determined by the method of Production Example 3.

(Examples 2 to 6, Comparative Examples 1 and 2)
Each curable composition was obtained in the same manner as in Example 1 except that the composition in Table 4 was followed.
In Examples 4 to 6, instead of “polyfunctional (meth) acrylate compound containing at least two (meth) acryloyl groups”, “containing at least one (meth) acryloyl group” is contained. As the “fluorine (meth) acrylate compound”, a bifunctional fluorine acrylate represented by the following formula (13) was used.

(Test example)
(1) Refractive index Each curable resin composition was applied onto a silicon wafer by a spin coater so that the thickness after drying was about 0.1 μm, and then 0.5 mJ using a high-pressure mercury lamp under nitrogen. It was cured by irradiating with ultraviolet rays under the light irradiation condition of / cm ² . The obtained cured product was measured refractive index at a wavelength 539nm at 25 ° C. using an ellipsometer to ^{_(n D 25).} The results are shown in Table 4.

(2) Scratch resistance 1 (cloth abrasion resistance test)
Each curable resin composition is coated on the curable resin composition coating substrate prepared in Production Example 11 using a wire bar coater (# 3), and dried in an oven at 80 ° C. for 1 minute. A coating film was formed. Next, ultraviolet rays were irradiated under a light irradiation condition of 0.5 mJ / cm ² using a high-pressure mercury lamp under nitrogen to prepare a sample for evaluation. When the film thickness of the cured product layer was estimated by reflectance measurement, it was about 100 nm.

The surface of the prepared sample for evaluation was rubbed with a cellulose nonwoven fabric impregnated with ethanol (trade name Bencott, Asahi Kasei Kogyo Co., Ltd.) 200 times by hand, and the scratch resistance of the sample surface for evaluation was determined as follows. Visual evaluation was made according to the criteria. The results are shown in Table 4.
A: The sample surface for evaluation is intact.
○: The surface of the sample for evaluation has fine scratches.
Δ: The surface of the evaluation sample is scratched.
X: Peeling of the coating film is observed.

(3) Scratch resistance test 2 (steel wool resistance test)
A sample for evaluation was produced in the same manner as scratch resistance 1 (cloth scratch resistance test).
The steel wool resistance test of this cured film was performed 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 a load of 200 g. By repeatedly rubbing 10 times under conditions, the presence or absence of scratches on the surface of the cured film was visually confirmed according to the following criteria. The results are shown in Table 4.
A: Hardened film peeling or scratches are hardly observed.
○: A thin scratch is observed in the cured film.
X: Peeling occurred in a part of the cured film, or streak scratches occurred on the surface of the cured film.

(4) Scratch resistance after immersion in alkaline aqueous solution The sample for evaluation prepared in (2) was immersed in a 2N aqueous sodium hydroxide solution at 25 ° C. for 2 minutes, washed with distilled water and air-dried. Using a non-woven fabric made of cellulose soaked in water (trade name: Bencott, Asahi Kasei Kogyo Co., Ltd.), the surface of the sample for evaluation was rubbed with an alkaline aqueous solution by visual inspection according to the following criteria. evaluated. The results are shown in Table 4.
A: The sample surface for evaluation is intact.
○: The surface of the sample for evaluation has fine scratches.
Δ: The surface of the evaluation sample is scratched.
X: Peeling of the coating film is observed.

(5) Contamination resistance A fingerprint was attached to the coating film surface of the sample for evaluation prepared in (2), and the coating film surface was wiped off with a nonwoven fabric (Bencotton). Contamination resistance was evaluated according to the following criteria. The results are shown in Table 4.
○: Fingerprint marks on the coating surface were almost completely wiped off.
X: Fingerprint traces remained on the sample surface without being wiped off.

  The curable resin composition of the present invention is excellent in scratch resistance, coating property and durability, and is particularly useful as an antireflection film.

It is sectional drawing of the antireflection film by one Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Antireflection film 12 Base material 16 High refractive index layer 18 Low refractive index layer

Claims (6)

The following components (A), (B) and (C):
(A) an ethylenically unsaturated group-containing fluoropolymer,
(B) 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,
(C) particles mainly composed of silica,
A curable resin composition comprising: The (A) ethylenically unsaturated group-containing fluoropolymer is
A compound containing one isocyanate group and at least one ethylenically unsaturated group;
A hydroxyl group-containing fluoropolymer,
2. The curable resin composition according to claim 1, which is an ethylenically unsaturated group-containing fluorine-containing polymer obtained by reacting at a molar ratio of isocyanate group / hydroxyl group of 1.1 to 1.9. The hydroxyl group-containing fluoropolymer comprises the following structural units (a) 20 to 70 mol%, (b) 10 to 70 mol% and (c) 5 to 70 mol%, and
The curable resin composition according to claim 2, wherein the polystyrene-reduced number average molecular weight measured by gel permeation chromatography is 5,000 to 500,000.
(A) A structural unit represented by the following formula (1).
(B) A structural unit represented by the following formula (2).
(C) A 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 glycidyl group. , X represents a number of 0 or 1, and represents a carboxyl group or an alkoxycarbonyl group]

[In formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a hydroxyalkyl group, and v represents a number of 0 or 1]   The curable resin composition according to any one of claims 1 to 3, wherein the (C) silica-based particles are surface-treated with an organic compound containing a polymerizable unsaturated group.   The curable resin composition according to any one of claims 1 to 4, wherein the (C) silica-based particles are hollow particles or porous particles.   The antireflection film which has a low-refractive-index layer which consists of hardened | cured material which hardened the curable resin composition as described in any one of Claims 1-5.

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