JP2008019402A - Curable resin composition and antireflection film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition excellent in scratch resistance, stainproofing properties and especially wiping properties of an oily dye, and to provide an antireflection film. <P>SOLUTION: The curable resin composition comprises (A) a fluorine-containing polymer containing an ethylenically unsaturated group, (B) a silicone compound having a siloxane skeleton and three or more (meth)acryloyl groups and having a number average molecular weight of 7,000 or more and (C) a (meth)acrylate compound other than the compounds (A) and (B). A cured film produced by curing the curable resin composition is provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a curable resin composition and an antireflection film.

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 demand for an antireflection film including a low refractive index layer made of an excellent cured film.
In these display panels, surface characteristics that can easily remove attached fingerprints, dust, etc. (antifouling properties) are required, and the surface is often wiped with gauze impregnated with ethanol, etc. to remove dust, Scratch resistance is required.

  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, such a fluororesin-based paint has a problem that it is poor in antifouling property, scratch resistance and durability.

  Therefore, in (Patent Document 4), by introducing a specific amount of polysiloxane skeleton into the main chain of the fluorine-based copolymer, the friction between the coating film surface and the cloth is reduced and the cloth abrasion resistance is improved. Is described.

JP 57-34107 A JP 59-189108 A JP 60-67518 A JP 2005-290119 A

However, the above-described conventional resin compositions have not been sufficient in the obtained scratch resistance and antifouling properties, particularly the wipeability of oily dyes.
Then, an object of this invention is to provide the curable resin composition and antireflection film which are excellent in abrasion resistance and antifouling property, especially the wipeability of an oil-based dye.

According to the present invention, the following curable resin composition, cured film and antireflection film are provided.
[1] (A) Ethylenically unsaturated group-containing fluoropolymer, (B) A silicone compound having a siloxane skeleton, having 3 or more (meth) acryloyl groups, and having a number average molecular weight of 7000 or more, ( C) (meth) acrylate compounds excluding (A) and (B),
A curable resin composition comprising:
[2] The curable resin composition according to [1], wherein the silicone compound has a (meth) acryloyl group at a terminal thereof.
[3] The curable resin composition according to [2], wherein the silicone compound has (meth) acryloyl groups at both ends thereof.
[4] The curable resin composition according to any one of [1] to [3], wherein the silicone compound has a (meth) acryloyl group in a side chain of the siloxane skeleton.
[5] The curable resin composition according to any one of [1] to [4], wherein the (meth) acrylate compound has two or more (meth) acryloyl groups.
[6] The curable resin composition according to any one of [1] to [5], further comprising (D) a particle having a number average particle diameter of 1 to 100 nm mainly composed of silica. .
[7] The curable resin composition according to any one of [1] to [6], wherein the curable resin composition is for an antireflection film.
[8] A cured film obtained by curing the curable resin composition according to any one of [1] to [7].
[9] An antireflection film comprising a layer comprising the film according to [8].

According to the curable resin composition of the present invention, a cured film having excellent antifouling properties and scratch resistance and an antireflection film containing the cured film can be obtained.
In addition, the cured film of the present invention contains a silicone compound, but when the coating film is rolled, the silicone compound is less likely to adhere to the back side of the coating film. There is no problem in the display manufacturing process.

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

1. Curable resin composition The curable resin composition of this invention (henceforth the composition of this invention) may contain the following component (A)-(G). Among these components, (A) to (C) are essential components, and (D) to (G) are optional components that can be appropriately contained.
(A) an ethylenically unsaturated group-containing fluoropolymer,
(B) Silicone compounds having a siloxane skeleton, having at least 3 (meth) acryloyl groups, and having a number average molecular weight of 4,000 or more (C) (A), (Meth) acrylate compounds excluding (B) ,
(D) Particles having a number average particle size of 1 to 100 nm mainly composed of silica,
(E) Compound that generates active species by irradiation of radiation or heat (F) Organic solvent (G) Other additives These components will be described below.

(A) Ethylenically unsaturated group-containing fluorinated polymer The ethylenically unsaturated group-containing fluorinated polymer (A) is a polymer of a fluorinated olefin. By the component (A), the composition of the present invention exhibits basic performance as a low refractive index material for an antireflection film such as low refractive index, antifouling property, chemical resistance, and water resistance.
The component (A) preferably has a (meth) acryl group in the side chain. Thereby, it can co-crosslink with a radically polymerizable (meth) acryl compound, and abrasion resistance improves.

  The ethylenically unsaturated group-containing fluoropolymer is obtained by reacting an ethylenically unsaturated group-containing isocyanate compound with a hydroxyl group-containing fluoropolymer. That is, the hydroxyl group of the hydroxyl group-containing fluoropolymer is modified with an ethylenically unsaturated group-containing isocyanate compound.

(1) Ethylenically unsaturated group-containing isocyanate compound The ethylenically unsaturated group-containing isocyanate compound may be a compound containing one isocyanate group and at least one ethylenically unsaturated group in the molecule. There is no particular limitation.
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.
Examples of the ethylenically unsaturated group-containing isocyanate compound include one kind of 2- (meth) acryloyloxyethyl isocyanate and 2- (meth) acryloyloxypropyl isocyanate, or a combination of two or more kinds.

The ethylenically unsaturated group-containing isocyanate compound can also be synthesized by reacting diisocyanate and a hydroxyl group-containing (meth) acrylate.
As examples of diisocyanates, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), and 1,3-bis (isocyanate methyl) cyclohexane are preferred.

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 an optical characteristic of the fluorine-containing material intended by the present invention, while the content is contained. 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).
(D) A structural unit represented by the following formula (4).

［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］

[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).

  (E) A structural unit represented by the following formula (6).

［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。］

[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).

  (F) A structural unit represented by the following formula (8).

［式（８）中、Ｒ¹⁸は乳化作用を有する基を示す］

[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.

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

［式（９）中、ｎは１〜２０の数、ｍは０〜４の数、ｕは３〜５０の数を示す］

[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 fluorine-containing polymer is preferably an isocyanate group / hydroxyl group molar ratio of the above-described ethylenically unsaturated group-containing isocyanate compound and a hydroxyl group-containing fluorine-containing polymer. Is obtained at a ratio 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 10 to 60% 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 10% by weight, the refractive index of the cured coating film of the radiation curable resin composition increases, and a sufficient antireflection effect may not be obtained. This is because if the amount exceeds 60% by weight, the scratch resistance of the cured coating film of the radiation curable resin composition may not be obtained.
For this reason, the amount of component (A) added is more preferably 15 to 55% by weight, and still more preferably 20 to 50% by weight.

(B) Silicone Compound A compound having a siloxane skeleton as the silicone compound, at least three (meth) acryloyl groups, and a number average molecular weight of 4,000 or more is blended in the composition of the present invention. By blending such a silicone compound, the scratch resistance and antifouling properties of the cured film obtained by curing the curable resin composition and the antireflection film using the cured resin composition, in particular, the wiping property of oily dyes is improved. .
Examples of the silicone compound include a compound having a (meth) acryloyl group at its terminal, a compound having a (meth) acryloyl group at both terminals, or a compound having a (meth) acryloyl group in the side chain of the siloxane skeleton. .

  Examples of the compound having a (meth) acryloyl group at the terminal or both terminals of the siloxane skeleton include a silicone compound (B) represented by the following formula (11).

式（１１）において、Ｒ^３２及びＲ^３３は、それぞれ独立に、炭素数１〜３のアルキル基であり、メチル基が好ましい。また、Ｒ^３１、Ｒ^３４のいずれか１以上は（メタ）アクリロイル基を有する基である。式（１１）で表されるシリコーン化合物として３以上の（メタ）アクリロイル基を有することが好ましい。ａは、シリコーン化合物（Ｂ）の数平均分子量が４，０００以上となる１以上の整数であり、通常は、４０〜５００の整数である。尚、シリコーン化合物（Ｂ）の数平均分子量は４，０００以上であるが、大きい方が滑りが良く防汚性が高くなるが、７，０００以上であることが好ましく、９，０００以上であることがさらに好ましい。ここで、シリコーン化合物（Ｂ）の数平均分子量は、ポリスチレンを分子量標準とするゲルパーミエーションクロマトグラフィー法によって測定したものである。ｂは１〜４の整数であり、３が好ましい。

In the formula (11), R ³² and R ³³ are each independently an alkyl group having 1 to 3 carbon atoms, preferably a methyl group. One or more of R ³¹ and R ³⁴ is a group having a (meth) acryloyl group. The silicone compound represented by the formula (11) preferably has 3 or more (meth) acryloyl groups. a is an integer greater than or equal to 1 where the number average molecular weight of the silicone compound (B) is 4,000 or more, and is usually an integer of 40 to 500. The number average molecular weight of the silicone compound (B) is 4,000 or more, but the larger one has better slipping and higher antifouling properties, but it is preferably 7,000 or more and 9,000 or more. More preferably. Here, the number average molecular weight of the silicone compound (B) is measured by a gel permeation chromatography method using polystyrene as a molecular weight standard. b is an integer of 1-4, and 3 is preferable.

  The compound having a (meth) acryloyl group in the side chain of the siloxane skeleton includes a structural unit represented by the following formula (12) and a structural unit represented by the following formula (13). And a compound having at least 3 structural units represented by

式（１２）において、Ｒ^３６、Ｒ^３７は、それぞれ独立に、炭素数１〜３のアルキル基であり、メチル基が好ましい。

In Formula (12), R ^<36> , R ^<37 > is a C1-C3 alkyl group each independently, and a methyl group is preferable.

式（１３）において、Ｒ^３８は炭素数１〜３のアルキル基であり、メチル基が好ましい。また、Ｒ^３９は少なくとも１以上の（メタ）アクリロイル基を有する基である。

In the formula ^{(13), R 38} is an alkyl group having 1 to 3 carbon atoms, preferably a methyl group. R ³⁹ is a group having at least one (meth) acryloyl group.

The amount of the component (B) added is not particularly limited, but is usually 0.1 to 20% by weight with respect to the total amount of the composition other than the organic solvent. The reason for this is that if the addition amount is less than 0.1% by weight, the antifouling property of the cured coating film of the radiation curable resin composition may be insufficient, while the addition amount is 20% by weight. This is because there may be inconveniences such as peeling of the silicon compound from the surface of the cured coating film.
For this reason, the amount of component (B) added is more preferably 0.5 to 10% by weight, and even more preferably 1 to 10% by weight.

(C) (Meth) acrylate compound The (meth) acrylate compound is a compound excluding the ethylenically unsaturated group-containing fluoropolymer (A) and the silicone compound (B), and is obtained by curing the curable resin composition. It is used to enhance the scratch resistance of the cured film and the antireflection film using the cured film.

The compound is not particularly limited as long as it is a compound containing at least one (meth) acryloyl group in the molecule.
Examples of the monomer having one (meth) acryloyl group include acrylamide, (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, and isobornyloxyethyl. (Meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (Meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopente (Meth) acrylate, N, N-dimethyl (meth) acrylamide tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2 -Tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate, vinylcaprolactam, N-vinylpyrrolidone, phenoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, pentachloropheny Compounds represented by (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, bornyl (meth) acrylate, methyltriethylenediglycol (meth) acrylate It can be illustrated. Of these monofunctional monomers, isobornyl (meth) acrylate, lauryl (meth) acrylate, and phenoxyethyl (meth) acrylate are particularly preferable.

  As a commercial item of these monofunctional monomers, for example, Aronix M-101, M-102, M-111, M-113, M-117, M-152, TO-1210 (above, manufactured by Toagosei Co., Ltd.) ), KAYARAD TC-110S, R-564, R-128H (Nippon Kayaku Co., Ltd.), Biscoat 192, Biscoat 220, Biscoat 2311HP, Biscoat 2000, Biscoat 2100, Biscoat 2150, Biscoat 8F, Biscoat 17F (above , Osaka Organic Chemical Industry Co., Ltd.).

Examples of the monomer having two or more (meth) acryloyl groups include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, Bis ((meth) acryloyloxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane (also referred to as “tricyclodecanediyldimethylene di (meth) acrylate”), tris (2-hydroxyethyl) isocyanurate Di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate Ethylene oxide (hereinafter referred to as “EO”) modified trimethylolpropane tri (meth) acrylate, propylene oxide (hereinafter referred to as “PO”) modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, bisphenol A diglycidyl ether end (meth) acrylic acid adduct, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acryl Rate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate , EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) acrylate, EO modified hydrogenated bisphenol A di (meth) acrylate, PO modified hydrogenated bisphenol A di (meth) acrylate, EO modified bisphenol F di In addition to (meth) acrylate, (meth) acrylate of phenol novolac polyglycidyl ether, etc., the compound represented by the following formula (14) can be exemplified. That.

［式（１４）中、「Ａｃｒｙｌ」は、アクリロイル基を示す。］

[In the formula (14), “Acryl” represents an acryloyl group. ]

  Examples of commercially available products of these multifunctional monomers include SA1002 (manufactured by Mitsubishi Chemical Corporation), biscoat 195, biscoat 230, biscoat 260, biscoat 215, biscoat 310, biscoat 214HP, biscoat 295, biscoat 300, Biscoat 360, Biscoat GPT, Biscoat 400, Biscoat 700, Biscoat 540, Biscoat 3000, Biscoat 3700 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Kayarad R-526, HDDA, NPGDA, TPGDA, MANDA, R-551, R-712, R-604, R-684, PET-30, GPO-303, TMPTA, THE-330, DPHA, DPHA-2H, DPHA-2C, DPHA-2I, D-310, D-330, DPCA 20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, T-1420, T-2020, T-2040, TPA-320, TPA-330, RP-1040, RP-2040, R-011, R-300, R-205 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-220, M-233, M-240, M-215, M-305, M- 309, M-310, M-315, M-325, M-400, M-6200, M-6400 (above, manufactured by Toagosei Co., Ltd.), light acrylate BP-4EA, BP-4PA, BP-2EA, BP-2PA, DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.), New Frontier BPE-4, BR-42M, GX-8345 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), ASF 400 (above, manufactured by Nippon Steel Chemical Co., Ltd.), Lipoxy SP-1506, SP-1507, SP-1509, VR-77, SP-4010, SP-4060 (above, Showa Polymer Co., Ltd.), NK ester A-BPE-4 (manufactured by Shin-Nakamura Chemical Co., Ltd.).

  Of these, the composition of the present invention preferably contains a compound containing at least two (meth) acryloyl groups in the molecule. More preferably, a compound containing at least 3 (meth) acryloyl groups in the molecule is particularly preferable. The three or more compounds can be selected from the tri (meth) acrylate compounds exemplified above, tetra (meth) acrylate compounds, penta (meth) acrylate compounds, hexa (meth) acrylate compounds, and the like. Of these, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) Acrylate is particularly preferred. Each of the above compounds may be used alone or in combination of two or more.

  Further, the (meth) acrylate compound may contain fluorine. Examples of such compounds include perfluorooctylethyl (meth) acrylate, octafluoropentyl (meth) acrylate, trifluoroethyl (meth) acrylate, and polyfunctional (meth) acrylate compounds represented by the following general formula (15) Or a combination of two or more. The (meth) acrylate compound containing fluorine is used for reducing the reflectance and improving the scratch resistance of a cured product obtained by curing a curable resin composition and an antireflection film using the cured product.

一般式（１５）で表される化合物の市販品としては、共栄社化学株式会社製ＬＩＮＣ−３Ａ（一般式（１５）で表される化合物の含有量：６５重量％、ペンタエリスリトールテトラアクリレート：３５重量％）が挙げられる。

As a commercial item of the compound represented by the general formula (15), Kyoeisha Chemical Co., Ltd. LINC-3A (content of the compound represented by the general formula (15): 65 wt%, pentaerythritol tetraacrylate: 35 wt% %).

The addition amount of the (meth) acrylate compound is not particularly limited, but is usually 1 to 88% by weight with respect to the total amount of the composition other than the organic solvent. The reason for this is that if the addition amount is less than 1% by weight, the scratch resistance of the cured coating film of the radiation curable resin composition may not be obtained, whereas if the addition amount exceeds 88% by weight. This is because the refractive index of the cured coating film of the radiation curable resin composition becomes high and a sufficient antireflection effect may not be obtained.
For this reason, the amount of component (C) added is more preferably 1 to 60% by weight, and even more preferably 1 to 40% by weight.

(D) Particles having a number average particle diameter of 1 to 100 nm mainly composed of silica. In the curable resin composition of the present invention, the scratch resistance of a cured film obtained by curing the curable resin composition of the present invention, In particular, in order to improve steel wool resistance, particles (D) having a number average particle diameter of 1 to 100 nm mainly composed of silica can be blended. The number average particle diameter is measured with a transmission electron microscope. The number average particle diameter of the component (D) is preferably 5 to 80 nm, and more preferably 10 to 60 nm.
As these particles containing silica as a main component, known particles can be used, and the shape is not particularly limited. As long as it is spherical, it is not limited to ordinary colloidal silica, and may be hollow particles, porous particles, core-shell type particles, or the like. Moreover, it is not limited to a spherical shape, and may be an irregularly shaped particle. Colloidal silica having a solid content of 10 to 40% by weight is preferred.

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 methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethylformamide and dimethyl Examples include amides such as acetamide 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 item of the particle | grains which have a silica as a main component, as a colloidal silica, for example, Nissan Chemical Industries Ltd. brand name: Methanol silica sol, IPA-ST, MEK-ST, MEK-ST-S, MEK-ST- L, IPA-ZL, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL etc. can be mentioned.

  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, those having NH2 groups as reactive groups, such as urea propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Methoxysilane and the like having an OH group, bis (2-hydroxyethyl) -3aminotripropylmethoxysilane and the like having an isocyanate group, 3-isocyanatopropyltrimethoxysilane and the like having a thiocyanate group 3- As those having an thiol group, such as (3-glycidoxypropyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. having an epoxy group such as thiocyanate propyltrimethoxysilane, Mercaptopropyltrimethoxy Silane, and the like can be given. A preferred compound is 3-mercaptopropyltrimethoxysilane.

  Moreover, it is preferable that the particle | grains (D) which have a silica as a main component are surface-treated by the organic compound containing a polymerizable unsaturated group. Such surface treatment enables co-crosslinking with the UV curable acrylic monomer and improves the scratch resistance.

  The amount of the silica-based particles (D) in the resin composition is usually 1 to 40% by weight based on the total amount of the composition other than the organic solvent, regardless of whether or not the surface treatment is performed. % By weight is preferred, and 1 to 10% by weight is more preferred. 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.

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

(1) Compound that generates active species upon irradiation with radiation As a compound that generates active species upon irradiation with radiation (hereinafter referred to as “photopolymerization initiator”), a photo radical generator that generates radicals as active species, etc. Is mentioned. Radiation is defined as energy rays that can decompose active compounds to generate active species. Examples of such radiation 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.

  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-dodecylphenyl) -2 -Hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, triphenylamine, 2,4,6-trimethylbenzoyldiphenyl Phosphine oxide, 1-H Roxycyclohexyl 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-benzoyl -4′-methyldiphenyl sulfide, benzyl, or a combination of BTTB and xanthene, thioxanthene, coumarin, ketocoumarin, a compound represented by formula (16), 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, a compound represented by the formula (16), and the like are preferable, and 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholine are more preferable. Linopropan-1-one, 2- (dimethylamino) -1- [4- (morpholinyl) Eniru] -2-phenyl-methyl) -1-butanone, can be exemplified compounds represented by the formula (16).
The photopolymerization initiator represented by the formula (16) is Irgacure 127 manufactured by Ciba Specialty Chemicals. Even when this initiator is used alone or in combination with another polymerization initiator, it is excellent in a cured product obtained by curing the composition of the present invention with a low irradiation light amount of 0.2 J / cm ² or less. High scratch resistance can be exhibited.

  The addition amount of the photopolymerization initiator is not particularly limited, but is preferably 0.1 to 10% 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 0.1% by weight, the curing reaction becomes insufficient, and the scratch resistance and the scratch resistance after immersion in an alkaline aqueous solution may be lowered. On the other hand, when the addition amount of the photopolymerization initiator exceeds 10% by weight, the refractive index of the cured film increases and the antireflection effect may be lowered. For this reason, the amount of photopolymerization initiator added is more preferably 1 to 5% by weight based on the total amount of the composition other than the organic solvent.

(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.

  Examples of thermal radical generators include benzoyl peroxide, tert-butyl-oxybenzoate, azobisisobutyronitrile, acetyl peroxide, lauryl peroxide, tert-butyl peracetate, cumyl peroxide, tert-butyl peroxide , Tert-butyl hydroperoxide, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc. The combination of the above can be mentioned.

  The addition amount of the thermal polymerization initiator is not particularly limited, but is preferably 0.1 to 10% 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 0.1% by weight, the curing reaction becomes insufficient, and the scratch resistance and the scratch resistance after immersion in an alkaline aqueous solution may be lowered. On the other hand, when the addition amount of the photopolymerization initiator exceeds 10% by weight, the refractive index of the cured film increases and the antireflection effect may be lowered. For this reason, it is more preferable to add 1 to 5% by weight of the thermal polymerization initiator based on the total amount of the composition other than the organic solvent.

(F) Organic solvent It is preferable to add an organic solvent to the curable resin composition. Thus, by adding an organic solvent, the low-refractive-index layer of the antireflection film which is a thin film can be formed uniformly, and as a result, the thickness of the antireflection film can also 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 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.

(G) Additive The curable resin composition has a photosensitizer, a polymerization inhibitor, a polymerization initiator, an ultraviolet absorber, an antioxidant, and an antistatic agent as long as the objects and effects of the present invention are not impaired. It is also preferable to further contain additives such as inorganic fillers or pigments and dyes other than the component (D).

2. Antireflective film The antireflective film of this invention contains the low refractive index layer which consists of a cured film which hardened | cured 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 cured film 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 film 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 1.47 or less. . This is because when the refractive index of the low refractive index film exceeds 1.47, the antireflection effect may be significantly reduced when combined with the high refractive index film. Further, the refractive index of the low refractive index film is more preferably 1.46 or less.
When a plurality of low refractive index films are provided, at least one of the low refractive index films only needs to have a refractive index value within the above-described range. Therefore, the other low refractive index films exceed 1.47. 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 set to 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. Further, 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.

(Synthesis of ethylenically unsaturated group-containing fluoropolymer A (methacryl-modified fluoropolymer))
First, a hydroxyl group-containing fluoropolymer was synthesized. A 2.0-liter stainless steel autoclave 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, 44.0 g of hydroxyethyl vinyl ether, Lauroyl oxide 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 nonionic reactive emulsifier (NE-30) 20.0 g (trade name) manufactured by Asahi Denka Kogyo Co., Ltd. was charged, cooled to −50 ° C. with dry ice-methanol, and then oxygen in the system was removed again with nitrogen gas.

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 referred to as a hydroxyl group-containing fluoropolymer. Table 1 shows the monomers and solvents used.

Attached to the obtained hydroxyl group-containing fluoropolymer, the number average molecular weight in terms of polystyrene by gel permeation chromatography and the fluorine content by the alizarin complexone method were measured. ^{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. 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)

Subsequently, an ethylenically unsaturated group-containing fluoropolymer was synthesized using the obtained hydroxyl group-containing fluoropolymer. In a 1-liter separable flask equipped with a magnetic stirrer, a glass cooling tube and a thermometer, 50.0 g of the hydroxyl group-containing fluoropolymer obtained in Production Example 1 was used as a polymerization inhibitor and 2,6-di- 0.01 g of t-butylmethylphenol and 370 g of methyl isobutyl ketone (MIBK) were charged and stirred at 20 ° C. until the hydroxyl group-containing fluoropolymer 1 was dissolved in MIBK and the solution became transparent 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 to 55. A MIBK solution of the ethylenically unsaturated group-containing fluoropolymer A 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.

(Regarding particle B containing silica as a main component)
As the particle B containing silica as a main component, methyl ethyl ketone hollow silica sol (manufactured by Catalyst Chemical Industry Co., Ltd., trade name: JX-1009 SIV (number average particle diameter 30 to 40 nm, silica concentration 30%)) was used.

(Compound C-1)
The compound C-1 has a number average molecular weight of 16,000, manufactured by Rad2600: Tego, and includes a structural unit represented by the following formula (17) and a structural unit represented by the following formula (18). And has six structural units represented by the following formula (18).

(Compound C-2)
Compound C-2 as shown in the following formula (19) was synthesized as follows. 95.26 parts of α, ω- (3-propylhydroxy) -polydimethylsiloxane (manufactured by Chisso Corporation, trade name: Silaplane FM-4425, number average molecular weight: 10,000) in dry air, dibutyltin lauryl For a solution of 0.08 part of the rate and 100 parts of methyl isobutyl ketone (MIBK), 4.74 parts of 1.1-bis (acryloyloxymethyl) ethyl isocyanate (manufactured by Showa Denko, trade name: Karenz BEI) at 60 ° C. After dropwise addition over 1 hour with stirring, the mixture was heated and stirred at 60 ° C. for 3 hours. Let the obtained compound be C-2.

［式（１９）中、ａは、化合物（Ｃ−２）の数平均分子量が１０，０００となる整数である。]

[In Formula (19), a is an integer with which the number average molecular weight of a compound (C-2) will be 10,000. ]

(Compound C-3)
Compound C-3 as shown in the following formula (20) was synthesized as follows. In dry air, 69.48 parts α-butyl-ω- (3-propylhydroxy) -polydimethylsiloxane (manufactured by Chisso Corporation, trade name: Silaplane FM-0425, number average molecular weight: 10,000), 0.08 parts of dibutyltin laurate and 3.54 parts of isophorone diisocyanate were added dropwise over 1 hour while stirring at 60 ° C., followed by heating and stirring at 60 ° C. for 3 hours. Thereafter, 8.15 parts of pentaerythritol triacrylate was added dropwise over 1 hour, followed by stirring with heating at 60 ° C. for 3 hours. Let the obtained compound be C-3.

［式（２０）中、ｂは、化合物（Ｃ−３）の数平均分子量が１０，０００となる整数である。]

[In Formula (20), b is an integer from which the number average molecular weight of a compound (C-3) becomes 10,000. ]

(Compound C-4)
Compound C-4 represented by the following formula (21) was synthesized as follows. In dry air, α, ω- (3-propylhydroxy) -polydimethylsiloxane (manufactured by Chisso Corporation, trade name: Silaplane FM-4425, number average molecular weight: 10,000), 76.62 parts, dibutyltin lauri 0.08 parts of the rate and 7.08 parts of isophorone diisocyanate were added dropwise over 1 hour while stirring at 60 ° C., followed by heating and stirring at 60 ° C. for 3 hours. Thereafter, 16.30 parts of pentaerythritol triacrylate was added dropwise over 1 hour, followed by stirring with heating at 60 ° C. for 3 hours. The obtained compound is designated as C-4.

［式（２１）中、ｃは、化合物（Ｃ−４）の数平均分子量が１０，０００となる整数である。］

[In formula (21), c is an integer with which the number average molecular weight of a compound (C-4) becomes 10,000. ]

(Compound C-5)
Compound C-5 as shown in the following formula (22) was synthesized as follows. In dry air, 69.48 parts α-butyl-ω- (3-propylhydroxy) -polydimethylsiloxane (manufactured by Chisso Corporation, trade name: Silaplane FM-0425, number average molecular weight: 5,000), 0.16 parts of dibutyltin laurate and 7.08 parts of isophorone diisocyanate were added dropwise with stirring at 60 ° C. over 1 hour, followed by heating and stirring at 60 ° C. for 3 hours. Thereafter, 16.30 parts of pentaerythritol triacrylate was added dropwise over 1 hour, followed by stirring with heating at 60 ° C. for 3 hours. Let the obtained compound be C-5.

［式（２２）中、ｄは、化合物（Ｃ−５）の数平均分子量が５，０００となる整数である。］

[In Formula (22), d is an integer from which the number average molecular weight of a compound (C-5) becomes 5,000. ]

(Compound C-6)
The structural formula and number average molecular weight of Compound C-6 are shown below. Azo group-containing polydimethylsiloxane represented by formula (23) (polycondensation product of 4,4′-azobis (4-cyanovaleric acid) and α, ω-bis (3-aminopropyl) polydimethylsiloxane) (VPS1001) : Wako Pure Chemical Industries, number average molecular weight: 60,000)

［式（２３）中、ｅ及びｆは、化合物（Ｃ−６）の数平均分子量が１０，０００となる整数である。］

[In formula (23), e and f are integers with which the number average molecular weight of the compound (C-6) is 10,000. ]

(Compound C-7)
The structural formula and number average molecular weight of the compound of compound C-7 are shown below.
Silaplane FM-0725: manufactured by Chisso Corporation, number average molecular weight: 10,000

［式（２４）中、ｇは、化合物（Ｃ−７）の数平均分子量が１０，０００となる整数である。］

[In Formula (24), g is an integer from which the number average molecular weight of a compound (C-7) will be 10,000. ]

(Compound C-8)
The structural formula and number average molecular weight of the compound C-8 are shown below.
Silaplane FM-7725: manufactured by Chisso Corporation, number average molecular weight: 10,000

［式（２５）中、ｈは、化合物（Ｃ−８）の数平均分子量が１０，０００となる整数である。］

[In Formula (25), h is an integer with which the number average molecular weight of a compound (C-8) becomes 10,000. ]

(Compound C-9)
The structural formula and number average molecular weight of the compound of Compound C-9 are shown below.
Silaplane FM0425: manufactured by Chisso Corporation, number average molecular weight: 10,000

［式（２６）中、ｉは、化合物（Ｃ−９）の数平均分子量が１０，０００となる整数である。］

[In Formula (26), i is an integer with which the number average molecular weight of a compound (C-9) becomes 10,000. ]

(Compound C-10)
Compound C-10 represented by the following formula (27) was synthesized as follows. In dry air, 69.48 parts α-butyl-ω- (3-propylhydroxy) -polydimethylsiloxane (manufactured by Chisso Corporation, trade name: Silaplane FM-0411, number average molecular weight: 1,000), 0.08 parts of dibutyltin laurate and 13.18 parts of isophorone diisocyanate were added dropwise with stirring at 60 ° C. over 1 hour, followed by heating and stirring at 60 ° C. for 3 hours. Thereafter, 17.34 parts of pentaerythritol triacrylate was added dropwise over 1 hour, and the mixture was heated and stirred at 60 ° C. for 3 hours. Let the obtained compound be C-10.

［式（２７）中、ｊは化合物（Ｃ−１０）の数平均分子量が１，０００となる数である。］

[In the formula (27), j is a number such that the number average molecular weight of the compound (C-10) is 1,000. ]

(Compound C-11)
The compound of compound C-11 has a number average molecular weight of 2,500, manufactured by Rad2100: Tego, and includes a structural unit represented by the above formula (17) and a structural unit represented by the above formula (18). And has 5 structural units represented by the above formula (18).

(Compound C-12)
Compound C-12 represented by the following formula (28) was synthesized as follows. 95.26 parts of α-butyl-ω- (3-propylhydroxy) -polydimethylsiloxane (manufactured by Chisso Corporation, trade name: Silaplane FM-0425, number average molecular weight: 10,000) in dry air; 60 parts of 1.37 parts of 1.1-bis (acryloyloxymethyl) ethyl isocyanate (made by Showa Denko, trade name: Karenz BEI) with respect to a solution of 0.08 parts of dibutyltin laurate and 100 parts of methyl isobutyl ketone (MIBK) The mixture was added dropwise over 1 hour while stirring at 0 ° C., and then heated and stirred at 60 ° C. for 3 hours. Let the obtained compound be C-12.

［式（２８）中、ｋは化合物Ｃ−１２数平均分子量が１０，０００となる数である。］

[In formula (28), k is a number which becomes the compound C-12 number average molecular weight 10,000. ]

(Preparation of silica particle-containing composition for hard coat layer)
In a container shielded from ultraviolet rays, particles containing silica as a main component are 30 parts as solids), 65 parts of dipentaerythritol hexaacrylate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopro By stirring 5 parts of pan-1-one and 44 parts of MIBK at 50 ° C. for 2 hours, a composition for a hard coat layer having a uniform solution was obtained. 2 g of this composition 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 50% by weight.

(Preparation of substrate for coating curable resin composition)
On the TAC film (thickness: 50 μm), the prepared silica particle-containing composition for hard coat layer was applied with a wire bar coater to a thickness of 3 μm, and dried in an oven at 80 ° C. for 1 minute to form a coating film. Formed. 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.

(Example 1)
As shown in Table 4, the MIBK solution of the ethylenically unsaturated group-containing fluorinated polymer A obtained by synthesis was 14 parts by weight, pentaerythritol triacrylate (PET-30, Nippon Kayaku Co., Ltd.) 5 parts by weight, 15 parts by weight of a polyfunctional acrylate represented by formula (15), 60 parts by weight of particles B containing silica as a main component, and a compound represented by formula (16) as a photopolymerization initiator ( Irgacure 127 (manufactured by Ciba Specialty Chemicals) 3 parts by weight, 3 parts by weight of compound C-1 and 100 parts by weight of MIBK were charged into a glass separable flask equipped with a stirrer and stirred at room temperature for 1 hour for uniform curing. A functional resin composition was obtained.

(Examples 2-11, Comparative Examples 1-7)
Each curable composition was obtained in the same manner as in Example 1 except that the composition in Table 4 was followed. The unit of composition of each component in the table is parts by weight.

(Evaluation Example 1) Refractive Index Measurement of Cured Film Each curable resin composition was applied onto a silicon wafer with a spin coater so that the thickness after drying was about 0.1 μm, and then a high-pressure mercury lamp was placed under nitrogen. It was cured by irradiating with ultraviolet rays under light irradiation conditions of 0.3 mJ / cm ² . About the obtained cured film, the refractive index (nD25) in wavelength 539nm in 25 degreeC was measured using the ellipsometer. The results are shown in Table 1.

(Evaluation example 2) Evaluation of the turbidity of a cured film About the obtained cured film, turbidity was evaluated by the permeation | transmission type | mold measurement method by Suga Test Co., Ltd. color haze meter * SC-3H. The evaluation criteria are as follows. The results are shown in Table 1.
○: 0.39 or less ×: 0.40 or more

(Evaluation example 3) Scratch resistance test of antireflection film (steel wool resistance test)
For the antireflection film obtained in Evaluation Example 1, steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) is used as a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.). The surface of the cured film was repeatedly rubbed 10 times under the condition of a load of 500 g, and 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 1.
A: Hardened film peeling or scratches are hardly observed.
○: Slight thin scratches are observed on the cured film.
Δ: Streaky scratches are observed on the entire surface of the cured film.
X: Peeling of the cured film occurs.

(Evaluation Example 4) Evaluation Method of Repeated Magic Wipe of Antireflection Film About 0.25 cm ² (0.5 cm × 0.5 cm) of the antireflection film surface obtained in Evaluation Example 1 is an oil-based dye ink type marking pen (Zebra Co., Ltd., trade name: Mackey). After naturally drying for 30 seconds, the area coated with the marker is wiped off with a non-woven fabric (Bencot) (first time). Further, the same portion was coated with an oil marker, and wiping was repeated in the same manner until the oil ink could not be wiped off. Table 1 shows the number of repetitions in which the oil-based ink could be wiped off.

(Evaluation example 5) Evaluation method of Si non-peelability from cured film surface Each curable resin composition was coated on a PET film using a wire bar coater so that the film thickness was about 200 nm, and at 80 ° C. It was dried for 1 minute to form a coating film. Next, using a high-pressure mercury lamp in a nitrogen atmosphere, ultraviolet rays were irradiated under a light irradiation condition of 0.3 mJ / cm ² to prepare a coated film.
Next, the coated film was cut into a length of 15 cm and a width of 5 cm, and then a sample that was overlapped so that the coated surface and the TAC were in contact with the TAC film cut into the same size was produced. A load of 3 kg / cm ² was applied to the center of this sample, and the sample was left in a constant temperature room (temperature 23 ° C., humidity 50%) for 24 hours. After 24 hours, the portion to which the sample was applied was peeled off, and the surface of the TAC film was subjected to X-ray photoelectron spectroscopy (ESCA) measurement (manufactured by ULVAC-PHI Co., Ltd., PHI Model 5400).
The measurement conditions are as follows.
Measuring angle: 45 degrees Measuring element: Si, C
Integration count: Si 10 times, C 1 time

Measurement was performed at three points per sample, and the average value was evaluated according to the following evaluation criteria.
A: Si amount with respect to C amount is 3% or less.
○: Si amount relative to C amount is 5% or less Δ: Si amount relative to C amount is 15% or less

The curable resin composition of the present invention is excellent in antifouling property, scratch resistance, coating property and durability, and is particularly useful as an antireflection film.
In addition, the cured film of the present invention contains a siloxane compound, but when the coating film is rolled, the Si component is less likely to adhere to the back side of the coating film. There is no problem in the display manufacturing process.

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 14 Hard-coat layer 16 High refractive index layer 18 Low refractive index layer

Claims (9)

(A) an ethylenically unsaturated group-containing fluoropolymer,
(B) A silicone compound having a siloxane skeleton and having at least three (meth) acryloyl groups and a number average molecular weight of 4,000 or more (C) (Meth) acrylate compounds excluding (A) and (B) ,
A curable resin composition comprising:   The curable resin composition according to claim 1, wherein the silicone compound has a (meth) acryloyl group at a terminal thereof.   3. The curable resin composition according to claim 2, wherein the silicone compound has (meth) acryloyl groups at both ends thereof.   The curable resin composition according to any one of claims 1 to 3, wherein the silicone compound has a (meth) acryloyl group in a side chain of the siloxane skeleton.   Curable resin composition in any one of Claims 1-4 WHEREIN: The (meth) acrylate compound has a 2 or more (meth) acryloyl group, The curable resin composition characterized by the above-mentioned.   Curable resin composition in any one of Claims 1-5 WHEREIN: Furthermore, (D) Curable resin composition containing the particle | grains whose number average particle diameters which have a silica as a main component are 1-100 nm.   The curable resin composition according to any one of claims 1 to 6, wherein the curable resin composition is used for an antireflection film.   A cured film obtained by curing the curable resin composition according to claim 1. An antireflection film comprising a layer comprising the film according to claim 8.

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