JP2008169364A - Curable resin composition and antireflection coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition capable of forming a cured product excellent in a low refractive index, scratch resistance and antifouling property, and to provide an antireflection coating having a layer of the low refractive index prepared from the cured product. <P>SOLUTION: This curable resin composition comprises (A) an ethylenically unsaturated group-containing fluoropolymer, (B) a compound represented by general formula (B-1) (wherein R<SP>b</SP>is a hydrogen atom or a methyl group), and (I) an organic solvent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a curable resin composition and an antireflection film. More specifically, it contains an ethylenically unsaturated group-containing fluorine-containing polymer and a (meth) acryloyl compound having a fluorine atom-containing substituent, has excellent coating properties, and has a low refractive index and scratch resistance when cured. The present invention relates to a curable resin composition from which a cured product having excellent properties can be obtained, and 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.

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). .

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 from the composition described in the above publication has a problem that the coating property and scratch resistance are not sufficient.

  In addition, in order to improve the scratch resistance of the antireflection film, a technique of adding silica particles to a low refractive index film that is the outermost layer of the antireflection film is widely used (for example, Patent Documents 5 and 6).

  Furthermore, in order to provide an antireflection film having a lower reflectivity, a material for a low refractive index film having a lower refractive index than before is desired. Therefore, by utilizing the fact that the refractive index of air is lower than that of a resin component such as acrylic, particles having voids inside the particles such as porous particles and hollow particles (hereinafter sometimes referred to as “hollow particles”). The technique used is known (for example, Patent Documents 7 to 9).

JP 57-34107 A JP 59-189108 A JP 60-67518 A JP 61-296073 A JP 2002-265866 A JP-A-10-316860 JP 2003-139906 A JP 2002-317152 A JP-A-10-142402

  Accordingly, an object of the present invention is to provide a curable resin composition that gives a cured product having a low refractive index, excellent scratch resistance and antifouling property, and an antireflection film having a low refractive index layer comprising the cured product. And

  In order to achieve the above object, the present inventors have conducted intensive research, and a curable resin composition obtained by adding a specific polyfunctional acrylic monomer to an ethylenically unsaturated group-containing fluoropolymer has an excellent low refractive index. The present invention was completed by finding that a cured product having scratch resistance was obtained.

［式（Ｂ−１）中、Ｒｂは水素原子又はメチル基である。］
２．さらに（Ｃ）２個以上の（メタ）アクリロイル基を有する（Ｂ）を除く化合物を含有する上記１に記載の硬化性樹脂組成物。
３．さらに（Ｈ）ポリジメチルシロキサン骨格を有する化合物を含有する、上記１又は２に記載の硬化性樹脂組成物。
４．下記成分（Ａ）、（Ｂ）及び（Ｉ）：
（Ａ）エチレン性不飽和基含有含フッ素重合体、
（Ｂ）下記一般式（Ｂ−１）で表される化合物、及び
（Ｉ）有機溶剤
を含有する硬化性樹脂組成物。

［式（Ｂ−１）中、Ｒｂは水素原子又はメチル基である。］
５．（Ａ）エチレン性不飽和基含有含フッ素重合体が、少なくとも１個のエチレン性不飽和基及び水酸基と反応可能な基を含有する化合物と、水酸基含有含フッ素重合体とを反応させて得られるエチレン性不飽和基含有含フッ素重合体である上記４に記載の硬化性樹脂組成物。
６．さらに、（Ｃ）２個以上の（メタ）アクリロイル基を有する（Ｂ）を除く化合物を含有する上記４又は５に記載の硬化性樹脂組成物。
７．さらに、（Ｄ）数平均粒径１〜１００ｎｍのシリカを主成分とする中空若しくは多孔質の粒子を含有する上記４〜６のいずれかに記載の硬化性樹脂組成物。
８．さらに、（Ｅ）数平均粒径１〜１００ｎｍのシリカを主成分とする中実の粒子を含有する上記４〜７のいずれかに記載の硬化性樹脂組成物。
９．前記（Ｄ）及び／又は（Ｅ）のシリカを主成分とする粒子が表面に（メタ）アクリロイル基を有する上記７又は８に記載の硬化性樹脂組成物。
１０．さらに、（Ｆ）１個の（メタ）アクリロイル基及び炭素数３以上の環状構造を有し、分子量が４００以下の化合物を含有する上記４〜９のいずれかに記載の硬化性樹脂組成物。
１１．さらに、（Ｇ）活性エネルギー線の照射により活性種を発生する化合物を含有する上記４〜１０のいずれかに記載の硬化性樹脂組成物。
１２．さらに、（Ｈ）ポリジメチルシロキサン骨格を有する化合物を含有する上記４〜１１のいずれかに記載の硬化性樹脂組成物。
１３０．さらに、（Ｊ）フッ素系界面活性剤を含有する上記４〜１２のいずれかに記載の硬化性樹脂組成物。
１４．反射防止膜用である上記１〜１３のいずれかに記載の硬化性樹脂組成物。
１５．上記１〜１３のいずれかに記載の硬化性樹脂組成物を硬化させて得られる硬化物。
１６．上記１５に記載の硬化物からなる低屈折率層を有する反射防止膜。 According to the present invention, the following curable resin composition and antireflection film are provided.
1. The following components (B), (D) and (I):
(B) a compound represented by the following general formula (B-1),
(D) A curable resin composition containing hollow or porous particles mainly composed of silica having a number average particle diameter of 1 to 100 nm, and (I) an organic solvent.

[In the formula (B-1), Rb represents a hydrogen atom or a methyl group. ]
2. The curable resin composition according to 1 above, further comprising (C) a compound other than (B) having two or more (meth) acryloyl groups.
3. The curable resin composition according to the above 1 or 2, further comprising (H) a compound having a polydimethylsiloxane skeleton.
4). The following components (A), (B) and (I):
(A) an ethylenically unsaturated group-containing fluoropolymer,
(B) A curable resin composition containing a compound represented by the following general formula (B-1) and (I) an organic solvent.

[In the formula (B-1), Rb represents a hydrogen atom or a methyl group. ]
5. (A) An ethylenically unsaturated group-containing fluoropolymer is obtained by reacting a compound containing at least one ethylenically unsaturated group and a group capable of reacting with a hydroxyl group with a hydroxyl group-containing fluoropolymer. 5. The curable resin composition as described in 4 above, which is an ethylenically unsaturated group-containing fluoropolymer.
6). Furthermore, (C) Curable resin composition of said 4 or 5 containing the compound except (B) which has a 2 or more (meth) acryloyl group.
7). Furthermore, (D) Curable resin composition in any one of said 4-6 containing the hollow or porous particle | grains which have a silica with a number average particle diameter of 1-100 nm as a main component.
8). Furthermore, (E) The curable resin composition in any one of said 4-7 containing the solid particle | grains which have a silica with a number average particle diameter of 1-100 nm as a main component.
9. 9. The curable resin composition according to 7 or 8 above, wherein the particles having (D) and / or (E) as a main component have a (meth) acryloyl group on the surface.
10. Further, (F) The curable resin composition according to any one of 4 to 9 above, which comprises a compound having one (meth) acryloyl group and a cyclic structure having 3 or more carbon atoms and having a molecular weight of 400 or less.
11. Furthermore, (G) Curable resin composition in any one of said 4-10 containing the compound which generate | occur | produces active species by irradiation of an active energy ray.
12 Furthermore, (H) The curable resin composition in any one of said 4-11 containing the compound which has polydimethylsiloxane frame | skeleton.
130. Furthermore, (J) Curable resin composition in any one of said 4-12 containing a fluorine-type surfactant.
14 The curable resin composition according to any one of 1 to 13 above, which is used for an antireflection film.
15. Hardened | cured material obtained by hardening the curable resin composition in any one of said 1-13.
16. 16. An antireflection film having a low refractive index layer comprising the cured product as described in 15 above.

ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition which gives the hardened | cured material which has a refractive index lower than before and excellent abrasion resistance is obtained.
Furthermore, according to the present invention, an antireflection film having a low refractive index layer made of the cured product and having excellent scratch resistance can be obtained.

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

［式（Ｂ−１）中、Ｒｂは水素原子又はメチル基である。］
（Ｃ）成分（Ｂ）以外の２個以上の（メタ）アクリロイル基を有する化合物
（Ｄ）数平均粒径１〜１００ｎｍのシリカを主成分とする中空若しくは多孔質の粒子
（Ｅ）数平均粒径１〜１００ｎｍのシリカを主成分とする中実の粒子
（Ｆ）１個の（メタ）アクリロイル基と炭素数３以上の環状構造を有する、分子量４００以下の化合物
（Ｇ）活性エネルギー線の照射により活性主を発生する化合物
（Ｈ）ポリジメチルシロキサン骨格を有する化合物
（Ｉ）有機溶剤
（Ｊ）フッ素系界面活性剤
（Ｋ）その他の添加剤 1. Curable resin composition The curable resin composition of the present invention (hereinafter sometimes referred to as the composition of the present invention) may include the following components (A) to (K). Among these components, in the first embodiment of the composition of the present invention, (A), (B) and (I) are essential components, and (C) to (H), (J) and (K). ) Is an optional component that can be included as appropriate. Moreover, in the 2nd aspect of the composition of this invention, (B), (D) and (I) are essential components, and others are the arbitrary components which can be contained suitably.
(A) Ethylenically unsaturated group-containing fluoropolymer (B) Compound represented by the following general formula (B-1)

[In the formula (B-1), Rb represents a hydrogen atom or a methyl group. ]
(C) Compound having two or more (meth) acryloyl groups other than component (B) (D) Hollow or porous particles (E) having a number average particle diameter of 1 to 100 nm as a main component (E) Number average particle Solid particles mainly composed of silica having a diameter of 1 to 100 nm (F) Compound having a (meth) acryloyl group and a cyclic structure having 3 or more carbon atoms and having a molecular weight of 400 or less (G) Irradiation with active energy rays (H) Compound having a polydimethylsiloxane skeleton (I) Organic solvent (J) Fluorosurfactant (K) Other additives

In the composition of the present invention, the component (B) contains fluorine and has a low refractive index as compared with the conventional polyfunctional (meth) acrylate compound, but the coating film hardness when used as a cured film is the conventional one. This is equivalent to using a polyfunctional (meth) acrylate compound. Therefore, in combination with the component (A) and the component (B) in the low refractive index material, the low refractive index property and antifouling property derived from the component (A) are expressed, and the high crosslinking density due to the component (B) A cured film (low refractive index film) having excellent scratch resistance is obtained. Further, even when the component (B) is used alone, a cured film (low refractive index film) having excellent scratch resistance can be obtained.
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.
Preferably, the component (A) is modified with a (meth) acrylic compound having a side chain hydroxyl group having an isocyanate group, an acid chloride group or a carboxylic acid group. Such modification allows co-crosslinking with the radically polymerizable (meth) acrylic compound and improves the scratch resistance.

  The ethylenically unsaturated group-containing fluorine-containing polymer is obtained by reacting a compound containing at least one ethylenically unsaturated group and a group capable of reacting with a hydroxyl group with a hydroxyl group-containing fluoropolymer.

(1) A compound containing at least one ethylenically unsaturated group and a group capable of reacting with a hydroxyl group. Such a compound is a compound containing at least one ethylenically unsaturated group in the molecule. Any functional group capable of reacting with the hydroxyl group of the fluoropolymer is not particularly limited.
Moreover, as said ethylenically unsaturated group, since the curable resin composition mentioned later can be hardened more easily, the compound which has a (meth) acryloyl group is more preferable.
Such compounds include (meth) acrylic acid, (meth) acryloyl chloride, anhydrous (meth) acrylic acid, 2- (meth) acryloyloxyethyl isocyanate, 2- (meth) acryloyloxypropyl isocyanate, 1,1- One kind of (bisacryloyloxymethyl) ethyl isocyanate or a combination of two or more kinds may be mentioned.
In addition, as a commercial item of the (meth) acrylate which has an isocyanate group, Showa Denko Co., Ltd. brand name Karenz MOI, AOI, and BEI are mentioned, for example.

Such a 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 contains the following structural unit (a), (b-1) and / or (b-2), and (c). Become.
(A) A structural unit represented by the following formula (1).
(B-1) A structural unit represented by the following formula (2-1).
(B-2) A structural unit represented by the following formula (2-2).
(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（２−１）中、Ｒ³は水素原子又はメチル基を、Ｒ⁴はアルキル基、−(ＣＨ₂)_ｄ−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、ｄ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 Formula (2-1), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, and a group represented by — (CH ₂ ) _d —OR ⁵ or —OCOR ⁵ (R ⁵ represents an alkyl group or A glycidyl group, d represents a number of 0 or 1, and a carboxyl group or an alkoxycarbonyl group]

［式中、Ｒ^３は式（２−１）で定義した通りであり、Ｒ^２４はフルオロアルキル基を示し、ｘは０〜２の数を示す］

[Wherein R ³ is as defined in formula (2-1), R ²⁴ represents a fluoroalkyl group, and x represents a number of 0 to 2]

［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.

The content of the structural unit (a) is 30 when the total of the structural unit (a), (b-1) and / or (b-2), and (c) is 100 mol%. -65 mol%. The reason for this is that when the content is less than 30 mol%, it is difficult to develop a low refractive index, which is an optical characteristic of the fluorine-containing material intended by the present invention, whereas This is because when the ratio exceeds 65 mol%, the solubility of the hydroxyl group-containing fluoropolymer in an organic solvent, transparency, or adhesion to a substrate may be lowered.
Moreover, for such reasons, the content of the structural unit (a) is set to 100 mol% of the total of the structural unit (a), (b-1) and / or (b-2), and (c). When it is, it is more preferable to set it as 35-60 mol%, and it is more preferable to set it as 40-55 mol%.

(Ii) Structural unit (b-1)
In formula (2-1), examples of the alkyl group represented by R ⁴ or R ⁵ include alkyl groups having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, and a lauryl group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

  The structural unit (b-1) can be introduced by using the above-described 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.

（式中、Ｒ^３は水素原子又はメチル基であり、ｘは０〜２の数を表す。また、上記式中、芳香環の中にFと記した基は、５つの水素の全てがフッ素原子で置換されていることを示す。） (Iii) Structural unit (b-2)
In the copolymer of the present invention, the structural unit (b-2) can be used together with the structural unit (b-1) or in place of the structural unit (b-1). The structural unit (b-2) can be introduced by using a vinyl monomer represented by the formula (2-2) as a polymerization component. Specific examples of such vinyl monomers include those having the following structural formula.

(In the formula, R ³ represents a hydrogen atom or a methyl group, and x represents a number from 0 to 2. In the above formula, the group marked F in the aromatic ring is all five hydrogens are fluorine. Indicates that the atom is substituted.)

The content of the structural unit (b-1) and / or (b-2) is the sum of the structural unit (a), (b-1) and / or (b-2), and (c). When the content is 100 mol%, it is 1 to 50 mol%. The reason for this is that when the content rate is less than 1 mol%, the solubility of the hydroxyl group-containing fluorine-containing copolymer in the organic solvent may be reduced, whereas when the content rate exceeds 50 mol%, This is because the optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluorine-containing copolymer may deteriorate.
For these reasons, the content of the structural units (b-1) and / or (b-2) is changed to the structural units (a), (b-1) and (b-2), and (c )) Is more preferably from 1 to 45 mol%. Moreover, the content rate of (b-1) and / or (b-2) shown above is the structural unit when the structural unit (b-1) or (b-2) is used alone. It means the content of either (b-1) or (b-2), and when the structural units (b-1) and (b-2) are used together, it means the total content of both. .

(Iv) 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.

The content of the structural unit (c) is 5 when the total of the structural units (a), (b-1) and / or (b-2), and (c) is 100 mol%. It is preferable to set it as -60 mol%. The reason for this is that when the content is less than 5 mol%, the hydroxyl group content of the fluoropolymer is lowered, and sufficient hardness of the cured coating film may not be obtained. On the other hand, the content is 60 mol. This is because if it exceeds%, optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluoropolymer may be deteriorated.
For these reasons, the content of the structural unit (c) is set to 100 mol% of the total of the structural units (a), (b-1) and / or (b-2), and (c). When it is, it is more preferable to set it as 5-55 mol%, and it is more preferable to set it as 10-50 mol%.

(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, the content rate of the structural unit (d) is 0.1 to the total 100 mol parts of the structural unit (a), (b-1) and / or (b-2), and (c). It is preferable to set it as 10 mol part. The reason for this is that when the content is less than 0.1 mol part, the surface slipperiness of the coated film after curing is lowered, and the scratch resistance of the coated film may be lowered. If the amount exceeds 10 parts by mole, 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.
Moreover, for such reasons, the content of the structural unit (d) is adjusted to 100 mol parts in total of the structural unit (a), (b-1) and / or (b-2), and (c). On the other hand, it is more preferable to set it as 0.1-5 mol part, and it is further more preferable to set it as 0.1-3 mol part. 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（９−１）中、ｎは１〜２０の数、ｍは０〜４の数、ｕは３〜５０の数を示す］

［式（９−２）中、ｎ、ｍ及びｕは、上記式（９−１）と同様である］ Examples of the group having such an emulsifying action include groups represented by the following formula (9-1) or (9-2).

[In Formula (9-1), 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]

[In Formula (9-2), n, m, and u are the same as in Formula (9-1) above]

  The structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component. Examples of such a reactive emulsifier include compounds represented by the following formula (10-1) or (10-2).

［式（１０−１）中、ｎ、ｍ及びｕは、上記式（９−１）と同様である］

［式（１０−２）中、ｎ、ｍ及びｕは、上記式（９−１）と同様である］

[In Formula (10-1), n, m, and u are the same as in Formula (9-1) above]

[In Formula (10-2), n, m, and u are the same as in Formula (9-1) above]

In addition, the content rate of the structural unit (f) is 0.1 to the total 100 mol parts of the structural unit (a), (b-1) and / or (b-2), and (c). It is preferable to set it as -5 mol part. The reason for this is that when the content is 0.1 mol part 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 parts, 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 adjusted to 100 mol parts in total of the structural unit (a), (b-1) and / or (b-2), and (c). On the other hand, it is more preferable to set it as 0.1-3 mol part, and it is further more preferable to set it as 0.2-3 mol part.

(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.

The amount of component (A) added is not particularly limited, but is usually 1 to 80% 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 1% by weight, the refractive index of the cured coating film of the curable resin composition increases, and a sufficient antireflection effect may not be obtained. If the amount exceeds 80% by weight, the scratch resistance of the cured coating film of the curable resin composition may not be obtained.
For these reasons, the amount of component (A) added is more preferably 1 to 70% by weight, and even more preferably 1 to 60% by weight.

［式（Ｂ−１）中、Ｒｂは水素原子又はメチル基である。］ (B) Compound Represented by General Formula (B-1) The component (B) is a polyfunctional (meth) acrylate compound containing fluorine represented by the following general formula (B-1). The component (B) is used to increase the reflectance and scratch resistance of a cured product obtained by curing the curable resin composition and an antireflection film using the cured product.

[In the formula (B-1), Rb represents a hydrogen atom or a methyl group. ]

式（Ｂ−１−１）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（（Ｂ）成分の含有量６５重量％、ペンタエリスリトールテトラアクリレートを３５重量％含む）が挙げられる。 In the above formula (B-1), a compound represented by the following formula (B-1-1) in which Rb is a hydrogen atom is preferable.

As a commercial item of the compound represented by Formula (B-1-1), Kyoeisha Chemical Co., Ltd. LINC-3A ((B) component content 65 weight%, pentaerythritol tetraacrylate is included 35 weight%). Can be mentioned.

The amount of component (B) added is not particularly limited, but is usually 1 to 80% by weight with respect to the total amount of the composition other than the organic solvent. This is because if the amount added is less than 1% by weight, a sufficiently low refractive index and high hardness may not be obtained. On the other hand, if the amount added exceeds 80% by weight, the antireflective film is used. This is because the antifouling property may not be obtained.
For this reason, the amount of component (B) added is more preferably 5 to 70% by weight, and even more preferably 5 to 60% by weight.

(C) Compound having two or more (meth) acryloyl groups other than component (B) Two or more (meth) acrylate compounds of component (C) are obtained by curing a curable resin composition. It is used for enhancing the scratch resistance of an object and an antireflection film using the same.

  This compound is not particularly limited as long as it is a compound containing two or more (meth) acryloyl groups in the molecule. Examples of the compound containing two or more (meth) acryloyl groups include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, tri Cyclodecanediyldimethylene di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanate Nurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide (hereinafter referred to as “EO”) modified trimethylolpropane tri (meth) acrylate, pro Renoxide (hereinafter referred to as “PO”) modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bisphenol A diglycidyl ether at both ends (meth) acrylic acid Adduct, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, Polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 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 (meth) acrylate, (meth) acrylate of phenol novolac polyglycidyl ether, etc. It can be illustrated. Commercially available products of these polyfunctional (meth) acrylate compounds include, for example, 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 (above, 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- 30, 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 (above, manufactured by Kyoeisha Chemical Co., Ltd.), New Frontier BPE-4, BR-42M, GX-8345 (above, Daiichi Kogyo Seiyaku ( )), 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) And NK ester A-BPE-4 (manufactured by Shin-Nakamura Chemical Co., Ltd.).

  In addition, among these, the compound which contains at least 3 or more (meth) acryloyl groups in a molecule | numerator is more preferable for the composition of this invention. 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, pentaerythritol hydroxytriacrylate and trimethylolpropane triacrylate are particularly preferred. Each of the above compounds can be used alone or in combination of two or more.

  Moreover, these (meth) acrylate compounds may contain fluorine. Examples of such compounds are perfluoro-1,6-hexanediol di (meth) acrylate, octafluorooctane-1,6-di (meth) acrylate, octafluorooctanediol and 2- (meth) acryloyloxyethyl. One kind alone or a combination of two or more kinds such as an isocyanate, 2- (meth) acryloyloxypropyl isocyanate, an adduct with 1,1- (bisacryloyloxymethyl) ethyl isocyanate may be mentioned.

The amount of component (C) added is not particularly limited, but is usually 1 to 60% 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 1% 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 60% 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 this reason, the amount of component (C) added is more preferably 1 to 50% by weight, and even more preferably 1 to 40% by weight.

(D) Hollow or porous particles mainly composed of silica having a number average particle diameter of 1 to 100 nm The composition of the present invention includes hollow or porous particles mainly composed of silica having a number average particle diameter of 1 to 100 nm. Particles (D) can be blended. The particle size is measured with a transmission electron microscope. By blending the particles (D), a cured product obtained by curing the composition of the present invention can exhibit a low refractive index and scratch resistance. (D) As a particle, a well-known thing can be used, Moreover, the shape is not restricted spherical and may be indefinite. Colloidal silica having a solid content of 5 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.
(D) As a commercial item of particle | grains, the product name: JX1008SIV, JX1009SIV, JX1010SIV etc. by a catalyst chemical industry Co., Ltd. can be mentioned, for example.

  (D) The compounding quantity of a component is 1-80 weight% normally with respect to composition whole quantity except an organic solvent, 10-80 weight% is preferable and 20-80 weight% is further more preferable. 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) Solid particles mainly composed of silica having a number average particle diameter of 1 to 100 nm Solid particles mainly composed of silica having a number average particle diameter of 1 to 100 nm are blended in the composition of the present invention. Can do. The particle size of the particles is measured with a transmission electron microscope.
By blending the solid particles (E) containing silica as a main component, it is possible to impart the scratch resistance of a cured product obtained by curing the composition of the present invention.
As the solid particles (E), known particles can be used, and the shape thereof is not limited to spherical, and may be irregular particles. Colloidal silica having a solid content of 5 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 solid particle which has 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 and the like.

  (E) The compounding quantity of a component is 1-40 weight% normally with respect to composition whole quantity except an organic solvent, 1-30 weight% is preferable and 1-10 weight% is further more preferable. 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.

As the particles (D) and (E) containing silica as a main component, particles whose surface has been subjected to a surface treatment such as chemical modification can be used. For example, hydrolyzed particles having one or more alkyl groups in the molecule. Those containing a decomposable silicon compound or 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 surface treatment of the particles (D) and (E) containing silica as a main component can be performed with an organic compound containing a polymerizable unsaturated group. As the organic compound containing a polymerizable unsaturated group, the specific organic compound described below can be used.

(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) Isocyanato), 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanate) Til) 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 (isocyanatemethyl) 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, trimethylolpropane di (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 (hereinafter also referred to as particles) The surface treatment method of the particles is not particularly limited, but a hydrolyzable silicon compound or a specific organic compound (hereinafter referred to as a surface treatment agent). It is also possible to produce the mixture by mixing particles and heating and stirring. The reaction is preferably carried out in the presence of water in order to efficiently combine the silanol group-generating site of the surface treatment agent with the particles. However, when the surface treatment agent 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 surface treatment agent.

  The reaction amount of the particles and the surface treatment agent 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.

  The amount of water consumed by hydrolysis of the alkoxysilane compound in the surface treatment agent at the time of the surface treatment may be an amount by which at least one alkoxy group on silicon in one molecule is 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 the surface treatment, after subjecting the surface treatment agent to a separate hydrolysis operation, this is mixed with powder particles or solvent dispersion sol of the particles, followed by heating and stirring operation; hydrolysis of the alkoxysilane compound; A method of performing in the presence of particles; or a method of performing surface treatment of particles in the presence of other components such as a polymerization initiator can be selected. 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 causing the reaction with the surface treatment agent to be performed smoothly and uniformly. 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 Y-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 . 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 surface treatment agent. 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. can be mentioned.
Among these, preferable examples of the acid include organic acids and unsaturated organic acids, and the base includes tertiary amines or quaternary ammonium hydroxides and aqueous ammonia.

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.

  In addition, the addition amount of the particle | grains (D) and (E) which have a silica as a main component is in the above-mentioned range irrespective of the presence or absence of surface treatment.

(F) A compound having a molecular weight of 400 or less having one (meth) acryloyl group and a cyclic structure having 3 or more carbon atoms. A compound having a molecular weight of 400 or less having one (meth) acryloyl group and a cyclic structure having 3 or more carbon atoms. The compound is used for improving the adhesion between the low refractive index cured product obtained by curing the curable resin composition and the base hard coat, and improving the anti-reflection film scratch resistance using the same. Component (F) partially penetrates into the hard coat layer, thereby causing the low refractive index cured product comprising the composition of the present invention and the hard coat layer to co-crosslink, or roughening (eroding) the hard coat surface. This brings about an anchor effect.

  The compound is not particularly limited as long as it is a compound containing at least one (meth) acryloyl group and a cyclic structure having 3 or more carbon atoms in the molecule and having a molecular weight of 400 or less. The following general formula (C-1)-(C-5) is mentioned as an example of the compound which gives an effect.

［式（Ｃ−１）〜（Ｃ−５）中、Ｘ^１は水素又はメチル基を示し、Ｘ^２及びＸ^３はそれぞれ独立して炭素数１〜６の直鎖状、分岐状又は環状アルキル基を示し、Ｘ^４はそれぞれ独立して水素、フッ素、フッ素によって置換されていてもよい炭素数１〜４のアルキル基を示す。］
具体的には、（メタ）アクリロイルモルホリン、ベンジル（メタ）アクリレート、テトラヒドロフルフリルアクリレート、４−（メタ）アクリロイルオキシメチル−２−メチル−２−エチル−１，３−ジオキソラン、４−（メタ）アクリロイルオキシメチル−２−メチル−２−イソブチル−１，３−ジオキソラン、４−（メタ）アクリロイルオキシメチル−２−メチル−２−シクロヘキシル−１，３−ジオキソラン、４−（メタ）アクリロイルオキシメチル−２，２-ジメチル−１，３−ジオキソラン等が挙げられる。これらの化合物うち（メタ）アクリロイルモルホリン、ベンジル（メタ）アクリレートが特に好ましい。
これらの化合物の市販品としては、例えばＭＭＤＯＬ３０、ＭＥＤＯＬ３０、ＭＩＢＤＯＬ３０、ＣＨＤＯＬ３０、ＭＥＤＯＬ１０、ＭＩＢＤＯＬ１０、ＭＩＢＤＯＬ１０、ＣＨＤＯＬ１０、ビスコート１５０、ビスコート１６０（以上、大阪有機化学工業（株）製）、ＡＣＭＯ（以上、（株）興人製）等を挙げることができる。

[In the formulas (C-1) to (C-5), X ¹ represents hydrogen or a methyl group, and X ² and X ³ are each independently a linear, branched or cyclic alkyl having 1 to 6 carbon atoms. And X ⁴ independently represents hydrogen, fluorine, or an alkyl group having 1 to 4 carbon atoms which may be substituted with fluorine. ]
Specifically, (meth) acryloylmorpholine, benzyl (meth) acrylate, tetrahydrofurfuryl acrylate, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4- (meth) Acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl- Examples include 2,2-dimethyl-1,3-dioxolane. Of these compounds, (meth) acryloylmorpholine and benzyl (meth) acrylate are particularly preferred.
Examples of commercially available products of these compounds include MMDOL30, MEDOL30, MIBDOL30, CHDOL30, MEDOL10, MIBDOL10, MIBDOL10, CHDOL10, Biscote 150, Biscote 160 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), ACMO (above, ) Manufactured by Kojin).

Component (F) is usually added in an amount of 0.1 to 30% by weight based on the total amount of the composition excluding the organic solvent. The reason for this is that when the addition amount is less than 0.1% by weight, the penetration (penetration) into the base hard coat layer is insufficient, the adhesion is not improved, and the scratch resistance of the cured coating film cannot be obtained. On the other hand, if the addition amount exceeds 30% by weight, the hardness of the cured coating film of the curable resin composition is lowered, and the scratch resistance of the cured coating film may not be obtained. .
For this reason, the amount of component (F) added is more preferably 0.5 to 25% by weight, and even more preferably 1 to 20% by weight.

(G) Compound that generates active species upon irradiation with active energy rays The compound that generates active species upon irradiation with active energy rays is a photopolymerization initiator, and the composition of the present invention is irradiated with active energy rays such as ultraviolet rays. It is a component used for curing.

  Examples of the photopolymerization initiator of component (G) 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-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.

  Examples of commercially available photopolymerization initiators include Irgacure 369 (manufactured by Ciba Specialty Chemicals, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1), Irgacure 907 ( Ciba Specialty Chemicals, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one) is preferred.

In addition, the photopolymerization initiator represented by the following formula (g-1) as the component (G) is Irg127 (2-hydroxy-1- {4- [4- (2-hydroxy-2-hydroxy) produced by Ciba Specialty Chemicals]. Methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one) Even when used alone or in combination with other polymerization initiators, low irradiation of 0.2 J / cm ² or less The scratch resistance excellent in the hardened | cured material which hardens the composition of this invention with a light quantity can be expressed.

  The compound represented by the above formula (g-1) is highly sensitive because it has two α-hydroxyketone groups, and can effectively cure the composition of the present invention even with a low irradiation light amount. Improve scratch resistance.

  In addition, an active energy ray is defined as an energy ray that can generate an active species by decomposing a compound (photopolymerization initiator) that generates an 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 because it has a certain energy level, has a high curing rate, is relatively inexpensive, and is compact.

(Ii) Addition amount The addition amount of (G) component is 0.1 to 20 weight% normally with respect to the composition whole quantity except an organic solvent. The reason for this is that if the amount added is less than 0.1% by weight, curing failure occurs. On the other hand, if the amount added exceeds 20% by weight, the coating strength decreases due to excessive components. is there. For this reason, the amount of component (G) added is more preferably 0.5 to 10% by weight, and even more preferably 0.5 to 8% by weight.

(H) Compound having a polydimethylsiloxane skeleton A compound having a polydimethylsiloxane skeleton has an effect of improving surface slipperiness and improving scratch resistance of a cured coating film, and can impart antifouling properties. . A compound having such polydimethylsiloxane is preferable, and it is preferable to have a reactive group such as a (meth) acryloyl group or a hydroxyl group. Specific examples of these include Silaplane FM-4411, FM-4421, FM-4425, FM-7711, FM-7721, FM-7725, FM-0411, FM-0421, FM-0425, FM-DA11, FM -DA21, FM-DA26, FM0711, FM0721, FM-0725, TM-0701, TM-0701T (manufactured by Chisso Corp.), UV3500, UV3510, UV3530 (manufactured by Big Chemie Japan Corp.), BY16-004, SF8428 (Toray Dow Corning Silicone Co., Ltd.), VPS-1001 (manufactured by Wako Pure Chemical Industries), and the like. Silaplane FM-7711, FM-7721, FM-7725, FM-0411, FM-0421, FM-0425, FM0711, FM0721, FM-0725, VPS-1001, and Rad2600 made by TEGO are particularly preferable.

(Ii) Addition amount The addition amount of (H) component is 0.01 to 20 weight% normally with respect to the composition whole quantity except an organic solvent. The reason for this is that when the addition amount is less than 0.01% by weight, the effect of improving the slipperiness cannot be sufficiently obtained. On the other hand, when the addition amount exceeds 20% by weight, the coating strength decreases due to an excessive amount of components. This is because the coatability deteriorates.
For this reason, the amount of component (H) added is preferably 0.1 to 15% by weight, and more preferably 0.5 to 10% by weight.

(I) Organic solvent The composition of the present invention contains an organic solvent. By containing the organic solvent, a thin antireflection film can be formed uniformly. Such organic solvents include acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, methyl amyl ketone and other ketones, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and other esters, propylene glycol monomethyl ether, methanol, ethanol , Sec-butanol, t-butanol, alcohols such as 2-propanol and isopropanol, aromatics such as benzene, toluene and chlorobenzene, and aliphatics such as hexane and cyclohexane, alone or in combination of two or more. It is done. Among these, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, methyl amyl ketone, esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methanol, ethanol, sec-butanol , T-butanol, 2-propanol, isopropanol and the like are preferable, more preferably methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, t-butanol, propylene glycol monomethyl ether acetate, or a combination of two or more. .

  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 solid content. 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.

(J) Fluorosurfactant Fluorosurfactant (hereinafter referred to as component (J)) has an effect of improving the antifouling property by modifying the surface of the coating film, and also improves coating properties. . The component (J) preferably has a hydrophilic group and / or a lipophilic group, and a perfluoroalkyl group. Examples of hydrophilic groups include acidic groups such as polyethylene oxide chains, carboxyl groups, and sulfonyl groups, or salts or esters thereof. Specific examples of these include Megafuck F-114, F410, F411, F450, F493, F494, F443, F444, F445, F446, F470, F471, F472SF, F474, F475, R30, F477, F478, F479, F480SF. F482, F483, F484, F486, F487, F172D, F178K, F178RM, ESM-1, MCF350SF, BL20, R08, R61, R90 (manufactured by Dainippon Ink & Chemicals, Inc.) and the like.
In addition, the compound of component (J) can be used in combination with the compound having a polydimethylsiloxane skeleton of component (H), so that surface slipperiness, antifouling property, and scratch resistance can be further improved. It is preferable to do.

Component (J) is usually added in an amount of 0.01 to 20% by weight based on the total amount of the composition excluding the organic solvent. The reason for this is that when the addition amount is less than 0.01% by weight, the effect of improving the slipperiness cannot be sufficiently obtained. On the other hand, when the addition amount exceeds 20% by weight, the coating strength decreases due to an excessive amount of components. This is because the coatability deteriorates.
For these reasons, the amount of component (J) added is preferably 0.1 to 10% by weight, more preferably 0.5 to 8% by weight.

(K) Additive In the composition of the present invention, inorganic particles other than silica particles, a photosensitizer, a thermal polymerization initiator, a polymerization inhibitor, and a polymerization initiation auxiliary agent are within the range not impairing the object and effect of the present invention. , Leveling agents, wettability improvers, surfactants, plasticizers, UV absorbers, antioxidants, antistatic agents, silane coupling agents, pigments, dyes, slip agents, etc. .
In particular, the inorganic particles are effective for improving the coating strength, and when added, the number average particle size is preferably in the range of 1 to 100 nm, and spherical, beaded, amorphous particles can be used, and Porous and hollow particles having voids in the internal structure can also be used. As the inorganic particles that can be used, inorganic oxides or fluorides are preferable, and examples thereof include alumina, titania, zirconia, and magnesium fluoride. In addition, the surface of these inorganic particles may be surface-modified with any organic group. By modifying with a (meth) acrylic group, compatibility with the curable resin composition is improved, and other properties may be obtained during curing. It is possible to co-crosslink with the curable composition, and it is possible to improve the scratch resistance of the cured film.

  The thermal polymerization initiator is a compound that generates active species by heat, and examples thereof include a thermal radical generator that generates radicals as 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.

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 can be prepared by adding the components (K) to the above (A) to (J) and depending on the situation and mixing them at room temperature or under heating conditions. . 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 composition of the present invention are not particularly limited. For example, when an active energy ray is used, it is preferable to set the amount of irradiation light within a range of 0.01 to 10 J / cm ² .
This is because when the irradiation light quantity is less than 0.01 J / cm ² , curing failure may occur. On the other hand, when the irradiation light quantity exceeds 10 J / cm ² , the curing time may become excessively long. Because there is.

The composition of the present invention can be further cured by heating. In this case, it is preferable to heat at a temperature in the range of 30 to 200 ° C. for 0.5 to 180 minutes. 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 0.5 to 120 minutes, and to heat at a temperature in the range of 80 to 150 ° C. for 1 to 60 minutes. Is more 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 a cross-sectional view of such an antireflection film. As shown in FIG. 1, a hard coat layer 3 and a low refractive index layer 4 are laminated on a substrate 2.
At this time, a high refractive index layer may be formed directly on the substrate 2 instead of the hard coat layer 3. Further, a high refractive index layer 5 may be provided between the hard coat layer 3 and the low refractive index layer 4 (FIG. 2). Further, an intermediate refractive index layer 6 may be provided between the hard coat layer 3 and the high refractive index layer 5 (FIG. 3).

(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 of the present invention (the refractive index of Na-D line, measurement temperature 25 ° C.), that is, the refractive index of the low refractive index film is 1.50 or less. It is preferable. This is because when the refractive index of the low refractive index film exceeds 1.50, the antireflection effect may be significantly reduced. Therefore, the refractive index of the low refractive index film is more preferably 1.48 or less, and further preferably 1.45 or less.
When a plurality of low refractive index films are provided, at least one of them should have a refractive index value within the above-mentioned range. It may be a value exceeding 50.

The thickness of the low refractive index layer is not particularly limited, but is preferably 50 to 200 nm, for example. This is because when the thickness of the low refractive index layer is less than 50 nm, the antireflection effect may not be sufficiently obtained. On the other hand, when the thickness exceeds 200 nm, optical interference occurs and antireflection is caused. This is because the effect may be reduced.
Therefore, the thickness of the low refractive index layer is more preferably 50 to 250 nm, and further preferably 70 to 150 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, usually the refractive index of these resins alone is 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, thermosetting, ultraviolet curing, and electron beam curing can be used, but among these, an ultraviolet curable composition with good productivity is more preferably used.

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 of the plurality of high refractive index layers is set to 50 to 30,000 nm. Good.
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 1-100 micrometers, and it is more preferable to set it as 3-30 micrometers. The reason for this is that when the thickness of the hard coat layer is less than 1 μm, the hardness as the hard coat may be reduced. On the other hand, when the thickness exceeds 100 μm, the base material is not cured due to curing shrinkage of the hard coat. This is because it may be deformed.

(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 Hereinafter, although an Example is given and this invention is demonstrated further in detail, the scope of the present invention is not limited to description of these Examples. “Parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified.

(Production Example 1)
Synthesis of hydroxyl group-containing fluoropolymer After a 2.0 liter stainless steel autoclave with a magnetic stirrer was sufficiently replaced with nitrogen gas, 11544 g of ethyl acetate, 3464 g of perfluoro (propyl vinyl ether), 938 g of ethyl vinyl ether, 1145 g of hydroxyethyl vinyl ether , 37.5 g of lauroyl peroxide, 225 g of an azo group-containing polydimethylsiloxane represented by the above formula (7) (VPS1001 (trade name), manufactured by Wako Pure Chemical Industries, Ltd.) and a nonionic reactive emulsifier (ER-30) (Product Name), manufactured by Asahi Denka Kogyo Co., Ltd., which had a solid composition obtained by distilling off all of the solvent in advance) was charged with 1125 g, cooled to −50 ° C. with dry ice-methanol, and then again with nitrogen gas. Oxygen was removed.

Next, 1953 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 about 5 kg 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. ER-30 is a nonionic reactive emulsifier wherein n is 10 to 14, m is 1 and u is 14 to 45 in the above formula (10-2).
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-1)
Hydroxyethyl vinyl ether (c)
ER-30 (f)
Polydimethylsiloxane skeleton (d)

(Production Example 2-1)
Synthesis of ethylenically unsaturated group-containing fluoropolymer A-1 (methacryl-modified fluoropolymer) (component (A)) In a 1-liter separable flask equipped with a magnetic stirrer, a glass condenser, and a thermometer. 120 g of the hydroxyl group-containing fluoropolymer obtained in Production Example 1, 0.02 g of 2,6-di-t-butylmethylphenol and 899 g of methyl isobutyl ketone (MIBK) as a polymerization inhibitor were charged at 20 ° C. Stirring was performed until the containing fluoropolymer was dissolved in MIBK and the solution became transparent and uniform.
Subsequently, 38.6 g of 2-methacryloyloxyethyl isocyanate was added to this system and stirred until the solution became homogeneous, then 0.3 g of dibutyltin dilaurate was added to start the reaction, and the temperature of the system was changed to 55 to 55. The MIBK solution of the ethylenically unsaturated group-containing fluoropolymer A-1 was obtained by maintaining at 65 ° C. and continuing stirring for 5 hours.
2 g of this solution was weighed in an aluminum dish, dried on a hot plate at 150 ° C. for 5 minutes, and weighed to determine the solid content, which was 15.0% by weight. The compounds used, solvent and solid content are shown in Table 3.

(Production Example 2-2)
Synthesis of ethylenically unsaturated group-containing fluoropolymer A-2 (methacryl-modified fluoropolymer) (component (A)) In a 1-liter separable flask equipped with a magnetic stirrer, a glass condenser, and a thermometer. 120 g of the hydroxyl group-containing fluoropolymer obtained in Production Example 1, 0.02 g of 2,6-di-t-butylmethylphenol and 862 g of methyl isobutyl ketone (MIBK) as a polymerization inhibitor were charged at 20 ° C. Stirring was performed until the containing fluoropolymer was dissolved in MIBK and the solution became transparent and uniform.
Next, to this system, 32.1 g of 2-methacryloyloxyethyl isocyanate was added and stirred until the solution became homogeneous, then 0.3 g of dibutyltin dilaurate was added to start the reaction, and the temperature of the system was changed to 55 to 55. The MIBK solution of the ethylenically unsaturated group-containing fluoropolymer A-1 was obtained by maintaining at 65 ° C. and continuing stirring for 5 hours.
2 g of this solution was weighed in an aluminum dish, dried on a hot plate at 150 ° C. for 5 minutes, and weighed to determine the solid content, which was 15.0% by weight. The compounds used, solvent and solid content are shown in Table 3.

(Production Example 3)
Preparation of composition for hard coat layer In a container shielded from ultraviolet rays, 95 parts by weight of pentaerythritol hydroxytriacrylate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 5 By stirring 2 parts by weight and 100 parts by weight of MIBK at 50 ° C. for 2 hours, a uniform hard coat layer composition 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.

(Production Example 4)
Preparation of substrate for coating curable resin composition A composition for hard coat layer prepared in Production Example 3 was applied to a TAC film (thickness 50 μm) with a wire bar coater so as to have a film thickness of 6 μm. Medium was dried at 80 ° C. for 1 minute to form a coating film. Next, ultraviolet rays were irradiated under a light irradiation condition of 300 mJ / cm ² using a high-pressure mercury lamp in the air to prepare a curable resin composition coating substrate.

(Production Example 5)
Manufacture of specific organic compound (S1) In dry air, a solution consisting of 23.0 parts of mercaptopropyltrimethoxysilane and 0.5 parts of dibutyltin dilaurate is stirred at 50 ° C. for 1 hour with 60.0 parts of isophorone diisocyanate. After dropping, the mixture was stirred at 70 ° C. for 3 hours. NK ester A-TMM-3LM-N (60% by weight of pentaerythritol triacrylate and 40% by weight of pentaerythritol tetraacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. (Only triacrylate.) After adding 202.0 parts dropwise at 30 ° C. over 1 hour, specific organic compound (S1) was obtained by heating and stirring at 60 ° C. for 3 hours.
In the infrared absorption spectrum of the product, the absorption peak of 2550 Kaiser characteristic of the mercapto group in the raw material and the absorption peak of 2260 Kaiser characteristic of the isocyanate group disappeared, and a new [—O—C (═O) A 1660 Kaiser peak characteristic of carbonyl in the —NH—] group and [—S—C (═O) —NH—] group and a peak of 1720 Kaiser characteristic of the acryloyl group are observed and polymerizability is observed. That a specific organic compound having both an acryloyl group as an unsaturated group, a [—S—C (═O) —NH—] group, and a [—O—C (═O) —NH—] group is formed. Indicated.

(Production Example 6)
Production of acrylic modified hollow silica particles D-1 (component (D)) 3.0 parts of the specific organic compound (S1) synthesized in Production Example 5, hollow silica particles (JX1009SIV, methyl isobutyl ketone sol, manufactured by Catalyst Chemical Industries) 137 Parts (solid content 30.1 parts), ion-exchanged water 0.1 parts, 0.05 mol / L dilute sulfuric acid 0.01 part mixture was stirred at 80 ° C. for 3 hours, and then orthoformate methyl ester 1.4. Particulate dispersion D-1 was obtained using a part. The solid content of D-1 was determined to be 25% by weight.
The average particle diameter of the silica-based particles was 50 nm. Here, the average particle diameter was measured with a transmission electron microscope.

(Production Example 7)
Production of methacryl-modified hollow silica particles D-2 (component (D)) 100 parts of hollow silica particles (JX1008SIV, isopropyl alcohol sol, manufactured by Catalyst Kasei Kogyo), 10 parts of 10% aqueous ammonia and 700 parts of ethanol were mixed at room temperature. While stirring, 3 parts of γ-methacryloxypropyltrimethoxysilane (manufactured by Toray Dow Corning Silicone Co., Ltd., trade name: SZ6030) was added. Then, it was made to react at 70 degreeC for 3 hours. The reaction mixture was cooled to room temperature, 700 parts of methyl isobutyl ketone was added, and the resulting mixture was concentrated to a solid concentration of 25% by weight using an evaporator to obtain a particle dispersion D-2. After weighing 2 g of D-2 in an aluminum dish, it was dried on a hot plate at 120 ° C. for 1 hour and weighed to determine the solid content, which was 25% by weight. The average particle diameter of the silica-based particles was 50 nm. Here, the average particle diameter was measured with a transmission electron microscope.

(Production Example 8)
Production of acrylic-modified solid silica particles E-1 (component (E)) 8.7 parts of the specific organic compound (S1) synthesized in Production Example 5, 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 the mixture was further heated and stirred at the same temperature for 1 hour to obtain colorless and transparent particle dispersion E-1. After weighing 2 g of E-1 in an aluminum dish, it was dried on a hot plate at 120 ° C. for 1 hour and weighed to determine the solid content, which was 35% by weight.
The average particle diameter of the silica-based particles was 20 nm. Here, the average particle diameter was measured with a transmission electron microscope.

(Example 1)
As shown in Table 4-1, 328 g of MIBK solution of ethylenically unsaturated group-containing fluoropolymer A-1 obtained in Production Example 2 (48 g as the solid content of component (A)), triacryloylheptadecafluoro Nonenyl pentaerythritol (LINC-3A, manufactured by Kyoeisha Chemical Co., Ltd.) 48 g (32 g as component (B), 16 parts of pentaerythritol tetraacrylate as component (C)), 2-hydroxy-1- {4- as photopolymerization initiator [4- (2-Hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (Irgacure 127, manufactured by Ciba Specialty Chemicals), polydimethylsiloxane H-1 ( FM0725 (manufactured by Chisso), 1 g of MIBK and 925 g of MIBK and 1200 g of t-butanol, It was charged to the scan separable flask made, to obtain a 1 hour stirring uniform curable resin composition at room temperature. Further, the solid content concentration determined by the method of Production Example 2 was 4.0% by weight.

(Examples 2-31 and Comparative Examples 1-3)
Each curable resin composition was obtained in the same manner as in Example 1 except that the compositions shown in Tables 4-1 to 4-6 were used.

The components in Table 4-1 to Table 4-6 are as follows.
Hollow particles: manufactured by Catalyst Kasei Co., Ltd., JX1009SIV (methyl isobutyl ketone sol, solid content concentration 22% by weight)
Triacryloyl heptadecafluoronenyl pentaerythritol: manufactured by Kyoeisha, LINC-3A (including 35 parts of pentaerythritol tetraacrylate)
Pentaerythritol hydroxytriacrylate: Nippon Kayaku, PET-30
Acryloylmorpholine: manufactured by Kojin, ACMO
Irgacure 127: 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, manufactured by Ciba Specialty Chemicals Dimethylsiloxane H-1: manufactured by Chisso, Silaplane FM-0725
Polydimethylsiloxane H-2: WPS Pure Chemicals, VPS1001
Hollow particle D-3: JX1009SIV manufactured by Catalytic Chemical Industry
Polydimethylsiloxane H-3: Rad2600 manufactured by TEGO
Perfluoroalkylethylene oxide adduct J-1: F-444 manufactured by Dainippon Ink and Chemicals, Inc.
Polydimethylsiloxane H-4: manufactured by Chisso, Silaplane FM-7711
Polydimethylsiloxane H-5: manufactured by Chisso, Silaplane FM-7721
Polydimethylsiloxane H-6: manufactured by Chisso, Silaplane FM-7725
Polydimethylsiloxane H-7: manufactured by Chisso, Silaplane FM-0721
Polydimethylsiloxane H-8: manufactured by Chisso, Silaplane TM0701T

(Evaluation example 1)
Evaluation of Appearance Each of the curable resin compositions obtained in Examples 1 to 31 and Comparative Examples 1 to 3 was obtained from the curable resin composition coating substrate obtained in Production Example 4 using a wire bar coater. The film was coated on the hard coat so as to have a film thickness of 0.1 μm, and dried at 80 ° C. for 1 minute to form a coating film. Next, under a nitrogen stream, an antireflection film was produced by irradiating ultraviolet rays at an irradiation light amount (mJ / cm ² ) shown in Tables 4-1 to 4-5 using a high-pressure mercury lamp. The appearance of the obtained antireflection film was visually evaluated. The evaluation criteria are as follows. The results are shown in Tables 4-1 to 4-6.
◎: Almost uniform coating with no coating unevenness ○: No coating unevenness △: Some coating unevenness ×: There is coating unevenness on the entire surface

(Evaluation example 2)
Haze The antireflection film obtained in Evaluation Example 1 was evaluated by measuring the haze with a color haze meter. The evaluation criteria are as follows. The results are shown in Tables 4-1 to 4-6.
○: Haze 0.3% or less △: Haze more than 0.3%, 1.0% or less ×: Haze more than 1.0%

(Evaluation example 3)
Refractive Index Measurement of Cured Film Each curable resin composition was coated on a silicon wafer with a spin coater so that the thickness after drying was about 0.1 μm, and then 0% using a high pressure mercury lamp under nitrogen. It was cured by irradiating with ultraviolet rays under a light irradiation condition of ³ J / cm ² . The obtained cured product was measured refractive index at a wavelength of 589nm at 25 ° C. using an ellipsometer to ^{_(n D 25).} The results are shown in Tables 4-1 to 4-6.

(Evaluation example 4)
The back surface of the antireflection film obtained in the reflectance evaluation example 1 of the antireflection film was painted with black spray, and a spectral reflectance measuring device (a self-recording spectrophotometer U- incorporating a large sample chamber integrating sphere attachment device 150-09090) was applied. 3410, manufactured by Hitachi, Ltd.), the reflectance was measured and evaluated from the substrate side in the wavelength range of 340 to 700 nm. Specifically, the reflectance of the antireflection laminate (antireflection film) at each wavelength is measured using the reflectance of the aluminum deposited film as a reference (100%), and from the reflectance of light at a wavelength of 550 nm, The antireflection property was evaluated according to the following criteria. The results are shown in Tables 4-1 to 4-6.
◎: Reflectance is 1.0% or less ○: Reflectance is over 1.0, 1.5% or less Δ: Reflectance is over 1.5%, 3.0% or less ×: Reflectance is 3.0% Super

(Evaluation example 5)
Scratch resistance test (steel wool resistance test)
The cured film obtained in Evaluation Example 1 was attached with steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) to 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 evaluation criteria are as follows. The results are shown in Tables 4-1 to 4-6.
A: The cured film is not damaged.
◯: Almost no peeling or scratching of the cured film is observed, or 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 6)
Contamination resistance A fingerprint was attached to the antireflection film obtained in Evaluation Example 1, and the surface of the coating film was wiped off with a non-woven fabric (trade name: Bencot S-2, manufactured by Asahi Kasei). Contamination resistance was evaluated according to the following criteria. The results are shown in Tables 4-1 to 4-6.
A: The film surface was completely wiped with a small number of wiping cycles.
○: The fingerprint on the surface of the coating film was completely wiped off.
X: Fingerprint traces remained on the sample surface without being wiped off.

(Evaluation example 7)
Scratch resistance (eraser)
An eraser (PE-03A, manufactured by a dragonfly pencil) was attached to an eraser testing machine, and the surface of the cured film obtained in Evaluation Example 1 was repeatedly rubbed 50 times under the condition of a load of 500 g. Was visually confirmed according to the following criteria. The evaluation criteria are as follows. The results are shown in Tables 4-4 to 4-6.
◎: No damage ○: No scratch but color change △: Scratch ×: Peeling over the entire surface

(Evaluation example 8)
Magic repeatability (number of wipes)
Apply about 0.25 cm ² (0.5 cm × 0.5 cm) of the antireflection film surface obtained in Evaluation Example 1 with an oil-based dye ink type marking pen (Zebra Co., Ltd., trade name: Mackey) without any gaps. Come on. 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. Tables 4-4 to 4-6 show the number of repetitions in which the oil-based ink could be wiped off.

From the results of Tables 4-1 to 4-6, the composition of the present invention provides a cured film having an excellent antireflection effect, excellent scratch resistance, and stain resistance by obtaining a low refractive index. I understand that.
From the results of Table 4-5, it can be seen that the cured film made of the composition of the present invention is excellent in scratch resistance (eraser) and repeated magic wiping.

  The curable resin composition of the present invention can provide a cured film excellent in scratch resistance, coating property and durability, and can be used as an antireflection film material or a polymer cladding, particularly for an antireflection film. Useful as a material.

FIG. 1 is a schematic view showing an embodiment of the antireflection film of the present invention. FIG. 2 is a schematic view showing another embodiment of the antireflection film of the present invention. FIG. 3 is a schematic view showing another embodiment of the antireflection film of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Antireflection film 2 Base material 3 Hard coat layer 4 Low refractive index layer 5 High refractive index layer 6 Middle refractive index layer

Claims (16)

The following components (B), (D) and (I):
(B) a compound represented by the following general formula (B-1),
(D) A curable resin composition containing hollow or porous particles mainly composed of silica having a number average particle diameter of 1 to 100 nm, and (I) an organic solvent.

[In the formula (B-1), R ^b represents a hydrogen atom or a methyl group. ]   The curable resin composition according to claim 1, further comprising (C) a compound excluding (B) having two or more (meth) acryloyl groups.   The curable resin composition according to claim 1, further comprising (H) a compound having a polydimethylsiloxane skeleton. The following components (A), (B) and (I):
(A) an ethylenically unsaturated group-containing fluoropolymer,
(B) A curable resin composition containing a compound represented by the following general formula (B-1) and (I) an organic solvent.

[In the formula (B-1), R ^b represents a hydrogen atom or a methyl group. ]   (A) An ethylenically unsaturated group-containing fluoropolymer is obtained by reacting a compound containing at least one ethylenically unsaturated group and a group capable of reacting with a hydroxyl group with a hydroxyl group-containing fluoropolymer. The curable resin composition according to claim 4, which is an ethylenically unsaturated group-containing fluoropolymer.   Furthermore, (C) The curable resin composition of Claim 4 or 5 containing the compound except (B) which has a 2 or more (meth) acryloyl group.   Furthermore, (D) The curable resin composition of any one of Claims 4-6 containing the hollow or porous particle | grains which have a silica with a number average particle diameter of 1-100 nm as a main component.   Furthermore, (E) The curable resin composition of any one of Claims 4-8 containing the solid particle | grains which have a silica with a number average particle diameter of 1-100 nm as a main component.   The curable resin composition according to claim 7 or 8, wherein the (D) and / or (E) silica-based particles have a (meth) acryloyl group on the surface.   The curable resin according to any one of claims 4 to 9, further comprising (F) a compound having one (meth) acryloyl group and a cyclic structure having 3 or more carbon atoms and having a molecular weight of 400 or less. Composition.   Furthermore, (G) Curable resin composition of any one of Claims 4-10 containing the compound which generate | occur | produces active species by irradiation of an active energy ray.   Furthermore, the curable resin composition of any one of Claims 4-11 containing the compound which has (H) polydimethylsiloxane frame | skeleton.   Furthermore, (J) Curable resin composition of any one of Claims 4-12 containing a fluorine-type surfactant.   The curable resin composition according to claim 1, which is used for an antireflection film.   Hardened | cured material obtained by hardening the curable resin composition of any one of Claims 1-13.   An antireflection film having a low refractive index layer comprising the cured product according to claim 15.

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