JP2008044979A - Curable resin composition and antireflection film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition giving a cured film, which has a low refractive index and is excellent in scratch resistance and excellently resistant to whitening on wiping-off, and an antireflection film having a low refractive index layer composed of the cured product. <P>SOLUTION: The curable resin composition comprises the following components (A)-(D): (A) an ethylenically unsaturated group-containing fluoropolymer; (B) a compound having at least two (meth)acryloyl groups; (C) a compound having a siloxane skeleton and a number-average molecular weight of at least 40,000; and (D) an organic solvent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

In various display panels such as liquid crystal display panels, cold cathode ray tube panels, plasma displays, etc., in order to prevent reflection of external light and improve image quality, it has low refractive index, scratch resistance, coatability, and durability. There is a 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 by the said gazette had the subject that it could not be said that coating property and abrasion resistance were 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). However, in many cases, since one type of silica particle having a relatively uniform particle size is used, the filling rate of the particles cannot be increased, and sufficient scratch resistance has not been obtained.

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, a technique using particles having voids inside the particles such as porous particles and hollow particles (hereinafter collectively referred to as hollow particles). Is known (for example, Patent Documents 7 to 9).
However, when hollow particles are used, there is a drawback that the scratch resistance of the cured film is reduced as compared with particles having no voids (solid particles).

Further, various radiation curable materials have been proposed with a focus on high productivity and curing at room temperature. However, the conventional radiation curable resin composition has not been able to obtain sufficient scratch resistance at a low irradiation light amount of 0.2 J / cm ² or less.

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, the present invention provides a curable resin composition that gives a cured product (cured coating film) having a low reflectivity, excellent scratch resistance and wiping resistance, and an antireflection film having a low refractive index layer comprising the cured product. The purpose is to provide.

  In order to achieve the above-mentioned object, the present inventors have conducted intensive research and obtained a curability obtained by adding a slip agent component having a specific molecular weight to an ethylenically unsaturated group-containing fluoropolymer and a specific (meth) acrylate compound. The present inventors have found that the resin composition has excellent surface slipperiness and scratch resistance, and in particular, gives a cured product (cured coating film) excellent in wiping whitening property, thereby completing the present invention.

［式（Ｃ−１）中、Ｒ¹⁸〜Ｒ²³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、Ｒ²⁴及びＲ²⁵は、同一でも異なっていてもよく、二価の有機基を示し、Ｒ²⁶及びＲ²⁷は、同一でも異なっていてもよく、（メタ）アクリロイル基を有する一価の有機基を示し、ｔ、ｕは１〜６の数、ａは１〜２００の数、ｂは１〜２０の数を示す。］
４．前記（Ｃ）数平均分子量が４０，０００以上のシロキサン骨格を有する化合物が下記一般式（Ｃ−２）で表される化合物からなる群から選択されることを特徴とする上記１に記載の硬化性樹脂組成物。

［式（Ｃ−２）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、ｒ、ｓは０〜６の数、ｙは１〜２００の数、ｚは１〜２０の数を示す。］
５．前記（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ことを特徴とする上記１〜４のいずれか記載の硬化性樹脂組成物。
６．前記（Ｂ）（メタ）アクリロイル基を有する化合物が、分子内に３個以上の（メタ）アクリロイル基を含有する化合物を含有することを特徴とする上記１〜５のいずれかに記載の硬化性樹脂組成物。
７．（Ｅ）シリカを主成分とする数平均粒径４０〜１００ｎｍの粒子、及び（Ｆ）シリカを主成分とする数平均粒径１〜３０ｎｍの粒子のいずれか一以上を含有することを特徴とする上記１〜６のいずれか１項に記載の硬化性樹脂組成物。
８．前記（Ｅ）及び（Ｆ）のシリカを主成分とする粒子の少なくとも一方が中空若しくは多孔質の粒子であることを特徴とする上記７に記載の硬化性樹脂組成物。
９．前記（Ｅ）及び（Ｆ）のシリカを主成分とする粒子の少なくとも一方が表面に（メタ）アクリロイル基を有することを特徴とする上記７又は８に記載の硬化性樹脂組成物。
１０．反射防止膜用である上記１〜９のいずれかに記載の硬化性樹脂組成物。
１１．上記１〜１０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。
１２．上記１１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 (A) to (D):
(A) an ethylenically unsaturated group-containing fluoropolymer,
(B) a compound having two or more (meth) acryloyl groups,
(C) A curable resin composition containing a compound (D) having a siloxane skeleton and a number average molecular weight of 40,000 or more (D) an organic solvent.
2. 2. The curable resin composition as described in 1 above, wherein the (C) compound having a siloxane skeleton and having a number average molecular weight of 40,000 or more has a (meth) acryloyl group.
3. 3. The curable resin composition according to 2 above, wherein the (C) compound having a siloxane skeleton and having a number average molecular weight of 40,000 or more is a compound represented by the following general formula (C-1): object.

[In Formula (C-1), R ^{18 to} R ²³ may be the same or different and each represents a hydrogen atom, an alkyl group or a cyano group, and R ²⁴ and R ²⁵ may be the same or different, R ²⁶ and R ^{27, which} may be the same or different, each represents a monovalent organic group having a (meth) acryloyl group, t and u are 1 to 6 and a is The number of 1-200 and b show the number of 1-20. ]
4). 2. The curing according to 1 above, wherein the compound (C) having a siloxane skeleton having a number average molecular weight of 40,000 or more is selected from the group consisting of compounds represented by the following general formula (C-2): Resin composition.

[In Formula (C-2), 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, A hydrogen atom or an alkyl group is shown, p and q are numbers 1 to 6, r and s are numbers 0 to 6, y is a number 1 to 200, and z is a number 1 to 20. ]
5. The (A) ethylenically unsaturated group-containing fluoropolymer contains an ethylenically unsaturated group-containing polymer obtained by reacting a compound containing at least one ethylenically unsaturated group with a hydroxyl group-containing fluoropolymer. 5. The curable resin composition as described in any one of 1 to 4 above, which is a fluoropolymer.
6). The curability according to any one of 1 to 5 above, wherein the compound having (B) (meth) acryloyl group contains a compound containing 3 or more (meth) acryloyl groups in the molecule. Resin composition.
7). (E) It contains any one or more of particles having a number average particle diameter of 40 to 100 nm mainly composed of silica and (F) particles having a number average particle diameter of 1 to 30 nm mainly composed of silica. The curable resin composition according to any one of 1 to 6 above.
8). 8. The curable resin composition as described in 7 above, wherein at least one of the particles (E) and (F) containing silica as a main component is hollow or porous particles.
9. 9. The curable resin composition as described in 7 or 8 above, wherein at least one of the (E) and (F) silica-based particles has a (meth) acryloyl group on the surface.
10. 10. The curable resin composition according to any one of 1 to 9 above, which is for an antireflection film.
11. Hardened | cured material obtained by hardening the curable resin composition in any one of said 1-10.
12 12. An antireflection film having a low refractive index layer comprising the cured product as described in 11 above.

According to the present invention, it is possible to obtain a curable resin composition that gives a cured product having a low reflectance, excellent scratch resistance and wiping-off whitening property.
Furthermore, according to the present invention, an antireflection film having a low refractive index layer composed of the cured product and having excellent scratch resistance and wiping-off whitening property can be obtained.

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

1. Curable resin composition The curable resin composition of this invention (henceforth the composition of this invention) may contain the following component (A)-(I). Among these components, (A) to (D) are essential components, and (E) to (I) are optional components that can be appropriately contained.
(A) Ethylenically unsaturated group-containing fluoropolymer (B) Compound having two or more (meth) acryloyl groups (C) Compound having a siloxane skeleton and a number average molecular weight of 40,000 or more (D) Organic Solvent (E) Particles having a number average particle size of 40 to 100 nm mainly composed of silica (F) Particles having a number average particle size of 1 to 30 nm mainly composed of silica (G) One (meth) acryloyl group and carbon Compound (H) photopolymerization initiator (I) and other additives having a cyclic structure of several 3 or more and a molecular weight of 400 or less

In the composition of the present invention, the surface slipperiness of the cured film obtained is improved by adding a compound having (C) siloxane skeleton as a slip agent component and having a number average molecular weight of 40,000 or more. In addition, it has excellent wiping resistance and whitening resistance. Here, “wiping whitening property” refers to a phenomenon in which the surface of the cured film looks white when the surface of the cured film is rubbed with a nonwoven fabric or the like, and it is assumed that fine holes are formed on the surface of the cured film. Further, “excellent in wiping-off whitening resistance” means that even when the surface of the cured film is rubbed with a nonwoven fabric or the like, there is little change in appearance, and fine holes are hardly formed on the surface.
Further, when the silica particles (E) and / or (F) have a porous or hollow structure, a lower reflectance can be obtained.
By adding the component (G), a part of the component (G) penetrates into the base hard coat layer, thereby increasing the adhesion between the hard coat layer and the low refractive index layer, and thus having high scratch resistance. A film (low refractive index film) is considered to be obtained.
Further, the composition of the present invention uses, as a photopolymerization initiator, a compound represented by the formula (H-1) described later as the component (H) alone, or other photopolymerization initiator (H). Can be used to provide a cured product having excellent scratch resistance even at a low irradiation light amount of 0.2 J / cm ² or less.
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.
In the component (A), the side chain hydroxyl group is preferably modified with a (meth) acrylic compound. Further, it is preferably modified with a (meth) acrylic compound having an isocyanate group. Such modification allows co-crosslinking with the radically polymerizable (meth) acrylic compound and improves the scratch resistance.

  The ethylenically unsaturated group-containing fluoropolymer is obtained by reacting a compound containing at least one ethylenically unsaturated group with a hydroxyl group-containing fluoropolymer.

(1) Compound containing at least one ethylenically unsaturated group As a compound containing at least one ethylenically unsaturated group, a compound containing at least one ethylenically unsaturated group in the molecule The functional group is not particularly limited as long as it has a functional group capable of reacting with the hydroxyl group of the hydroxyl group-containing fluoropolymer.
Moreover, since the curable resin composition mentioned later can be hardened more easily as said ethylenically unsaturated group, the compound which has a (meth) acryloyl group is more preferable.
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 (meth) acrylate which has an isocyanate group, Showa Denko Co., Ltd. brand name Karenz MOI, AOI, BEI etc. 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)_ｆ−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、ｆ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 ) _f —OR ⁵ or —OCOR ⁵ (R ⁵ represents an alkyl group or A glycidyl group, f represents a number of 0 or 1), 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 R7, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 5-hydroxypentyl group, A 6-hydroxyhexyl group may be mentioned.

The structural unit (c) can be introduced by using a hydroxyl group-containing vinyl monomer as a polymerization component. Examples of such hydroxyl group-containing vinyl monomers include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-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、ｒ、ｓ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. Or, it represents an alkyl group, p and q are numbers 1 to 6, r and s 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、ｒ、ｓ及びｙは、上記式（５）と同じである。］ (E) A structural unit represented by the following formula (6).

Wherein ^{(6), R 10 ~R 13} , R 14 ~R 17, p, q, r, s and y are the same as in the formula (5). ]

In the formulas (5) and (6), examples of the alkyl group represented by R ^{10 to} R ¹³ include alkyl groups having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, and a cyclohexyl group. Examples of the alkyl group of ^{14 to} R ¹⁷ include an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group.

  In the present invention, the azo group-containing polysiloxane compound represented by the above formula (5) is particularly preferably a compound represented by the following formula (7).

［式（７）中、ｙ及びｚは、上記式（５）と同じである。］

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

In addition, it is preferable that the content rate of a structural unit (d) shall be 0.1-10 mol part with respect to a total of 100 mol parts of the structural units (a)-(c) in a hydroxyl-containing fluoropolymer. . 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.
For these reasons, the content of the structural unit (d) is 0.1 to 5 mol with respect to 100 mol parts in total of the structural units (a) to (c) in the hydroxyl group-containing fluoropolymer. The amount is more preferably 0.1 to 3 mol parts. For the same reason, the content of the structural unit (e) is desirably determined so that the content of the structural unit (d) contained therein is in the above range.

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

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

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

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

［式（９）中、ｎは１〜２０の数、ｍは０〜４の数、ｋは３〜５０の数を示す］

［式（１０）中、ｇは０〜４の数、ｈは１４〜４５の数、ｊは１０〜１４の数を示す］ Examples of the group having such an emulsifying action include groups represented by the following formulas (9) and (10).

[In Formula (9), n is a number from 1 to 20, m is a number from 0 to 4, and k is a number from 3 to 50]

[In Formula (10), g is a number from 0 to 4, h is a number from 14 to 45, and j is a number from 10 to 14.]

  The structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component. Examples of such reactive emulsifiers include compounds represented by the following formulas (11) and (12).

［式（１１）中、ｎ、ｍ及びｋは、上記式（９）と同様である］

［式（１２）中、ｇ、ｈ及びｊは、上記式（１０）と同様である］

[In formula (11), n, m, and k are the same as those in formula (9) above]

[In Formula (12), g, h, and j are the same as those in Formula (10) above]

In addition, it is preferable that the content rate of a structural unit (f) shall be 0.1-5 mol part with respect to a total of 100 mol parts of the structural units (a)-(c) in a hydroxyl-containing fluoropolymer. . 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 these reasons, the content of the structural unit (f) is set to 0.1 to 3 moles with respect to a total of 100 mole parts of the structural units (a) to (c) in the hydroxyl group-containing fluoropolymer. More preferably, it is more preferably 0.2 to 3 mole parts.

(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 3 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 3% by weight, the refractive index of the cured coating film of the curable resin composition becomes high, and a sufficient antireflection effect may not be obtained. 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 this reason, the amount of component (A) added is more preferably 5 to 60% by weight, and even more preferably 5 to 40% by weight.

(B) Compound having two or more (meth) acryloyl groups Two or more (meth) acrylate compounds are a cured product obtained by curing a curable resin composition and anti-scratch of an antireflection film using the cured product. Used to enhance the sex.

  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 having two or more (meth) acryloyl groups include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, and tricyclo Decanediyldimethylene di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanurate Tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide (hereinafter referred to as “EO”) modified trimethylolpropane tri (meth) acrylate, propylene Xoxide (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. Can do. Examples of commercially available products of these multifunctional monomers include SA1002 (manufactured by Mitsubishi Chemical Corporation), biscoat 195, biscoat 230, biscoat 260, biscoat 215, biscoat 310, biscoat 214HP, biscoat 295, biscoat 300, Biscoat 360, Biscoat GPT, Biscoat 400, Biscoat 700, Biscoat 540, Biscoat 3000, Biscoat 3700 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Kayarad R-526, HDDA, NPGDA, TPGDA, MANDA, R-551, R-712, R-604, R-684, PET-30, GPO-303, TMPTA, THE-330, DPHA, DPHA-2H, DPHA-2C, DPHA-2I, D-310, D-330, DPCA 20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, T-1420, T-2020, T-2040, TPA-320, TPA-330, RP-1040, RP-2040, R-011, R-300, R-205 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-220, M-233, M-240, M-215, M-305, M- 309, M-310, M-315, M-325, M-400, M-6200, M-6400 (above, manufactured by Toagosei Co., Ltd.), light acrylate BP-4EA, BP-4PA, BP-2EA, BP-2PA, DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.), New Frontier BPE-4, BR-42M, GX-8345 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), ASF 400 (above, manufactured by Nippon Steel Chemical Co., Ltd.), Lipoxy SP-1506, SP-1507, SP-1509, VR-77, SP-4010, SP-4060 (above, Showa Polymer Co., Ltd.), NK ester A-BPE-4 (manufactured by Shin-Nakamura Chemical Co., Ltd.).

  In addition, among these, the compound containing 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 (B) added is not particularly limited, but is usually 5 to 70% by weight with respect to the total amount of the composition other than the organic solvent. The reason for this is that when the addition amount is less than 5% by weight, the scratch resistance of the cured coating film of the curable resin composition may not be obtained, whereas when the addition amount exceeds 70% 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 (B) added is more preferably 10 to 60% by weight, and even more preferably 10 to 50% by weight.

(C) A compound having a siloxane skeleton and a number average molecular weight of 40,000 or more A compound having a siloxane skeleton has an effect of improving surface slipperiness and improving scratch resistance of a cured coating film, and antifouling properties. Further, a compound having a siloxane skeleton having a number average molecular weight of 40,000 or more can impart excellent wiping-off whitening properties to the resulting cured film.
In the composition of the present invention, only the compound of component (C) may be used as a slip agent added to improve surface slipperiness, or other slip agent components may be used in combination.

The compound of component (C) needs to have a polystyrene equivalent number average molecular weight of 40,000 or more measured by gel permeation chromatography using tetrahydrofuran as a solvent. This is because if the number average molecular weight is less than 40,000, sufficient wiping-off whitening property may not be obtained.
For such reasons, the polystyrene-equivalent number average molecular weight of the component (C) compound is more preferably 40,000 to 150,000, and more preferably 50,000 to 120,000.
More preferably.

  Moreover, what has a (meth) acryloyl group can also be used as a compound of a component (C). As (C) component which has a (meth) acryloyl group, the compound represented by the following general formula (C-1) is used suitably. By having a (meth) acryloyl group, there is an effect of improving the dispersibility and stability of the component (C) in a cured film obtained by curing the composition.

［式（Ｃ−１）中、Ｒ¹⁸〜Ｒ²³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、Ｒ²⁴及びＲ²⁵は、同一でも異なっていてもよく、二価の有機基を示し、Ｒ²⁶及びＲ²⁷は、同一でも異なっていてもよく、（メタ）アクリロイル基を有する一価の有機基を示し、ｔ、ｕは１〜６の数、ａは１〜２００の数、ｂは１〜２０の数を示す。］

[In Formula (C-1), R ^{18 to} R ²³ may be the same or different and each represents a hydrogen atom, an alkyl group or a cyano group, and R ²⁴ and R ²⁵ may be the same or different, R ²⁶ and R ^{27, which} may be the same or different, each represents a monovalent organic group having a (meth) acryloyl group, t and u are 1 to 6 and a is The number of 1-200 and b show the number of 1-20. ]

  The compound represented by the above formula (C-1) forms an intermediate containing an isocyanate group by, for example, reacting a compound containing two isocyanate groups with a polysiloxane having hydroxyl groups at both ends. The isocyanate remaining in the intermediate can then be reacted with an active hydrogen-containing polymerizable unsaturated compound.

  In addition, as an example of the commercial item of the polysiloxane which has a hydroxyl group in both terminals, the Chisso Co., Ltd. product, Silaplane FM-4411, FM-4421, FM-4425, etc. are mentioned.

  Examples of compounds containing two isocyanate groups include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 1,3-xylylene diisocyanate. 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanate) Toethyl) 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 addition, as an example of the active hydrogen-containing polymerizable unsaturated compound, one active hydrogen atom capable of forming a [—O—C (═O) —NH—] group by addition reaction with an isocyanate group in the molecule. Examples thereof include compounds having at least one and having at least one polymerizable unsaturated group. 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.

  Moreover, as a compound of a component (C), what does not have a (meth) acryloyl group can be used. In the curable resin composition of the present invention, a component having a number average molecular weight of 40,000 or more is used as the component (C), and excellent wiping resistance even when a compound having no (meth) acryloyl group is used. Has whitening properties. As (C) component which does not have a (meth) acryloyl group, the compound represented by the following general formula (C-2) is used suitably.

式（Ｃ−２）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、ｒ、ｓは０〜６の数、ｙは１〜２００の数、ｚは１〜２０の数を示す。

In formula (C-2), 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 hydrogen An atom or an alkyl group is shown, p and q are numbers 1 to 6, r and s are numbers 0 to 6, y is a number 1 to 200, and z is a number 1 to 20.

式（Ｃ−２ａ）中、ｙ及びｚは、上記式（Ｃ−２）と同じである。 As the compound represented by the above formula (C-2), it is preferable to use a high molecular weight azo group-containing polysiloxane represented by the following general formula (C-2a).

In formula (C-2a), y and z are the same as those in formula (C-2).

  The compounds represented by the formulas (C-2) and (C-2a) are raw materials for producing the (A) ethylenically unsaturated group-containing fluoropolymer used in the composition of the present invention. Since it is the same as the compound represented by the formulas (5) and (7) described as the compounds to be the structural units (d) and (e) constituting the hydroxyl group-containing fluoropolymer, detailed description is omitted here. To do.

  Specific examples of the compound represented by the above formula (C-2) (including the compound represented by the above formula (C-2a)) include VPS-1001 (manufactured by Wako Pure Chemical Industries, number average molecular weight 60,000), VPS-1001N, VPS0501, VPS0501N (made by Wako Pure Chemical Industries), etc. are mentioned. VPS-1001 is particularly preferable.

The amount of component (C) added is usually 0.01 to 20% by weight based on the total amount of the composition excluding the organic solvent. The reason for this is that if the amount added is less than 0.01% by weight, the effect of improving the slipperiness may not be sufficiently obtained. There is a case where deterioration of coating property and deterioration of coating property occur.
For this reason, the amount of component (C) added is more preferably 0.1 to 10% by weight, and even more preferably 0.5 to 8% by weight.

(D) Organic solvent The curable resin composition contains an organic solvent. By adding an organic solvent, a thin antireflection film can be formed uniformly. Specific examples of the organic solvent include 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, 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, and methyl isobutyl ketone, methyl amyl ketone and t-butanol are used alone or in 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.

(E) Particles having a number average particle diameter of 40 to 100 nm mainly composed of silica, and (F) Particles having a number average particle diameter of 1 to 30 nm mainly composed of silica (1) Particles mainly composed of silica In the composition, either or both of particles (E) having a number average particle size of 40 to 100 nm mainly composed of silica and particles (F) having a number average particle size of 1 to 30 nm mainly composed of silica are contained. Can be blended. Furthermore, these two types of particles having different particle diameters can be blended alone or in combination. The particle size of the particles mainly composed of silica is measured with a transmission electron microscope.
By blending particles (E) having a number average particle size of 40 to 100 nm mainly composed of silica, a cured product obtained by curing the composition of the present invention can exhibit a low refractive index and scratch resistance. it can.
By blending particles (F) having a number average particle diameter of 1 to 30 nm mainly composed of silica, the scratch resistance of the cured product obtained by curing the composition of the present invention, particularly the steel wool resistance can be improved. it can.
As these particles mainly composed of silica, known particles can be used, and if the shape is spherical, not only ordinary colloidal silica but also hollow particles, porous particles, core-shell particles And so on. However, from the viewpoint of reducing the refractive index of the composition, hollow particles and porous particles are preferable, and it is particularly preferable that either one or both of the components (E) and (F) are hollow particles or porous particles. Moreover, it is not limited to a spherical shape, and may be an irregularly shaped particle. Colloidal silica having a solid content of 10 to 40% by weight is preferred.

The dispersion medium is preferably water or an organic solvent. Examples of organic solvents include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol and ethylene glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethylformamide and dimethyl Examples include amides such as acetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and γ-butyrolactone; and organic solvents such as ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in combination of two or more as a dispersion medium.
As a commercial item of the particle | grains which have a silica as a main component, as a colloidal silica, for example, Nissan Chemical Industries Ltd. brand name: Methanol silica sol, IPA-ST, MEK-ST, MEK-ST-S, MEK-ST- L, IPA-ZL, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL etc. can be mentioned.

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

  The particles (E) and (F) containing silica as a main component have been subjected to surface treatment with an organic compound (hereinafter sometimes referred to as “specific organic compound”) containing at least one polymerizable unsaturated group. Preferably there is. Such surface treatment enables co-crosslinking with the UV curable acrylic monomer and improves the scratch resistance.

(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 may be a compound further containing a group represented by the following formula (13) 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（１３）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 (13), 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 (13) The specific organic compound preferably further includes a group represented by Formula (13) in the molecule. Specific examples of the group [—X—C (═Y) —NH—] represented by the formula (13) 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 (14).

In the formula (14), R ²⁸ and R ²⁹ 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 d is 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 ²⁸ O) _d R ²⁹ _3-d Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.

R ³⁰ 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 ³¹ 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 (13). Can also be included.

R ³² is an (e + 1) -valent organic group, and is 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. E 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 (14), (i) 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 (14), 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 with a specific organic compound (hereinafter also referred to as particles) The surface treatment method of particles with a specific organic compound is not particularly limited. It is also possible to manufacture by mixing, heating and stirring. The reaction is preferably carried out in the presence of water in order to efficiently combine the silanol group-forming site of the specific organic compound with the particles. However, when the specific organic compound has a silanol group, there is no need for water. Therefore, the surface treatment can be performed by a method including an operation of mixing at least the particles and the specific organic compound.

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

Hereinafter, the surface treatment method will be described in more detail using the alkoxysilyl group-containing compound (alkoxysilane compound) represented by the formula (14) as an example of the specific organic compound.
The amount of water consumed by hydrolysis of the alkoxysilane compound during the surface treatment may be an amount that allows at least one alkoxy group on silicon in one molecule to be hydrolyzed. Preferably, the amount of water added or present during hydrolysis is at least one third of the number of moles of all alkoxy groups on the silicon, more preferably one half of the number of moles of all alkoxy groups. It is less than 3 times. The product obtained by mixing the alkoxysilane compound and the particles in a completely moisture-free condition is a product in which the alkoxysilane compound is physically adsorbed on the particle surface, and particles composed of such components are not included. In the hardened | cured material of the composition to contain, the effect of expression of high hardness and abrasion resistance is low.

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

In the case of using a powdery powder during the surface treatment, an organic solvent may be added for the purpose of smoothly and uniformly carrying out the reaction with the alkoxysilane compound. Examples of such organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate and 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 specific organic compound. Here, an organic solvent which is uniformly compatible with water may be added for the purpose of ensuring the uniformity at the initial stage of the reaction and allowing the reaction to proceed smoothly.

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

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

(E) The compounding quantity of a component is 1-80 weight% normally with respect to composition whole quantity except an organic solvent, 10-75 weight% is preferable and 20-70 weight% is more preferable.
(F) 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.

(G) 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 composition of the present invention contains one (meth) acryloyl group and a cyclic structure having 3 or more carbon atoms. It is preferable to add a compound having a structure and having a molecular weight of 400 or less. This compound is used to improve the adhesion between the low refractive index cured product obtained by curing the curable resin composition and the base hard coat, and to improve the scratch resistance of the antireflection film using the same. . The component (G) 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.

［式（Ｇ−１）〜（Ｇ−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。 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 (G-1)-(G-5) is mentioned as an example of the compound which gives an effect.

[In formulas (G-1) to (G-5), X ¹ represents hydrogen or a methyl group, and X ² and X ³ each independently represent a linear, branched or cyclic alkyl having 1 to 6 carbon atoms. Indicates a group. ]
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).

The amount of component (G) added is usually 0.5 to 40% 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 0.5% by weight, the penetration (penetration) into the base hard coat layer is insufficient and 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 40% 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 (G) added is more preferably 1 to 40% by weight.

(H) Compound that generates active species upon irradiation with active energy rays Component (H) is a so-called photopolymerization initiator, and is a component used for curing the composition of the present invention with active energy rays such as ultraviolet rays. .

  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.

  Examples of the photopolymerization initiator of component (H) include, for example, 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, as component (H), Irg127 (2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl)-] manufactured by Ciba Specialty Chemicals represented by the following formula (H-1): Benzyl] -phenyl} -2-methyl-propan-1-one), when used alone or in combination with other polymerization initiators, a low irradiation light quantity of 0.2 J / cm ² or less Thus, excellent scratch resistance can be exhibited in a cured product obtained by curing the composition of the present invention.

  The compound represented by the above formula (H-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.

［式中、Ｒ³³及びＲ³⁴はそれぞれ独立に炭素数１〜４のアルキル基を表し、Ｒ³⁵は水酸基又は炭素数１〜４のアルキル基を表し、Ｒ³⁶は水素原子又はメチル基を表す。］
本発明の光重合開始剤は上記式（Ｈ−２）が複数連なった構造であってもよく、その場合の分子量は３５０〜１０，０００の範囲が好ましい。
上記式（Ｈ−２）の構造を有する光重合開始剤を用いることにより、汎用の重合開始剤を用いる場合と比べて、本発明の組成物を硬化させて得られる硬化膜の耐スチールウール性やエタノール耐性等の耐擦傷性が向上する。 Moreover, it is also preferable to mix | blend the photoinitiator which has a structure represented by a following formula (H-2) as (H) component.

[Wherein, R ³³ and R ³⁴ each independently represent an alkyl group having 1 to 4 carbon atoms, R ³⁵ represents a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, and R ³⁶ represents a hydrogen atom or a methyl group. . ]
The photopolymerization initiator of the present invention may have a structure in which a plurality of the above formulas (H-2) are connected, and the molecular weight in that case is preferably in the range of 350 to 10,000.
By using a photopolymerization initiator having the structure of the above formula (H-2), compared to the case of using a general-purpose polymerization initiator, the steel wool resistance of a cured film obtained by curing the composition of the present invention. And scratch resistance such as ethanol resistance is improved.

The amount of component (H) added is usually 0.1 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 0.1% by weight, curing failure may occur. 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 it may happen.
For this reason, the amount of component (H) added is more preferably 0.5 to 10% by weight, and even more preferably 0.5 to 8% by weight.

(I) 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 aid are within the range not impairing the purpose 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, a method for preparing the composition of the present invention and curing conditions will be described.
The composition of this invention can be prepared by adding (I) component according to said (A)-(H) and a condition, respectively, and mixing under room temperature or 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.
In addition, when the photopolymerization initiator of the formula (H-1) of the component (H) is blended in the composition of the present invention, excellent scratch resistance even at a low irradiation light amount of 0.2 J / cm ² or less. The cured film which has can be obtained. Accordingly, it is possible to select a low irradiation light amount in consideration of irradiation time and production efficiency.

Moreover, the composition of this invention can also be heated and dried, and it is preferable to heat for 0.5 to 180 minutes at the temperature within the range of 30-200 degreeC in this case. 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 30 to 150 ° C. for 0.5 to 120 minutes, and to heat at a temperature in the range of 40 to 120 ° 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 composition of the said invention. 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 composition of this invention. Since the composition and the like of the 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 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 preferably 1.50 or less. . 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, whereas when the thickness exceeds 200 nm, the antireflection effect decreases. Because there is.
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 This is because if the thickness exceeds 30,000 nm, the antireflection effect may decrease.
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 fluorine-containing polymer A stainless steel autoclave having an internal volume of 1.0 liter with a magnetic stirrer was sufficiently replaced with nitrogen gas, and then 600 g of ethyl acetate, 138.5 g of perfluoro (propyl vinyl ether), 37.5 g of ethyl vinyl ether, Hydroxyethyl vinyl ether 45.9 g, lauroyl peroxide 1.5 g, azo group-containing polydimethylsiloxane (VPS1001 (trade name), manufactured by Wako Pure Chemical Industries, Ltd.) 9.0 g and nonionic reactive emulsifier (ER-30 ( (Product name), manufactured by Asahi Denka Kogyo Co., Ltd.) 45 g, cooled to −50 ° C. with dry ice-methanol, and then oxygen in the system was removed again with nitrogen gas.

Next, 85.9 g of hexafluoropropylene was charged and the temperature increase was started. The pressure when the temperature in the autoclave reached 55 ° C. was 4.1 × 10 ⁵ Pa. Thereafter, the reaction was continued with stirring at 70 ° C. for 20 hours. When the pressure dropped to 2.0 × 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 30.0%. The obtained polymer solution was put into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 250 g of a hydroxyl group-containing fluoropolymer. This is referred to as a hydroxyl group-containing fluoropolymer. Table 1 shows the monomers and solvents used.

It attached to the obtained hydroxyl-containing fluoropolymer, and measured the polystyrene conversion number average molecular weight by gel permeation chromatography. Moreover, the ratio of each monomer component which comprises a hydroxyl-containing fluoropolymer was determined from both NMR analysis results and elemental analysis results of ¹ H-NMR and ¹³ C-NMR. 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 h is a number from 14 to 45 and j is 10 to 14 in the above formula (12).
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)
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. 50.0 g of the hydroxyl group-containing fluoropolymer obtained in Production Example 1, 0.01 g of 2,6-di-t-butylmethylphenol and 359 g of methyl isobutyl ketone (MIBK) as a polymerization inhibitor were charged at 20 ° C. The hydroxyl group-containing fluoropolymer 1 was dissolved in MIBK and stirred until the solution became transparent and uniform.
Next, 13.4 g of 2-methacryloyloxyethyl isocyanate was added to this system and stirred until the solution became homogeneous, then 0.1 g of dibutyltin dilaurate was added to start the reaction, and the temperature of the system was changed to 55 to 55. 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.

(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. This consists of NK ester A-TMM-3LM-N (60% by mass of pentaerythritol triacrylate and 40% by mass 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 at 2550 cm ⁻¹ characteristic for the mercapto group in the raw material and the absorption peak at 2260 cm ⁻¹ characteristic for the isocyanate group disappear, and [−O—C (= O) -NH-] group and [-S-C (= O) -NH-] peak characteristic 1720 cm ^-1 to the carbonyl in the group the peak and acryloyl groups characteristic 1660 cm ^-1 - click is observed And a specific organic compound having both an acryloyl group as a polymerizable unsaturated group, a [—S—C (═O) —NH—] group, and a [—O—C (═O) —NH—] group is formed. Showed that.

(Production Example 6)
Production of acrylic-modified hollow silica particles E-1 (component (E)) 2.1 parts of the specific organic compound (S1) synthesized in Production Example 5, hollow silica particle sol (manufactured by Catalyst Kasei, trade name: JX1009-SIV (particles) (Concentration 21%)) 137 parts (solid content 28.8 parts), p-hydroquinone monomethyl ether 0.01 part, and ion-exchanged water 0.06 part mixed solution at 80 ° C. for 3 hours, and then orthoformate methyl ester 0.7 part was added, and further, colorless and transparent particle dispersion E-1 was obtained by heating and stirring at the same temperature for 1 hour. After weighing 2 g of E-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 22.1% 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 acrylic-modified solid silica particles F-1 (component (F)) 2.0 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 size 0.022 μm, silica concentration 30%)) 91.3 parts (solid content 27.4 parts), p-hydroquinone monomethyl ether 0.01 parts, ion-exchanged water 0.1 parts After stirring at 80 ° C. for 3 hours, 1.3 parts of methyl orthoformate was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain a colorless transparent particle dispersion F-1. After weighing 2 g of F-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 31% 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.

［式（Ｃ−１−１）中、Acrylはアクリロイル基を示し、ａは１から２００の数、ｂは１〜２０の数を示す。] (Production Example 8)
Production of high molecular weight polydimethylsiloxane C-1-1 (component (C)) A compound (C-1-1) represented by the following formula was synthesized as follows. In a separable flask having a capacity of 0.3 liter equipped with a magnetic stirrer, a glass cooling tube, and a thermometer, 98.2 g of hydroxyl group-containing polydimethylsiloxane (manufactured by Chisso Corporation, trade name: Silaplane FM4425). Then, 0.06 g of 2,6-di-t-butylmethylphenol and 0.08 g of dibutyltin dilaurate were charged as a polymerization inhibitor and stirred at 20 ° C. until the solution became uniform.
Next, 1.71 g of toluene diisocyanate was added dropwise to this system to start the reaction, and the temperature of the system was maintained at 55 to 65 ° C., and stirring was continued for 3 hours. Thereafter, 5.3 g of methyl ethyl ketone and 0.13 g of hydroxyethyl acrylate were added dropwise and stirred for 3 hours to obtain a reaction product C-1-1. About the product in this reaction liquid, when the amount of residual isocyanate was measured by FT-IR similarly to manufacture example 5, it was 0.1 mass% or less, and it was confirmed that reaction was performed substantially quantitatively. . Moreover, it confirmed that a molecule | numerator contained a urethane bond and an acryloyl group (polymerizable unsaturated group) in a molecule | numerator. Furthermore, when the reaction product C-1-1 was measured by gel permeation chromatography using tetrahydrofuran as a solvent, it was confirmed that the polystyrene-equivalent number average molecular weight was 70,000.

[In formula (C-1-1), Acryl represents an acryloyl group, a represents a number from 1 to 200, and b represents a number from 1 to 20. ]

(Example 1)
As shown in Table 3 below, 2.33 g of the MIBK solution of the ethylenically unsaturated group-containing fluoropolymer A-1 obtained in Production Example 2 (0.35 g as the solid content of the component (A)), pentaerythritol Hydroxytriacrylate 0.88 g (PET-30, Nippon Kayaku, (B) component), acryloylmorpholine 0.23 g (ACMO, manufactured by Kojin), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (Irgacure 127, manufactured by Ciba Specialty Chemicals, (H) component) 0.13 g, High molecular weight azo group-containing polydimethylsiloxane (VPS1001, manufactured by Wako Pure Chemical Industries, Ltd.) 0.13 g, acrylic-modified solid silica particles (F-2) 0.67 g 0.21 g as a solid content), 9.43 g of acrylic-modified hollow silica particles (E-1) (2.08 g as a solid content), and 86.21 g of MIBK were charged into a glass separable flask equipped with a stirrer and brought to room temperature. And stirred for 3 hours to obtain a uniform curable resin composition. Further, the solid content concentration determined by the method of Production Example 2 was 4.0% by weight.

(Examples 2-3, Comparative Examples 1-3)
Each curable resin composition was obtained in the same manner as in Example 1 except that the composition shown in Table 3 below was used.

(Evaluation example 1)
Evaluation of Appearance Each of the curable resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3 was a 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 ultraviolet ray was irradiated with an irradiation light amount of 0.2 J / cm ² using a high pressure mercury lamp to produce an antireflection film. The appearance of the obtained antireflection film was visually confirmed and evaluated according to the following evaluation criteria. The results are shown in Table 3.
○: No coating unevenness Δ: Some coating unevenness ×: 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 Table 3.
○: Haze 0.3% or less △: Haze more than 0.3%, 1.0% or less ×: Haze more than 1.0%

(Evaluation example 3)
Reflectivity of antireflection film The back surface of the antireflection film obtained in Evaluation Example 1 was painted with black spray, and a spectral reflectance measurement device (a self-recording spectrophotometer U- incorporating a large sample chamber integrating sphere attachment device 150-09090 was installed. 3410, manufactured by Hitachi, Ltd.), the reflectance was measured from the substrate side in the wavelength range of 300 to 800 nm and evaluated. Specifically, the reflectance of the antireflection laminate (antireflection film) at each wavelength is measured using the reflectance of the aluminum deposited film as a reference (100%), and the reflectance of light at a wavelength of 550 nm is measured. did. The results are shown in Table 3.

(Evaluation example 4)
Scratch resistance test (steel wool resistance test)
The surface of the antireflection film obtained in Evaluation Example 1 was repeatedly rubbed with steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) 10 times under the condition of a load of 500 g. The presence or absence of occurrence was visually confirmed and evaluated according to the following evaluation criteria. The results are shown in Table 3.
Here, the “white spot” refers to a phenomenon in which fine holes are formed on the surface and the surface of the cured film looks white.

(Evaluation example 5)
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 Table 3.
○: 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 6)
Wipe resistance whitening resistance The coating surface of the antireflection film obtained in Evaluation Example 1 was repeatedly rubbed by hand 10 times with a non-woven fabric (product name: Bencot S-2, manufactured by Asahi Kasei). The wipe whitening resistance was evaluated according to the following criteria. The results are shown in Table 3. Here, “wipe-off whitening resistance” refers to a phenomenon in which when a cured film surface is rubbed with a nonwoven fabric or the like, fine holes are formed on the surface, and the cured film surface appears to be white.
○: The coating surface does not change ×: The coating surface becomes white

The product names in Table 3 represent the following.
PET-30: pentaerythritol hydroxytriacrylate, manufactured by Nippon Kayaku Co., Ltd. ACMO: acryloylmorpholine, manufactured by Kojin IRGACURE127: 2-hydroxy-1- {4- [2- (2-hydroxy-2-methyl-propionyl) -benzyl] -Phenyl} -2-methyl-propan-1-one, manufactured by Ciba Specialty Chemicals FM-0725: Silaplane FM-0725, acrylic modified polydimethylsiloxane, manufactured by Chisso, number average molecular weight 10,000
FM-0425: Silaplane FM-0425, polydimethylsiloxane, manufactured by Chisso, number average molecular weight 10,000
VPS1001: High molecular weight azo group-containing polydimethylsiloxane, manufactured by Wako Pure Chemical Industries, Ltd .; polydimethylsiloxane represented by formula (C-2a) (4,4′-azobis (4-cyanovaleric acid) and α, ω-bis (3-aminopropyl) polydimethylsiloxane polycondensate (VPS1001: manufactured by Wako Pure Chemical Industries, Ltd., number average molecular weight: 60,000)

  From the results of Table 3, the compositions of Examples containing the high molecular weight azo group-containing polydimethylsiloxane (VPS1001) or the high molecular weight polydimethylsiloxane C-2-1 as the component (C) are resistant to contamination and scratch. It is found that a cured film excellent in wiping resistance and whitening resistance is obtained. On the other hand, it can be seen that the composition of Comparative Example 1 which does not contain any compound having a siloxane skeleton has poor stain resistance. It can be seen that in Comparative Examples 2 and 3 containing a compound having a siloxane skeleton having a number average molecular weight of less than 40,000, the scratch resistance and wiping whitening resistance are insufficient.

  The curable resin composition of the present invention is excellent in coating property, has a low refractive index and low reflectance, and can give a cured film excellent in scratch resistance and wiping-off whitening property, particularly as an antireflection film material. Useful.

It is sectional drawing of the antireflection film by one Embodiment of this invention. It is sectional drawing of the anti-reflective film by other embodiment of this invention. It is sectional drawing of the anti-reflective film by other embodiment of this invention.

Explanation of symbols

2 Base material 3 Hard coat layer 4 Low refractive index layer 5 High refractive index layer 6 Medium refractive index layer

Claims (12)

The following components (A) to (D):
(A) an ethylenically unsaturated group-containing fluoropolymer,
(B) a compound having two or more (meth) acryloyl groups,
(C) A curable resin composition containing a compound (D) having a siloxane skeleton and a number average molecular weight of 40,000 or more (D) an organic solvent.   2. The curable resin composition according to claim 1, wherein the (C) compound having a siloxane skeleton and having a number average molecular weight of 40,000 or more has a (meth) acryloyl group. 3. The curable resin according to claim 2, wherein the compound (C) having a siloxane skeleton and having a number average molecular weight of 40,000 or more is a compound represented by the following general formula (C-1): Composition.

[In Formula (C-1), R ^{18 to} R ²³ may be the same or different and each represents a hydrogen atom, an alkyl group or a cyano group, and R ²⁴ and R ²⁵ may be the same or different, R ²⁶ and R ^{27, which} may be the same or different, each represents a monovalent organic group having a (meth) acryloyl group, t and u are 1 to 6 and a is The number of 1-200 and b show the number of 1-20. ] The compound (C) having a siloxane skeleton having a number average molecular weight of 40,000 or more is selected from the group consisting of compounds represented by the following general formula (C-2). Curable resin composition.

[In Formula (C-2), 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, A hydrogen atom or an alkyl group is shown, p and q are numbers 1 to 6, r and s are numbers 0 to 6, y is a number 1 to 200, and z is a number 1 to 20. ]   The (A) ethylenically unsaturated group-containing fluoropolymer contains an ethylenically unsaturated group-containing polymer obtained by reacting a compound containing at least one ethylenically unsaturated group with a hydroxyl group-containing fluoropolymer. It is a fluoropolymer, The curable resin composition of any one of Claims 1-4 characterized by the above-mentioned.   6. The compound according to claim 1, wherein the (B) (meth) acryloyl group-containing compound contains a compound containing 3 or more (meth) acryloyl groups in the molecule. Curable resin composition.   (E) It contains any one or more of particles having a number average particle diameter of 40 to 100 nm mainly composed of silica and (F) particles having a number average particle diameter of 1 to 30 nm mainly composed of silica. The curable resin composition according to any one of claims 1 to 6.   The curable resin composition according to claim 7, wherein at least one of the particles (E) and (F) containing silica as a main component is a hollow or porous particle.   9. The curable resin composition according to claim 7, wherein at least one of the (E) and (F) particles containing silica as a main component has a (meth) acryloyl group on the surface.   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 1-10. An antireflection film having a low refractive index layer made of the cured product according to claim 11.

Images