JP2007284546A - Thermosetting resin composition and antireflection film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition for providing a cured film having high transparency, a low refractive index and yet excellent scratch resistance and stain resistance, and an antireflection film. <P>SOLUTION: The thermosetting resin composition comprises (A) a fluorine-containing olefin-based polymer which has 10-50 mol% of a structural unit derived from a hydroxy group-containing monomer and a polysiloxane segment in the main chain, (B) a hollow particle and (C) a crosslinkable compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thermosetting resin composition, and more particularly to a thermosetting resin composition and an antireflection film that form a cured film having high transparency, a low refractive index, and good antireflection properties.

  Currently, with the development of multimedia, various developments have been seen in various display devices (display devices). Among various types of display devices, especially those used outdoors, mainly for portable use, the improvement in visibility has become increasingly important, and even in large display devices, it is easier to see. This is a technical issue as it is required by consumers.

  Conventionally, as one means for improving the visibility of a display device, an antireflection film made of a low refractive index material is coated on a substrate of the display device, and a method of forming the antireflection film For example, a method of forming a fluorine compound thin film by a vapor deposition method is known. However, in recent years, there has been a demand for a technique capable of forming an antireflection film for a large display device at a low cost centering on a liquid crystal display device. However, in the case of the vapor deposition method, it is difficult to form a high-efficiency and uniform antireflection film on a large-area substrate, and a vacuum apparatus is required, so that the cost can be reduced. Have difficulty.

  Under such circumstances, a method of forming an antireflection film by preparing a liquid composition by dissolving a fluorine-based polymer having a low refractive index in an organic solvent and applying it to the surface of a substrate has been studied. Yes. For example, it has been proposed to apply a fluorinated alkylsilane to the surface of a substrate (see, for example, Patent Document 1 and Patent Document 2). In addition, a method of applying a fluorine-based polymer having a specific structure has been proposed (see, for example, Patent Document 3).

In various display panels such as liquid crystal display panels, cold cathode ray tube panels, and plasma displays, the surface is often wiped with gauze impregnated with ethanol to remove attached fingerprints, dust, etc., and scratch resistance is required. ing.
Furthermore, there is a need for a curable resin composition that provides a cured film having a lower refractive index.

JP 61-40845 A Japanese Examined Patent Publication No. 6-98703 Japanese Patent Application Laid-Open No. 6-1115023

Conventional anti-reflective coatings made of fluorine-based materials are not sufficiently in close contact with the substrate, and particularly when subjected to repeated rubbing, the anti-reflective coating layer is peeled off. In addition, the anti-reflective coating for liquid crystal displays, etc. There is a problem in that dust and dust in the air adhere to the surface, reducing visibility.
The present invention has been made against the background of the above circumstances, and its objectives are high transparency, low refractive index, high adhesion to the substrate, and excellent scratch resistance and dust wiping. It is providing the thermosetting resin composition which can form the cured film which has property.
Another object of the present invention is to provide an antireflection film having high transparency, high adhesion to a substrate, and excellent scratch resistance and dust wiping properties.

［式（Ｃｐ−１）及び（Ｃｐ−２）中、Ｒ^２５、Ｒ^２７、Ｒ^２９はメチレン基又は炭素数２〜４のアルキレン基を示し、Ｒ^２６、Ｒ^２８、Ｒ^３０は水素又は炭素数１〜４のアルキル基を示す。］
８．（Ｃ）架橋性化合物がアルコキシアルキル化メラミン化合物である上記１〜７のいずれかに記載の熱硬化性樹脂組成物。
９．さらに、（Ｄ）酸触媒を含有する上記１〜８のいずれかに記載の熱硬化性樹脂組成物。
１０．さらに、（Ｅ）有機溶剤を含有する上記１〜９のいずれかに記載の熱硬化性樹脂組成物。
１１．反射防止膜用材料である上記１〜１０のいずれかに記載の熱硬化性樹脂組成物。
１２．上記１〜１１のいずれかに記載の熱硬化性樹脂組成物を熱硬化させて得られる硬化物。
１３．上記１２に記載の硬化物からなる低屈折率層を有する反射防止膜。 In order to achieve the above object, the present inventors have intensively studied and cured a resin composition containing a fluorine-containing olefin polymer having a specific structure and a hollow particle component, thereby reducing the refractive index. The inventors have found that a cured film excellent in scratch resistance can be obtained, and completed the present invention.
That is, this invention provides the following thermosetting resin composition, hardened | cured material, and antireflection film.
1. The following components (A) to (C):
(A) Fluorine-containing olefin polymer (B) hollow particles (C) containing 10 mol% to 50 mol% of a structural unit derived from a monomer containing a hydroxyl group and having a polysiloxane segment in the main chain ) A thermosetting resin composition containing a crosslinkable compound.
2. 2. The thermosetting resin composition according to 1 above, wherein the component (A) has a fluorine content of 30% by weight or more and a number average molecular weight in terms of polystyrene of 5000 or more.
3. The thermosetting resin composition according to 1 or 2, wherein the component (A) further contains 0 mol% to 10 mol% of a structural unit derived from a reactive emulsifier.
4). 4. The thermosetting resin composition according to any one of 1 to 3 above, wherein the component (B) is a particle mainly composed of silica.
5). The thermosetting resin composition according to any one of 1 to 4 above, wherein the number average particle diameter of the component (B) is in the range of 1 to 200 nm.
6). The thermosetting resin composition according to any one of 1 to 5 above, wherein the refractive index of the component (B) is 1.35 or less.
7). (C) The thermosetting resin composition according to any one of 1 to 6, wherein the crosslinkable compound is a compound having a structure represented by the following general formula (Cp-1) or (Cp-2).

[In the formulas (Cp-1) and (Cp-2), R ²⁵ , R ²⁷ and R ²⁹ represent a methylene group or an alkylene group having 2 to 4 carbon atoms, and R ²⁶ , R ²⁸ and R ³⁰ represent hydrogen or carbon. The alkyl group of number 1-4 is shown. ]
8). (C) The thermosetting resin composition according to any one of 1 to 7, wherein the crosslinkable compound is an alkoxyalkylated melamine compound.
9. Furthermore, (D) The thermosetting resin composition in any one of said 1-8 containing an acid catalyst.
10. Furthermore, (E) The thermosetting resin composition in any one of said 1-9 containing an organic solvent.
11. The thermosetting resin composition according to any one of 1 to 10 above, which is a material for an antireflection film.
12 Hardened | cured material obtained by thermosetting the thermosetting resin composition in any one of said 1-11.
13. 13. An antireflection film having a low refractive index layer comprising the cured product as described in 12 above.

According to the present invention, a thermosetting resin composition that can form a cured film having high transparency, low refractive index, high adhesion to a substrate, and excellent scratch resistance and dust wiping properties. Can be provided.
According to the present invention, it is possible to provide an antireflection film having high transparency, high adhesion to a substrate, and excellent scratch resistance and dust wiping properties.

I. Curable resin composition The thermosetting resin composition of the present invention (hereinafter referred to as the composition of the present invention) contains the following components (A) to (F). Among the following components, the components (A) and (B) are essential components, and the components (C) to (F) are optional additional components that are blended as necessary.
(A) Fluorine-containing olefin polymer (B) hollow particles (C) containing 10 mol% to 50 mol% of a structural unit derived from a monomer containing a hydroxyl group and having a polysiloxane segment in the main chain ) Crosslinkable compound (D) Acid catalyst (E) Organic solvent (F) additive Each component will be described below.

(A) Fluorine-containing olefin polymer containing 10 mol% to 50 mol% of a structural unit derived from a monomer containing a hydroxyl group and having a polysiloxane segment in the main chain (A) ) -Containing olefin polymer contains a hydroxyl group and a polysiloxane segment in the main chain. Hereinafter, the component (A) is referred to as a “hydroxyl group-containing fluoropolymer”.
The hydroxyl group-containing fluoropolymer preferably comprises the following structural unit (a), (b-1) and / or (b-2), and (c).
(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)_ｎ−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、ｎ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 ) _n —OR ⁵ or —OCOR ⁵ (R ⁵ represents an alkyl group or A glycidyl group, n represents 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はフロ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 a combination of these is more preferable.

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 application, whereas the content is This is because the solubility of the hydroxyl group-containing fluoropolymer in an organic solvent, transparency, or adhesion to a substrate may be deteriorated when the content exceeds 65 mol%.
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 such as octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether or cycloalkyl vinyl ethers; allyl ethers such as ethyl allyl ether, butyl allyl ether; vinyl acetate, vinyl propionate, vinyl butyrate, pivalin Carboxylic acid vinyl ester such as vinyl acid vinyl, vinyl caproate, vinyl vinyl versatate, vinyl stearate Tellurium; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- ( (Meth) acrylic acid esters such as n-propoxy) ethyl (meth) acrylate; (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^２０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 (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 ²⁰ represents a hydrogen atom or a methyl group, and x represents a number from 0 to 2. Also, 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. On the other hand, 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 contents of the structural units (b-1) and (b-2) are changed to the structural units (a), (b-1) and / or (b-2), and (c )) Is more preferably from 1 to 45 mol%. Moreover, the content rate of (b-1) and / or (b-2) shown above is the structural unit when the structural unit (b-1) or (b-2) is used alone. It means the content of either (b-1) or (b-2), and when the structural units (b-1) and (b-2) are used together, it means the total content of both. .

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

The structural unit (c) can be introduced by using a hydroxyl group-containing vinyl monomer as a polymerization component. Examples of such hydroxyl group-containing vinyl monomers include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, Examples include hydroxyl group-containing vinyl ethers such as 6-hydroxyhexyl vinyl ether, hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether, allyl alcohol, and the like.
In addition to the above, the hydroxyl group-containing vinyl monomer includes 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone (meth) acrylate, and 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%.

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

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

[In formula (4), R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group]

In the formula (4), the alkyl group of R ⁸ or R ^{9 is} an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group, and the halogenated alkyl group is a trifluoromethyl group or perfluoro group. C1-C4 fluoroalkyl groups, such as an ethyl group, a perfluoropropyl group, a perfluorobutyl group, etc., A phenyl group, a benzyl group, a naphthyl group etc. are each mentioned as an aryl group.

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

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

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

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

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

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

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

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

［式（７）中、ｙ及びｚは、上記式（５）と同じである。］

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

In addition, the content rate of the structural unit (d) is 0.1 to the total 100 mol parts of the structural unit (a), (b-1) and / or (b-2), and (c). It is preferable to set it as 10 mol part. The reason for this is that when the content is less than 0.1 mol part, the surface slipperiness of the coated film after curing is lowered, and the scratch resistance of the coated film may be lowered. If the amount exceeds 10 parts by mole, the transparency of the hydroxyl group-containing fluoropolymer is inferior, and when used as a coating material, repelling and the like are likely to occur during coating.
Moreover, for such reasons, the content of the structural unit (d) is adjusted to 100 mol parts in total of the structural unit (a), (b-1) and / or (b-2), and (c). On the other hand, it is more preferable to set it as 0.1-5 mol part, and it is further more preferable to set it as 0.1-3 mol part. For the same reason, the content of the structural unit (e) is desirably determined so that the content of the structural unit (d) contained therein is in the above range.

(Vi) 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. Specific examples include Adeka Soap NE-30 and ER-30 manufactured by Asahi Denka Kogyo.

In addition, the content rate of the structural unit (f) is 0.1 to the total 100 mol parts of the structural unit (a), (b-1) and / or (b-2), and (c). It is preferable to set it as -5 mol part. The reason for this is that when the content is 0.1 mol part or more, the solubility of the hydroxyl group-containing fluoropolymer in the solvent is improved. On the other hand, if the content is within 5 mol parts, the composition of the present invention. This is because the adhesiveness of the film does not increase excessively, handling becomes easy, and moisture resistance does not decrease even when used as a coating material.
For such reasons, the content of the structural unit (f) is adjusted to 100 mol parts in total of the structural unit (a), (b-1) and / or (b-2), and (c). On the other hand, it is more preferable to set it as 0.1-3 mol part, and it is further more preferable to set it as 0.2-3 mol part.

(Vi) Molecular Weight The hydroxyl group-containing fluoropolymer preferably has a polystyrene-equivalent number average molecular weight of 5,000 to 500,000 measured by gel permeation chromatography using tetrahydrofuran as a solvent. The reason for this is that when the number average molecular weight is less than 5,000, the mechanical strength of the hydroxyl group-containing fluoropolymer may be lowered. On the other hand, when the number average molecular weight exceeds 500,000, it will be described later. This is because the viscosity of the composition of the present invention 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.

  Examples of radical polymerization initiators that can be used in combination with component (c) include (1) diacyl peroxides such as acetyl peroxide and benzoyl peroxide; (2) ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide. (3) Hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide; (4) Di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc. Dialkyl peroxides; (5) peroxyesters such as tert-butylperoxyacetate and tert-butylperoxypivalate; (6) azo-based compounds such as azobisisobutyronitrile and azobisisovaleronitrile; Compounds like; (7) ammonium persulfate, sodium persulfate, persulfates such as potassium persulfate; Other can be exemplified.

  Specific examples other than the above radical polymerization initiator include, for example, perfluoroethyl iodide, perfluoropropyl iodide, perfluorobutyl iodide, (perfluorobutyl) ethyl iodide, perfluorohexyl iodide, 2- (Perfluorohexyl) ethyl iodide, perfluoroheptyl iodide, perfluorooctyl iodide, 2- (perfluorooctyl) ethyl iodide, perfluorodecyl iodide, 2- (perfluorodecyl) ethyl iodide, heptafluoro 2-iodopropane, perfluoro-3-methylbutyl iodide, perfluoro-5-methylhexyl iodide, 2- (perfluoro-5-methylhexyl) ethyl iodide, perfluoro-7-methyloctyl iodide 2- (perfluoro-7-methyloctyl) ethyl iodide, perfluoro-9-methyldecyl iodide, 2- (perfluoro-9-methyldecyl) ethyl iodide, 2,2,3,3-tetrafluoropropyl iodide 1H, 1H, 5H-octafluoropentyl iodide, 1H, 1H, 7H-dodecafluoroheptyl iodide, tetrafluoro-1,2-diiodoethane, octafluoro-1,4-diiodobutane, dodecafluoro-1,6-diiodohexane And iodine-containing fluorine compounds. The iodine-containing fluorine compound can be used alone or in combination with the organic peroxide, azo compound or persulfate.

  As a polymerization mode for producing the fluorine-containing olefin polymer, any of an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method or a solution polymerization method using a radical polymerization initiator can be used. However, an appropriate one can be selected from batch, semi-continuous or continuous operations.

  The polymerization reaction for obtaining the fluorine-containing olefin polymer is preferably performed in a solvent system using a solvent. Examples of preferable organic solvents include (1) esters such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, and cellosolve; (2) ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; (3) Cyclic ethers such as tetrahydrofuran and dioxane; (4) Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; (5) Aromatic hydrocarbons such as toluene and xylene; be able to. Further, if necessary, alcohols, aliphatic hydrocarbons and the like can be mixed and used.

  The fluorine-containing olefin polymer obtained as described above may be able to use the reaction solution obtained by the polymerization reaction as it is as the composition of the present invention. It is also free to perform post-processing. As this post-treatment, for example, a general method represented by a purification method in which a polymerization reaction solution is added dropwise to an insolubilizing solvent for the fluorine-containing olefin polymer made of alcohol or the like to solidify the fluorine-containing olefin polymer. Reprecipitation treatment can be performed, and then the solution of the fluorine-containing olefin polymer can be prepared by dissolving the obtained solid copolymer in a solvent. Moreover, what removed the residual monomer from the polymerization reaction solution can also be used as a solution of a fluorine-containing olefin polymer as it is.

The content of the component (A) in the composition of the present invention is usually 5 to 70% by weight, with the total amount of the composition excluding the organic solvent being 100% by weight. When the content of component (A) is less than 5% by weight,
The reflectance and antifouling property may be insufficient, and if it exceeds 70% by weight, the hardness of the cured coating film may be reduced due to an excessive component (A).
For the above reasons, the content of the component (A) is preferably 10 to 60% by weight, and more preferably 10 to 50% by weight.

(B) Hollow particles The hollow particles of the component (B) are blended for the purpose of improving the scratch resistance, particularly the steel wool resistance, of a cured product obtained by curing the composition of the present invention. In addition, the refractive index of the obtained hardened | cured material can be made lower by being hollow.
As the hollow particles of the component (B), particles containing hollow silica as a main component (hereinafter referred to as “hollow silica particles” or simply from the viewpoint of lowering the refractive index of a cured film obtained by curing the composition of the present invention). “Silica particles” are preferred.
Further, the silica particles are preferable in that they have a silanol group on the surface, so that they can be co-crosslinked with the thermosetting component and can further improve the scratch resistance.
The term “hollow particles” as used in the present invention is a concept that includes not only the so-called hollow particles but also the porous particles having many bubble cavities.

(1) Hollow silica particles The shape of the hollow silica particles is not limited to a spherical shape, and may be an irregular shape. The number average particle diameter of the particles determined with a transmission electron microscope is preferably 1 to 200 nm, and more preferably 5 to 100 nm. As the hollow silica particles, commercially available products may be used. For example, JX1008SIV (isopropyl alcohol sol, solid concentration 22%), JX1009 SIV (methyl isobutyl ketone sol, solid concentration 22%), JX1010 SIV (isopropyl alcohol sol, solid concentration) 22%) (both manufactured by Catalytic Chemical Industry).

  The dispersion medium for the hollow silica particles 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 preferable, and ketones are more preferable. These organic solvents can be used alone or in combination of two or more as a dispersion medium.

Moreover, what carried out surface treatments, such as chemical modification, on the surface of a hollow silica particle can be used, for example, the hydrolyzable silicon compound which has one or more alkyl groups in a molecule | numerator, or its hydrolyzate Etc. 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 and the like having an OH group, bis (2-hydroxyethyl) -3aminotripropylmethoxysilane and the like having an isocyanate group, 3-isocyanatopropyltrimethoxysilane and the like having a thiocyanate group 3 As 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.

Surface treatment method of hollow silica particles The surface treatment method of the hollow silica particles by the hydrolyzable silicon compound is not particularly limited, but the hydrolyzable silicon compound and the hollow silica particles are mixed, heated and stirred. It is also possible to manufacture by. Therefore, the surface treatment can be performed by a method including an operation of mixing at least the particles and the hydrolyzable silicon compound. The reaction is preferably carried out in the presence of water in order to efficiently combine the silanol group-forming site of the hydrolyzable silicon compound with the particles.

  The reaction amount of the particles and the hydrolyzable silicon compound is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, particularly preferably, based on 100% by weight of the total of the particles and the hydrolyzable silicon compound. Is 1% by weight or more. 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.
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. That's it.

  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 120 ° C. or lower. The processing time is usually in the range of 5 minutes to 24 hours.

When powdery hollow silica particles are used 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 γ-butyrolactone. Esters such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone . 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 hollow silica particles, it can be produced by mixing at least the solvent-dispersed sol and the hydrolyzable silicon 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 oxalic 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.

The content of component (B) in the composition of the present invention is usually 10 to 90% by weight, with the total amount of the composition excluding the organic solvent being 100% by weight. When the content of the component (B) is less than 10% by weight, a coating film having a low refractive index may not be obtained. When the content exceeds 90% by weight, the binder amount with respect to the particles is low and the binding force between the particles is insufficient. There are cases.
For the above reasons, the content of the component (B) is preferably 20 to 80% by weight, and more preferably 30 to 80% by weight.

(C) Crosslinkable compound In practice, the composition of the present invention is required to have curability, and when the fluorine-containing olefin polymer itself does not have sufficient curability, a crosslinkable compound is used. By blending, necessary curability can be imparted and curing characteristics can be improved.
Examples of the crosslinkable compound include various amino compounds, various hydroxyl group-containing compounds such as pentaerythritol, polyphenol, and glycol, and others.

  The amino compound used as the crosslinkable compound is a total of two amino groups capable of reacting with a hydroxyl group present in the fluorine-containing olefin polymer, for example, one or both of a hydroxyalkylamino group and an alkoxyalkylamino group. Specific examples of the compound that can be used include melamine compounds, urea compounds, benzoguanamine compounds, glycoluril compounds, and the like.

  Melamine compounds are generally known as compounds having a skeleton in which a nitrogen atom is bonded to a triazine ring, and specific examples include melamine, alkylated melamine, methylol melamine, alkoxylated methyl melamine, and the like. However, it is preferable to have one or both of a methylol group and an alkoxylated methyl group in one molecule in total. Specifically, methylolated melamine obtained by reacting melamine and formaldehyde under basic conditions, alkoxylated methylmelamine, or a derivative thereof is preferable, and particularly, the composition of the present invention has good storage stability. Alkoxylated methyl melamine is preferable in that it can be obtained and good reactivity can be obtained. There are no particular restrictions on the methylolated melamine and the alkoxylated methylmelamine used as the crosslinkable compound. For example, the methylolated melamine and the alkoxylated methylmelamine can be obtained by the method described in the document “Plastic Materials Course [8] Urea Melamine Resin” (Nikkan Kogyo Shimbun). Various resinous materials can be used.

  In addition to urea, examples of the urea compound include polymethylolated urea, alkoxylated methylurea which is a derivative thereof, methylolated uron having a uron ring, and alkoxylated methyluron. And also about compounds, such as a urea derivative, the use of the various resinous materials described in said literature is possible.

式（Ｃｐ−１）及び（Ｃｐ−２）中、Ｒ^２５、Ｒ^２７、Ｒ^２９はメチレン基又は炭素数２〜４のアルキレン基を示し、好ましくはメチレン基である。Ｒ^２６、Ｒ^２８、Ｒ^３０は水素又は炭素数１〜４のアルキル基を示し、好ましくはメチル基である。
上記一般式（Ｃｐ−１）又は（Ｃｐ−２）で示される構造を有する化合物の例としては、サイメル３００、３０１、３０３、３５０、３７０、７７１、３２５、３２７、７０３、７１２、２７２、２０２、２０７、２１２、２５３、２５４、５０６、５０８、１１２３、１１２３−１０、１１２８、１１７０、１１７２、１１４１、１１２５−８０、マイコート１０２、１０５、１０６、１３０（いずれも三井サイテック製）等が挙げられる。 As the crosslinkable compound, a compound having a structure represented by the following general formula (Cp-1) or (Cp-2) is preferable.

In formulas (Cp-1) and (Cp-2), R ²⁵ , R ²⁷ and R ²⁹ represent a methylene group or an alkylene group having 2 to 4 carbon atoms, preferably a methylene group. R ²⁶ , R ²⁸ and R ³⁰ represent hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably a methyl group.
Examples of the compound having the structure represented by the general formula (Cp-1) or (Cp-2) include Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, 272, 202. 207, 212, 253, 254, 506, 508, 1123, 1123-10, 1128, 1170, 1172, 1141, 1125-80, My Coat 102, 105, 106, 130 (all manufactured by Mitsui Cytec) It is done.

The content of the component (C) in the composition of the present invention is usually 1 to 60% by weight, with the total amount of the composition excluding the organic solvent being 100% by weight. When the content of the component (C) is less than 1% by weight, the added effect cannot be obtained, that is, the durability of the thin film formed by the obtained composition of the present invention may be insufficient, and 60% by weight. When it exceeds%, the cured film does not have a low refractive index, and the cured product may become brittle.
For the above reason, the content of the component (C) is preferably 5 to 50% by weight, and more preferably 10 to 50% by weight.

  In the present invention, the hydroxyl group-containing fluoropolymer of component (A) and the crosslinkable compound of component (C) can be reacted in advance and used. For example, a crosslinkable compound may be added to a solution of an organic solvent in which a fluoropolymer is dissolved, and the reaction system may be made uniform by heating, stirring, or the like for an appropriate time. The heating temperature for this reaction is preferably in the range of 30 to 150 ° C, more preferably in the range of 50 to 120 ° C. When the heating temperature is less than 30 ° C, the reaction proceeds very slowly. When the heating temperature exceeds 150 ° C, in addition to the intended reaction, a crosslinking reaction due to the reaction between methylol groups and alkoxylated methyl groups in the crosslinkable compound occurs. This is not preferable because a gel is formed. The progress of the reaction is quantitative by measuring the amount of methylol group or alkoxylated methyl group by infrared spectroscopic analysis or by collecting the dissolved polymer by reprecipitation method and measuring the increase. Can be confirmed.

  In addition, for the reaction between the fluorine-containing olefin polymer and the crosslinkable compound, it is preferable to use the same organic solvent as that used in the production of the fluorine-containing olefin polymer, for example. In the present invention, the reaction solution obtained by the fluorine-containing olefin polymer and the crosslinkable compound thus obtained can be used as it is as the solution of the composition of the present invention, and various additives can be used as necessary. It can also be used after blending.

(D) Acid catalyst An acid catalyst is added for the purpose of improving the hardness and durability of the cured film formed from the composition of the present invention.
The acid catalyst that can be blended in the composition of the present invention is a substance that can improve the heating conditions to be milder when the coating film of the composition of the present invention is heated and cured. is there.
Examples of the acid catalyst that can be used in the present invention include a thermal acid generator that generates an acid by heating and a photosensitive acid generator that generates an acid by irradiation with radiation.

(iv) Thermal acid generator Specific examples of the thermal acid generator include, for example, various aliphatic sulfonic acids and salts thereof, various aliphatic carboxylic acids such as citric acid, acetic acid, and maleic acid and salts thereof, benzoic acid, and phthalates. Examples thereof include various aromatic carboxylic acids such as acids and salts thereof, alkylbenzene sulfonic acids and ammonium salts thereof, various metal salts, phosphoric acid esters of organic acids and the like.

(v) Photosensitive acid generator The photosensitive acid generator imparts photosensitivity to the coating film of the composition of the present invention and, for example, photocures the coating film by irradiating radiation such as light. It is a substance that makes it possible. Examples of the photosensitive acid generator include (1) various onium salts such as iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, ammonium salts, pyridinium salts; (2) β-ketoesters, β-sulfonylsulfones and these. sulfone compounds such as α-diazo compounds; (3) sulfonic acid esters such as alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates; and (4) sulfonimides represented by the following general formula (11) Compounds: (5) Diazomethane compounds represented by the following general formula (12);

式中、Ｘは、アルキレン基、アリレーン基、アルコキシレン基等の２価の基を示し、Ｒ^１９は、アルキル基、アリール基、ハロゲン置換アルキル基、ハロゲン置換アリール基等の１価の基を示す。

In the formula, X represents a divalent group such as an alkylene group, an arylene group or an alkoxylene group, and R ¹⁹ represents a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group. Show.

式中、Ｒ^２０及びＲ^２１は、互いに同一でも異なってもよく、アルキル基、アリール基、ハロゲン置換アルキル基、ハロゲン置換アリール基等の１価の基を示す。

In the formula, R ²⁰ and R ²¹ may be the same as or different from each other, and represent a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group.

  The thermal acid generator and the photosensitive acid generator can be used in combination, and each can be used alone or in combination of two or more. The thermal acid generator or the photosensitive acid generator is used for the purpose of improving the hardness and durability of the cured film to be formed, and in particular, does not decrease the transparency after curing of the composition of the present invention, and is a solution thereof. It is preferable to select and use one that dissolves uniformly.

The content of component (D) in the composition of the present invention is usually 0.01 to 20% by weight, with the total amount of the composition excluding the organic solvent being 100% by weight. When the content of the component (D) is less than 0.01% by weight, the added effect may not be obtained, and when it exceeds 20% by weight, the strength of the obtained cured film may be lowered.
For the above reason, the content of the component (D) is preferably 0.1 to 15% by weight, and more preferably 1 to 10% by weight.

(E) Organic solvent The organic solvent is usually used for the reaction of (A) the solvent used in the production of the fluorine-containing olefin polymer or (A) the fluorine-containing olefin polymer and (C) the crosslinkable compound. Therefore, usually, the solvent is contained as it is, but the solvent of the composition of the present invention is improved to improve the coating property, etc. can do.

  Further, preferred solvents contained in the composition of the present invention include ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetone, esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate, methanol, ethanol, Examples include alcohols such as isopropyl alcohol, sec-butanol, t-butanol, and propylene glycol monomethyl ether; aromatics such as benzene, toluene, xylene, nitrobenzene, chlorobenzene, and phenol; and ethers such as dimethyl ether and diethyl ether. . Of these solvents, ketones, alcohols and esters are particularly preferred.

  The content of the component (E) in the composition of the present invention is usually 100 to 10,000% by weight, preferably 500 to 5000 parts by weight, preferably 1000 to 5000% by weight, with 100% by weight of the total composition excluding the organic solvent. Part is more preferred.

(F) Additive The composition of the present invention includes, for example, various polymers having a hydroxyl group for the purpose of improving the coating properties of the composition and the physical properties of the thin film after curing, and imparting photosensitivity to the coating film. Various additives such as pigments, monomers, pigments or dyes, stabilizers such as anti-aging agents and UV absorbers, surfactants, polymerization inhibitors, solvents, solid particles mainly composed of silica, etc. It can be included.

(i) Polymer having hydroxyl group The polymer having a hydroxyl group that can be blended in the composition of the present invention is obtained, for example, by copolymerizing a hydroxyl group-containing copolymerizable monomer such as hydroxyethyl (meth) acrylate. Examples of the polymer, novolak resin or resol resin include resins having a known phenol skeleton.

(ii) Colorant such as pigment or dye Examples of the colorant that can be incorporated into the composition of the present invention include (1) extender pigments such as alumina white, clay, barium carbonate, and barium sulfate; (2) zinc Inorganic pigments such as white, lead white, yellow lead, red lead, ultramarine, bitumen, titanium oxide, zinc chromate, bengara, carbon black; (3) Brilliant Carmine 6B, Permanent Red 6B, Permanent Red R, Benzidine Yellow, Phthalocyanine Organic pigments such as blue and phthalocyanine green; (4) basic dyes such as magenta and rhodamine; (5) direct dyes such as direct scarlet and direct orange; (6) acidic dyes such as roserine and methanyl yellow; be able to.

(iii) Stabilizers such as anti-aging agents and UV absorbers As anti-aging agents and UV absorbers that can be blended in the composition of the present invention, known ones can be used.
Specific examples of the antioxidant include, for example, di-tert-butylphenol, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone Monopropyl ether, 4,4 '-[1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] diphenol, 1,1,3-tris (2,5-dimethyl) -4-hydroxyphenyl) -3-phenylpropane, diphenylamines, phenylenediamines, phenothiazine, mercaptobenzimidazole, and the like.

  Specific examples of ultraviolet absorbers include, for example, salicylic acid ultraviolet absorbers represented by phenyl salicylate, benzophenone ultraviolet absorbers such as dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone, and benzotriazole ultraviolet absorbers. Ultraviolet absorbers used as additives for various plastics such as cyanoacrylate-based ultraviolet absorbers can be used.

(vi) Surfactant A surfactant can be added to the composition of the present invention for the purpose of improving the coating property of the composition. As this surfactant, known ones can be used. Specifically, for example, various anionic surfactants, cationic surfactants, and nonionic surfactants can be used. In particular, a cationic surfactant is preferably used so that the cured film has excellent strength and good optical properties. Furthermore, a quaternary ammonium salt is preferable, and among them, the use of a quaternary polyether ammonium salt is particularly preferable because dust wiping property is further improved. Examples of cationic surfactants that are quaternary polyether ammonium salts include Adekacol CC-15, CC-36, and CC-42 manufactured by Asahi Denka Kogyo Co., Ltd. The use ratio of the surfactant is preferably 5 parts by weight or less with respect to 100 parts by weight of the composition of the present invention.

(v) Polymerization inhibitor Examples of the thermal polymerization inhibitor that can be incorporated into the composition of the present invention include pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, and amyloxy. Hydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4 ′-[1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] diphenol, 1,1, Examples include 3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane. This thermal polymerization inhibitor is preferably used in an amount of 5 parts by weight or less with respect to 100 parts by weight of the composition of the present invention.

(vi) Solid particles mainly composed of silica In the composition of the present invention, for the purpose of improving the scratch resistance of the cured product of the composition, particularly the resistance to steel wool, silica other than the component (B) is added. Solid particles as the main component can be blended. As the solid particles mainly composed of silica, known particles can be used, and the shape of the solid particles is not limited to ordinary colloidal silica as long as it is spherical, and may be core-shell type particles or the like. I do not care. Moreover, it is not limited to a spherical shape, and may be an irregularly shaped particle. Colloidal silica having a number average particle size determined by a dynamic light scattering method of 1 to 100 nm and 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, 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 admixture of two or more as a dispersion medium.
Examples of commercially available particles mainly composed of silica include ST-S, ST-M, ST-L, ZL, and ST-UP manufactured by Nissan Chemical Industries, Ltd.

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) -3-aminotripropylmethoxysilane or the like having an isocyanate group, 3-isocyanatopropyltrimethoxysilane or the like having a thiocyanate group As those having an thiol group such as (3-glycidoxypropyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like having an epoxy group such as 3-thiocyanate propyltrimethoxysilane, 3-mercaptopropyltrimeth Examples include xylsilane. A preferred compound is 3-mercaptopropyltrimethoxysilane.

II. Antireflective film The composition of the present invention can be applied to various substrates in the form of a solution, and by curing the obtained coating film, for example, when the substrate is a transparent substrate, it is excellent. An antireflection film is formed.
As shown in FIG. 1, the specific structure of the antireflection film is usually a laminate of a substrate 10, a hard coat layer 12 and a cured product obtained by curing the composition of the present invention as a low refractive index film 14. Further, a high refractive index layer other than the hard coat layer or an antistatic layer may be interposed between the substrate and the low refractive index film. For example, as shown in FIG. 2, a base material 10, a high refractive index film 13 and a cured product obtained by curing the composition of the present invention are laminated as a low refractive index film 14. In this case, the high refractive index film also functions as a hard coat. Further, as shown in FIG. 3, a base material 10, an antistatic layer 15 and a cured product obtained by curing the composition of the present invention are laminated as a low refractive index film 14. In this case, the antistatic layer serves as a hard coat and a high refractive index layer, and the resulting antireflection film has an antistatic ability. Further, a high refractive index layer or an antistatic layer may be interposed between the hard coat layer having the layer structure shown in FIG. 1 and the low refractive index layer, and as shown in FIG. The antistatic layer 15 and the low refractive index film 14 obtained by curing the composition of the present invention are laminated.

  Although the kind of base material used for the antireflection film of the present invention is not particularly limited, for example, a base material made of glass, polycarbonate resin, polyester resin, acrylic resin, triacetyl cellulose resin (TAC) or the like. 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. As the coating method, a known coating method can be used, and in particular, various methods such as a dip method, a coater method, and a printing method can be applied.

  The coating film of the composition of the present invention formed by coating is preferably given a heat history by heating in order to form a cured film having excellent optical properties and durability by curing. Of course, even when left at room temperature, the curing reaction proceeds with the passage of time, and the desired cured film is formed. However, in practice, curing by heating is effective in reducing the required time. Is. Moreover, the curing reaction can be further promoted by adding a thermal acid generator as a curing catalyst. As the curing catalyst, as described above, the above-mentioned various acids and salts used as curing agents for general urea resins, melamine resins and the like can be used, and in particular, ammonium salts are preferably used. Can do. The heating conditions for the curing reaction can be selected as appropriate, but the heating temperature needs to be equal to or lower than the heat resistant limit temperature of the substrate to be coated.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to these Examples. In the following description, “parts” and “%” represent parts by weight and% by weight, respectively, unless otherwise specified.

Production Example 1
Production of fluorine-containing olefin polymer After sufficiently substituting a stainless steel autoclave with an internal volume of 2.0 liters with a magnetic stirrer with nitrogen gas, 400 g of solvent ethyl acetate, 76.3 g of component (a) perfluoro (propyl vinyl ether), (E) component ethyl vinyl ether (EVE) 34.4 g, (b) component hydroxyethyl vinyl ether 42.0 g, (d) component nonionic reactive emulsifier “ADEKA rear soap NE-30” (Asahi Denka Kogyo) 20.0 g (manufactured by Co., Ltd.), 6.0 g of “VPS-1001” (manufactured by Wako Pure Chemical Industries, Ltd.) as the azo group-containing polydimethylsiloxane of component (c) and 1. lauroyl peroxide (LPO) as a polymerization initiator. 0g was charged, cooled to -50 ° C with dry ice-methanol cryogen, and then again with nitrogen gas The oxygen inside was removed.

  Next, 100.4 g of component (a) hexafluoropropylene (HFP) was charged, and the temperature was raised. The pressure when the temperature in the autoclave reached 60 ° C. was 60 Pa. Thereafter, the reaction was continued for 20 hours with stirring at 60 ° C., and when the pressure dropped to 25 Pa, the autoclave was cooled with water to stop the reaction. After the reaction product reached room temperature, unreacted monomers were released and the autoclave was opened to obtain a polymer solution. The obtained polymer solution was put into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 230 g of a fluorine-containing polymer A1. Table 1 shows the amount of monomers charged to obtain this fluorine-containing polymer A1.

Using a 0.5% solution prepared by dissolving this fluorine-containing polymer A1 in tetrahydrofuran (THF), the number average molecular weight in terms of polystyrene was determined by gel permeation chromatography and found to be 35,000. Furthermore, the glass transition temperature (Tg) by the differential thermal analysis method (DSC), the fluorine content by the alizarin complexone method, and the hydroxyl value by the acetylation method using acetic anhydride were measured. In addition, both ¹ H-NMR and ¹³ C-NMR NMR analysis and elemental analysis were performed, and the inorganic silica content was measured from the fluorine content, hydroxyl value, and residual weight after firing at 600 ° C. The ratio of each monomer component constituting the containing polymer A1 was determined. The results are shown in Table 2.

VPS-1001: azo group-containing polydimethylsiloxane represented by the above general formula (7), y = 120 to 150, z = 7 to 10, number average molecular weight is 70000 to 90000, and the molecular weight of the polysiloxane segment is about 5000 ( Wako Pure Chemical Industries, Ltd.)
NE-30: Nonionic reactive emulsifier “NE-30” (manufactured by Asahi Denka Kogyo Co., Ltd.) represented by the following general formula (9), where n = 9, m = 1, and s = 30

Production Example 2
Preparation of hollow particles B1 mainly composed of silica A mixture of 100 g of silica sol having an average particle diameter of 5 nm and a SiO ₂ concentration of 20% by weight and 1900 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor was 10.5, and 9000 g of a 1.17 wt% sodium silicate aqueous solution as SiO ₂ and 9000 g of a 0.83 wt% sodium aluminate aqueous solution as Al ₂ O ₃ were simultaneously added to the mother liquor. . Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition, and hardly changed thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO ₂ .Al ₂ O ₃ core particle dispersion with a solid concentration of 20 wt%.
1,700 g of pure water is added to 500 g of this core particle dispersion and heated to 98 ° C., and while maintaining this temperature, a silicic acid solution (SiO ₂₎ obtained by dealkalizing a sodium silicate aqueous solution with a cation exchange resin. A dispersion of core particles in which a silica outer shell was formed by adding 3,000 g (concentration: 3.5% by weight) was obtained.

  Next, 1,125 g of pure water was added to 500 g of a dispersion of core particles formed with a silica shell having a solid content concentration of 13 wt% by washing with an ultrafiltration membrane, and concentrated hydrochloric acid (35.5%) was further added. The solution was dropped to pH 1.0, and dealumination was performed. Subsequently, the aluminum salt dissolved in the ultrafiltration membrane is separated while adding 10 liters of pH 3 hydrochloric acid aqueous solution and 5 liters of pure water, and then the solvent is replaced with ethanol by using the ultrafiltration membrane to form a silica outer shell. A dispersion B1 of hollow silica particles was prepared. 2 g of the resulting hollow silica particle sol 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 20.0% by weight. The hollow silica particles had an average particle size of 50 nm and a refractive index of 1.29. Here, the average particle diameter was measured with a transmission electron microscope.

(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, and an oven Medium was dried at 80 ° C. for 1 minute to form a coating film. Subsequently, 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 substrate for coating a curable resin composition.

Example 1
20 g of fluorine-containing polymer A1 obtained in Production Example 1 (component (A)), 1225 g of hollow silica particle sol B obtained in Production Example 2 (45 g as the solid content of hollow silica particles, component (B)), 30 g of melamine resin (Cymel 300, manufactured by Mitsui Cytec, component (C)), 5 g of p-toluenesulfonic acid (component (D)) as an acid catalyst, 1550 g of methyl isobutyl ketone (MIBK), and 670 g of t-butanol, a glass equipped with a stirrer The mixture was placed in a separable flask and stirred at room temperature for 1 hour 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 2-8 and Comparative Examples 1-2
According to the composition shown in Table 3 and Table 4, a curable resin composition was produced in the same manner as in Example 1 except that the fluorine-containing polymer A1, hollow silica particles, a crosslinkable compound, and a curing catalyst were added.

<Characteristic evaluation of cured product>
On each of the curable resin compositions obtained in Examples 1 to 8 and Comparative Examples 1 and 2 on the hard coat of the curable resin composition coating substrate obtained in Production Example 4 using a wire bar coater. The film was coated to a thickness of 0.1 μm, heated at 140 ° C. for 3 minutes to form a coating film, and an antireflection film sample was obtained. About this, the various physical properties shown below were measured.

(Evaluation example 1)
Appearance Evaluation The appearance of the antireflection film obtained as described above was visually confirmed and evaluated according to the following criteria. The results are shown in Tables 4 and 5.
○: No coating unevenness Δ: Some coating unevenness ×: Coating unevenness on the entire surface

(Evaluation example 2)
Haze The antireflection film obtained as described above was evaluated by measuring the haze with a color haze meter. The evaluation criteria are as follows. The results are shown in Tables 4 and 5.
○: Haze 0.3% or less △: Haze more than 0.3%, 1.0% or less ×: Haze more than 1.0%

(Evaluation example 3)
Measurement of Refractive Index of Cured Film Each curable resin composition was applied on a silicon wafer by a spin coater so that the thickness after drying was about 0.1 μm, and then heat-cured at 140 ° C. for 3 minutes. The obtained cured product was measured refractive index at a wavelength of 589nm at 25 ° C. using an ellipsometer to ^{_(n D 25).} The results are shown in Tables 4 and 5.

(Evaluation example 4)
Reflectivity of antireflection film The back surface of the antireflection film obtained as described above was painted with black spray, and a spectral reflectance measuring device (a self-recording spectrophotometer U incorporating a large sample chamber integrating sphere attachment device 150-09090 was incorporated. -3410, manufactured by Hitachi, Ltd.), the reflectance was measured from the substrate side in the wavelength range of 340 to 700 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 from the reflectance of light at a wavelength of 550 nm, The antireflection property was evaluated according to the following criteria. The results are shown in Tables 4 and 5.
◎: Reflectance is 1.3% or less ○: Reflectance is over 1.3%, 2.0% or less △: Reflectance is over 2.0%, 3.0% or less ×: Reflectance is 3.0 %Super

(Evaluation example 5)
Scratch resistance test (steel wool resistance test)
The cured film (antireflection film) obtained as described above is made of steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) using a Gakushin type friction fastness tester (AB-301, tester industry ( The surface of the cured film was repeatedly rubbed 10 times under the condition of a load of 500 g, the presence or absence of scratches on the surface of the cured film was visually confirmed, and evaluated according to the following criteria. The results are shown in Tables 4 and 5.
A: The cured film is not damaged.
◯: Almost no peeling or scratching of the cured film is observed, or slight thin scratches are observed on the cured film.
Δ: Streaky scratches are observed on the entire surface of the cured film.
X: Peeling of cured film occurs.

(Evaluation example 6)
Contamination resistance A fingerprint was attached to the antireflection film obtained in Production Example 5, and the surface of the coating film was wiped off with a non-woven fabric (trade name: Bencot S-2, manufactured by Asahi Kasei). Contamination resistance was evaluated according to the following criteria. The results are shown in Tables 4 and 5.
○: 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.

The trade names in Table 3 and Table 4 represent the following.
Cymel 300: A compound represented by the following formula (10) self-condensed into an average 1.35 mer Cymel 303: A compound represented by the following formula (10) self-condensed to an average 1.7 mer Hollow silica particles B2: JX1008SIV (catalyst chemical industry) (isopropyl alcohol sol, solid content concentration 22%, number average particle size 40 nm, refractive index 1.29)
Hollow silica particle B3: JX1009SIV (catalyst chemical industry) (methyl isobutyl ketone sol, solid content concentration 22%, number average particle size 40 nm, refractive index 1.29)

  From the results of Tables 3 and 4, it is clear that the curable resin compositions according to the examples are excellent in appearance, haze, reflectance, scratch resistance and stain resistance, and have a low refractive index. In contrast, it can be seen that Comparative Example 1 that does not contain hollow silica particles has poor scratch resistance. Moreover, it turns out that the characteristics other than a refractive index and a reflectance are inferior in the comparative example 2 which does not contain a fluorine-containing polymer.

  The thermosetting resin composition of the present invention exhibits good thermosetting, and the cured product formed from the thermosetting resin composition of the present invention has a low refractive index, scratch resistance and stain resistance. Excellent. Therefore, the thermosetting resin composition of the present invention can be advantageously used for the formation of an optical material such as an antireflection film and an optical fiber sheath material, and also has a weather resistance by utilizing the high fluorine content. Can be suitably used as a coating material, a weather-resistant film material, a coating material, or the like for a base material that requires the above. In addition, the cured film has excellent adhesion to the base material, high scratch resistance, and imparts a good antireflection effect. Therefore, the cured film is extremely useful as an antireflection film, and can be applied to various display devices. The visibility can be improved.

It is a schematic diagram of the anti-reflective film which concerns on one Embodiment of this invention. It is a schematic diagram of the anti-reflective film which concerns on other embodiment of this invention. It is a schematic diagram of the anti-reflective film which concerns on other embodiment of this invention. It is a schematic diagram of the anti-reflective film which concerns on other embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Antireflection film 10 Base material 12 Hard coat layer 13 High refractive index film 14 Low refractive index film 15 Antistatic layer

Claims (13)

The following components (A) to (C):
(A) Fluorine-containing olefin polymer (B) hollow particles (C) containing 10 mol% to 50 mol% of a structural unit derived from a monomer containing a hydroxyl group and having a polysiloxane segment in the main chain ) A thermosetting resin composition containing a crosslinkable compound.   The thermosetting resin composition according to claim 1, wherein the fluorine content of the component (A) is 30% by weight or more, and the number average molecular weight in terms of polystyrene is 5000 or more.   The thermosetting resin composition according to claim 1 or 2, wherein the component (A) further contains 0 mol% to 10 mol% of a structural unit derived from a reactive emulsifier.   The thermosetting resin composition according to any one of claims 1 to 3, wherein the component (B) is a particle mainly composed of silica.   The thermosetting resin composition according to any one of claims 1 to 4, wherein the number average particle diameter of the component (B) is in the range of 1 to 200 nm.   The thermosetting resin composition according to claim 1, wherein the refractive index of the component (B) is 1.35 or less. The thermosetting resin composition according to any one of claims 1 to 6, wherein the crosslinkable compound (C) is a compound having a structure represented by the following general formula (Cp-1) or (Cp-2). .

[In the formulas (Cp-1) and (Cp-2), R ²⁵ , R ²⁷ and R ²⁹ represent a methylene group or an alkylene group having 2 to 4 carbon atoms, and R ²⁶ , R ²⁸ and R ³⁰ represent hydrogen or carbon. The alkyl group of number 1-4 is shown. ]   (C) The crosslinkable compound is an alkoxyalkylated melamine compound, The thermosetting resin composition according to any one of claims 1 to 7.   Furthermore, (D) The thermosetting resin composition of any one of Claims 1-8 containing an acid catalyst.   Furthermore, (E) The thermosetting resin composition of any one of Claims 1-9 containing the organic solvent.   The thermosetting resin composition according to any one of claims 1 to 10, which is a material for an antireflection film.   Hardened | cured material obtained by thermosetting the thermosetting resin composition of any one of Claims 1-11. An antireflection film having a low refractive index layer made of the cured product according to claim 12.

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