JP4904885B2 - Curable resin composition, cured film, antireflection film laminate and method for producing cured film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a curable resin composition providing a cured film having excellent scratch resistance and chemical resistance and a long pot life, a cured film obtained by curing the same and an antireflection film and to provide a method for producing a cured film. <P>SOLUTION: The curable resin composition comprises (A) a hydroxy group-containing fluorine-containing polymer, (B) a thermosetting compound, (C) a compound to generate an acid by irradiation with radiation, (D) an ethylenic unsaturated group-containing fluorine-containing polymer, (E) a compound containing two or more (meth)acryloyl groups, (F) a compound to generate an active species by irradiation with radiation and (G) an organic solvent. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention comprises a curable resin composition, a cured film comprising a cured product of the curable resin composition, and a low refractive index layer comprising the cured film and excellent in scratch resistance, coating property, and durability. The present invention relates to an antireflection film.

In various display panels such as liquid crystal display panels, cold cathode ray tube panels, plasma displays, etc., in order to prevent reflection of external light and improve image quality, it has low refractive index, scratch resistance, coatability, and durability. There is a demand for an antireflection film including a low refractive index layer made of an excellent cured film.
In these display panels, the surface is often wiped with gauze impregnated with ethanol or the like in order to remove attached fingerprints, dust, and the like, and scratch resistance is required.
In particular, in a liquid crystal display panel, the antireflection film is provided on the liquid crystal unit in a state of being bonded to a polarizing plate. In addition, for example, triacetyl cellulose is used as the base material. However, in an antireflection film using such a base material, an alkali is usually used in order to increase the adhesiveness when being bonded to the polarizing plate. It is necessary to saponify with an aqueous solution.
Therefore, in the use of a liquid crystal display panel, an antireflection film excellent in alkali resistance is particularly required in terms of durability.

As a material for a low refractive index layer of an antireflection film, for example, a fluororesin-based paint containing a hydroxyl group-containing fluoropolymer is known (Patent Documents 1 to 3).
However, in such a fluororesin-based paint, in order to cure the coating film, it is necessary to heat and crosslink the hydroxyl group-containing fluoropolymer and a curing agent such as melamine resin in the presence of an acid catalyst. Depending on the heating 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 problems, an isocyanate group-containing unsaturated compound having at least one isocyanate group and at least one ethylenically unsaturated group and a hydroxyl group-containing fluoropolymer are converted into the number of isocyanate groups. A coating composition containing an unsaturated group-containing fluorinated vinyl polymer obtained by reacting at a ratio of / number of hydroxyl groups of 0.01 to 1.0 has been proposed (Patent Document 4).

JP 57-34107 A JP 59-189108 A JP 60-67518 A Japanese Patent Publication No. 6-35559

However, in the coating composition described in Patent Document 4, when preparing the unsaturated group-containing fluorinated vinyl polymer, an amount of isocyanate sufficient to react all the hydroxyl groups of the hydroxyl group-containing fluorinated polymer. An unreacted hydroxyl group was positively left in the polymer without using a group-containing unsaturated compound.
For this reason, a coating composition containing such a polymer can be cured at a low temperature in a short time. However, the coating film obtained from the composition of Patent Document 4 is a coating There was a problem that the property and scratch resistance were not sufficient.

  Further, the conventional heat / UV hybrid type curable resin composition is a two-component type in which a curing agent (p-toluenesulfonic acid) is added afterwards in order to suppress a side reaction of the crosslinking agent in the solution. . Therefore, a process of mixing the liquid at the time of coating is required, and when the coating takes a long time, the side reaction of the crosslinking agent proceeds, so that the characteristics of the composition change over time. is there. In the method using an amine block type thermal acid generator, there is a problem that aggregation of silica particles occurs and optical characteristics are deteriorated.

  In view of the above situation, the present invention provides a cured film excellent in scratch resistance and chemical resistance, and has a long pot life, a cured film obtained by curing it, an antireflection film, and It aims at providing the manufacturing method of a cured film.

  In order to achieve the above object, the present inventors have conducted intensive research, and if a photoacid generator is used as a curing catalyst, it does not generate an acid that causes a polymerization reaction to proceed until UV irradiation. The pot life of the resin composition was remarkably improved, and at the same time, it was found that a cured film having excellent properties such as scratch resistance and chemical resistance was obtained, and the present invention was completed.

［一般式（１）中、Ｒ^１はフッ素原子、フルオロアルキル基、又は−ＯＲ^２で表される基（Ｒ^２はアルキル基、又はフルオロアルキル基を示す）を示す］

［一般式（２）中、Ｒ^３は水素原子又はメチル基を、Ｒ^４はアルキル基、−（ＣＨ_２）_ｘ−ＯＲ^５若しくは−ＯＣＯＲ^５で表される基（Ｒ^５はアルキル基、又はグリシジル基を、ｘは０又は１の数を示す）、カルボキシル基、又はアルコキシカルボニル基を示す］

［一般式（３）中、Ｒ^６は水素原子、又はメチル基を、Ｒ^７は水素原子、又はヒドロキシアルキル基を、ｖは０又は１の数を示す］
３．前記（Ａ）水酸基含有含フッ素重合体が、前記構造単位（ａ）、（ｂ）及び（ｃ）の合計１００モル部に対して、下記構造単位（ｄ）を０．１〜１０モル部含む、上記１又は２に記載の硬化性樹脂組成物。
（ｄ）下記一般式（４）で表される構造単位

［一般式（４）中、Ｒ^１０〜Ｒ^１３は水素原子、アルキル基、又はシアノ基を示し、Ｒ^１４〜Ｒ^１７は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の数を示す。］
４．前記（Ａ）水酸基含有含フッ素重合体が、前記構造単位（ａ）、（ｂ）及び（ｃ）の合計１００モル部に対して、下記構造単位（ｅ）を０．１〜５モル部含む上記１〜３のいずれか一に記載の硬化性樹脂組成物。
（ｅ）下記一般式（５）で表される構造単位

［一般式（５）中、Ｒ^１８は下記式（６）で示される基を示す］

［一般式（６）中、ｎは１〜２０の数、ｍは０〜４の数、ｕは３〜５０の数を示す］
５．前記（Ｃ）放射線照射により酸を発生する化合物が、ＵＶ照射により有機スルホン酸を発生する酸発生剤である上記１〜４いずれかに記載の硬化性樹脂組成物。
６．さらに（Ｄ）エチレン性不飽和基含有含フッ素重合体を含み、前記（Ｄ）エチレン性不飽和基含有含フッ素重合体が、１個のイソシアネート基と、少なくとも１個のエチレン性不飽和基とを含有する化合物と、前記（Ａ）水酸基含有含フッ素共重合体と、を反応させて得られたものである上記１〜５のいずれかに記載の樹脂組成物。
７．前記１個のイソシアネート基と、少なくとも１個のエチレン性不飽和基とを含有する化合物が、２−（メタ）アクリロイルオキシエチルイソシアネートである上記６に記載のエチレン性不飽和基含有含フッ素重合体。
８．前記（Ｅ）２個以上の（メタ）アクリロイル基を有する化合物が、３個以上の（メタ）アクリロイル基を有する化合物である、上記１〜７のいずれかに記載の硬化性樹脂組成物。
９．さらに、（Ｈ）シリカ粒子を含有する、上記１〜８のいずれかに記載の硬化性樹脂組成物。
１０．前記（Ｈ）シリカ粒子が、エチレン性不飽和基を有する、上記９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なる、Ｎａ−Ｄ線の屈折率が１．４５以下の硬化膜。
１２．上記１〜１０のいずれかに記載の硬化性樹脂組成物の塗布膜を、加熱し、次いで放射線を照射する工程により硬化させる、硬化膜の製造方法。
１３．上記１１に記載の硬化膜を含む反射防止膜積層体。 According to the present invention, the following curable resin composition, a cured film comprising the same, and an antireflection film laminate are provided.
1. The following ingredients,
(A) a hydroxyl group-containing fluoropolymer,
(B) a thermosetting compound,
(C) a compound that generates an acid upon irradiation with radiation,
(E) a compound having two or more (meth) acryloyl groups,
(F) A curable resin composition containing a compound that generates active species upon irradiation with radiation, and (G) an organic solvent.
2. The (A) hydroxyl group-containing fluoropolymer is represented by the structural unit (a) represented by the following formula (1), the structural unit (b) represented by the following formula (2), and the following formula (3). Structural unit (c)
The structural units (a), (b) and (c) are added in an amount of (a) 20 to 70 mol%, (b) 5 to 70 mol% and (c) 5 to 70 mol% with respect to 100 mol% in total. The curable resin composition as described in 1 above, which is contained in a proportion of
(A) Structural unit represented by the following general formula (1) (b) Structural unit represented by the following general formula (2) (c) Structural unit represented by the following general formula (3)

[In General Formula (1), R ¹ represents a fluorine atom, a fluoroalkyl group, or a group represented by —OR ² (R ² represents an alkyl group or a fluoroalkyl group)]

[In General Formula (2), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, a group represented by — (CH ₂ ) _x —OR ⁵ or —OCOR ⁵ (R ⁵ represents an alkyl group, or A glycidyl group, x represents a number of 0 or 1), a carboxyl group, or an alkoxycarbonyl group]

[In General 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]
3. The (A) hydroxyl group-containing fluoropolymer contains 0.1 to 10 mole parts of the following structural unit (d) with respect to 100 mole parts in total of the structural units (a), (b) and (c). The curable resin composition according to 1 or 2 above.
(D) Structural unit represented by the following general formula (4)

[In General Formula (4), R ^{10 to} R ¹³ represent a hydrogen atom, an alkyl group, or a cyano group, R ^{14 to} R ¹⁷ represent a hydrogen atom or an alkyl group, and p and q are numbers of 1 to 6, s and t are numbers from 0 to 6, and y is a number from 1 to 200. ]
4). The (A) hydroxyl group-containing fluoropolymer contains 0.1 to 5 mole parts of the following structural unit (e) with respect to 100 mole parts in total of the structural units (a), (b) and (c). Curable resin composition as described in any one of said 1-3.
(E) Structural unit represented by the following general formula (5)

[In General Formula (5), R ¹⁸ represents a group represented by the following Formula (6)]

[In General Formula (6), n is a number from 1 to 20, m is a number from 0 to 4, and u is a number from 3 to 50]
5. 5. The curable resin composition according to any one of 1 to 4 above, wherein the compound that generates an acid upon irradiation with radiation (C) is an acid generator that generates an organic sulfonic acid upon irradiation with UV.
6). And (D) an ethylenically unsaturated group-containing fluoropolymer, wherein the (D) ethylenically unsaturated group-containing fluoropolymer comprises one isocyanate group, at least one ethylenically unsaturated group, 6. The resin composition as described in any one of 1 to 5 above, which is obtained by reacting a compound containing a hydroxyl group-containing fluorine-containing copolymer (A).
7). 7. The ethylenically unsaturated group-containing fluoropolymer according to 6 above, wherein the compound containing one isocyanate group and at least one ethylenically unsaturated group is 2- (meth) acryloyloxyethyl isocyanate. .
8). The curable resin composition according to any one of 1 to 7, wherein the compound (E) having two or more (meth) acryloyl groups is a compound having three or more (meth) acryloyl groups.
9. Furthermore, (H) Curable resin composition in any one of said 1-8 containing a silica particle.
10. 10. The curable resin composition according to 9 above, wherein the (H) silica particles have an ethylenically unsaturated group.
11. A cured film having a refractive index of Na-D line of 1.45 or less, obtained by curing the curable resin composition according to any one of 1 to 10 above.
12 The manufacturing method of a cured film which hardens the coating film of the curable resin composition in any one of said 1-10 by the process of heating and then irradiating a radiation.
13. An antireflection film laminate comprising the cured film as described in 11 above.

According to the curable resin composition of the present invention, a cured film having excellent scratch resistance and chemical resistance can be obtained.
Since the curable resin composition of the present invention does not cause a polymerization reaction during storage, the pot life is long.
Conventionally, a two-component type was unavoidable in order not to cause a polymerization reaction during storage, but the curable resin composition of the present invention does not cause a polymerization reaction during storage, so that it is a one-component type. It is possible.
According to the present invention, an antireflection film laminate having a cured film having excellent scratch resistance and chemical resistance can be obtained.

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

1. Curable resin composition The curable resin composition of the present invention (hereinafter sometimes referred to as the composition of the present invention) contains the following components (A) to (I). Components (A), (B), (C), (E), (F) and (G) are essential components, and components (D), (H) and (I) are added as necessary. It is an optional component.
(A) a hydroxyl group-containing fluoropolymer,
(B) a thermosetting compound,
(C) a compound that generates an acid upon irradiation with radiation,
(D) an ethylenically unsaturated group-containing fluoropolymer (E) a compound having two or more (meth) acryloyl groups,
(F) A compound that generates active species upon irradiation with radiation, and (G) an organic solvent (H) silica particles (I) other additives.

(1) Component of curable resin composition (A) Hydroxyl group-containing fluoropolymer Hydroxyl group-containing fluoropolymer is a polymer having a hydroxyl group and a carbon-fluorine bond in the molecule, and the fluorine content is 30% by mass or more. It is preferable that Here, the fluorine content is a value measured by the alizarin complexone method.

  The (A) hydroxyl group-containing fluoropolymer used in the present invention is preferably a copolymer of at least the following structural units (a), (b) and (c).

[1] Structural unit (a)
The structural unit (a) is a structural unit represented by the following general formula (1).

［一般式（１）中、Ｒ^１はフッ素原子、フルオロアルキル基、又は−ＯＲ^２で表される基（Ｒ^２はアルキル基、又はフルオロアルキル基を示す）を示す］
上記一般式（１）において、Ｒ^１及びＲ^２のフルオロアルキル基としては、トリフルオロメチル基、パーフルオロエチル基、パーフルオロプロピル基、パーフルオロブチル基、パーフルオロヘキシル基、パーフルオロシクロヘキシル基等の炭素数１〜６のフルオロアルキル基が挙げられる。また、Ｒ^２のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、シクロヘキシル基等の炭素数１〜６のアルキル基が挙げられる。

[In General Formula (1), R ¹ represents a fluorine atom, a fluoroalkyl group, or a group represented by —OR ² (R ² represents an alkyl group or a fluoroalkyl group)]
In the general formula (1), examples of the fluoroalkyl group of R ¹ and R ² include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorocyclohexyl group. And a C1-C6 fluoroalkyl group. 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), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether); perfluoro (alkoxyalkyl vinyl ether) such as perfluoro (propoxypropyl vinyl ether) ) A single species or a combination of two or more species.
Among these, hexafluoropropylene and perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether) are more preferable, and it is more preferable to use these in combination.

In addition, the content rate of structural unit (a) is 20-70 mol% with respect to a total of 100 mol% of structural units (a), (b), and (c) in a hydroxyl-containing fluoropolymer. The reason for this is that when the content is less than 20 mol%, it is sometimes difficult to develop a low refractive index, which is an optical characteristic of the fluorine-containing material intended by the present invention, while the content is contained. This is because when the ratio exceeds 70 mol%, the solubility of the hydroxyl group-containing fluoropolymer in an organic solvent, transparency, or adhesion to a substrate may be lowered.
For this reason, the content of the structural unit (a) is more preferably 25 to 65 mol% with respect to a total of 100 mol% of the structural units (a), (b) and (c). Preferably, it is more preferable to set it as 30-60 mol%.

[2] Structural unit (b)
The structural unit (b) is a structural unit represented by the following general formula (2).

［一般式（２）中、Ｒ^３は水素原子又はメチル基を、Ｒ^４はアルキル基、−（ＣＨ_２）_ｘ−ＯＲ^５若しくは−ＯＣＯＲ^５で表される基（Ｒ^５はアルキル基、又はグリシジル基を、ｘは０又は１の数を示す）、カルボキシル基、又はアルコキシカルボニル基を示す］
一般式（２）において、Ｒ^４又はＲ^５のアルキル基としては、メチル基、エチル基、プロピル基、ヘキシル基、シクロヘキシル基、ラウリル基等の炭素数１〜１２のアルキル基が挙げられ、アルコキシカルボニル基としては、メトキシカルボニル基、エトキシカルボニル基等が挙げられる。

[In General Formula (2), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, a group represented by — (CH ₂ ) _x —OR ⁵ or —OCOR ⁵ (R ⁵ represents an alkyl group, or A glycidyl group, x represents a number of 0 or 1), a carboxyl group, or an alkoxycarbonyl group]
In the general formula (2), examples of the alkyl group represented by R ⁴ or R ⁵ include alkyl groups having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, and a lauryl group. Examples of the carbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

  The structural unit (b) can be introduced by using the above-mentioned vinyl monomer having a substituent as a polymerization component. Examples of such vinyl monomers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n -Alkyl vinyl ethers or cycloalkyl vinyl ethers such as octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether; allyl ethers such as ethyl allyl ether, butyl allyl ether; vinyl acetate, vinyl propionate, vinyl butyrate, pivalin Carboxylic acid vinyl ester such as vinyl acid vinyl, vinyl caproate, vinyl vinyl versatate, vinyl stearate Tellurium; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- ( (Meth) acrylic acid esters such as n-propoxy) ethyl (meth) acrylate; (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and other unsaturated carboxylic acids, etc. The combination of is mentioned.

In addition, the content rate of a structural unit (b) is 5-70 mol% with respect to a total of 100 mol% of the structural units (a), (b), and (c) in a hydroxyl-containing fluoropolymer. This is because if the content is less than 5 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced. On the other hand, if the content exceeds 70 mol%, the hydroxyl group This is because optical properties such as transparency and low reflectivity of the fluorinated polymer may be deteriorated.
For these reasons, the content of the structural unit (b) is set to 5 to 5% with respect to 100 mol% in total of the structural units (a), (b) and (c) in the hydroxyl group-containing fluoropolymer. It is more preferable to set it as 65 mol%, and it is still more preferable to set it as 5-60 mol%.

[3] Structural unit (c)
The structural unit (c) is a structural unit represented by the following general formula (3).

［一般式（３）中、Ｒ^６は水素原子、又はメチル基を、Ｒ^７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］
一般式（３）において、Ｒ^７のヒドロキシアルキル基としては、２−ヒドロキシエチル基、２−ヒドロキシプロピル基、３−ヒドロキシプロピル基、４−ヒドロキシブチル基、３−ヒドロキシブチル基、５−ヒドロキシペンチル基、６−ヒドロキシヘキシル基が挙げられる。

[In General 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]
In the general formula (3), as the hydroxyalkyl group of R ⁷ , 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 5-hydroxypentyl Group, 6-hydroxyhexyl group.

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

The content of the structural unit (c) is 5 to 70 mol% with respect to a total of 100 mol% of the structural units (a), (b) and (c) in the hydroxyl group-containing fluoropolymer. Is preferred. This is because if the content is less than 5 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced. On the other hand, if the content exceeds 70 mol%, the hydroxyl group This is because optical properties such as transparency and low reflectivity of the fluorinated polymer may be deteriorated.
For these reasons, the content of the structural unit (c) is set to 5 to 5% with respect to 100 mol% in total of the structural units (a), (b) and (c) in the hydroxyl group-containing fluoropolymer. It is more preferable to set it as 65 mol%, and it is still more preferable to set it as 5-60 mol%.

[4] Structural unit (d)
Moreover, it is also preferable that the hydroxyl group-containing fluoropolymer further comprises the structural unit (d). The structural unit (d) is a structural unit represented by the following general formula (4).

[In General Formula (4), R ^{10 to} R ¹³ represent a hydrogen atom, an alkyl group, or a cyano group, R ^{14 to} R ¹⁷ represent a hydrogen atom or an alkyl group, and p and q are numbers of 1 to 6, s and t are numbers from 0 to 6, and y is a number from 1 to 200. ]

  The structural unit (d) can be introduced by using an azo group-containing polysiloxane compound represented by the following formula (7).

［一般式（７）中、Ｒ^１０〜Ｒ^１３、Ｒ^１４〜Ｒ^１７、ｐ、ｑ、ｓ、ｔ、及びｙは、上記一般式（４）と同じであり、ｚは１〜２０の数である。］

[In General Formula (7), R ^{10 to} R ¹³ , R ^{14 to} R ¹⁷ , p, q, s, t, and y are the same as those in General Formula (4), and z is a number from 1 to 20. It is. ]

  In the present invention, the azo group-containing polysiloxane compound represented by the general formula (7) is particularly preferably a compound represented by the following general formula (8).

［一般式（８）中、ｙ及びｚは、上記一般式（７）と同じである。］

[In general formula (8), y and z are the same as the said general formula (7). ]

In addition, it is preferable that the content rate of a structural unit (d) shall be 0.1-10 mol part with respect to the total 100 mol part of the said structural unit (a), (b) and (c). 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 decreased, and the scratch resistance of the coated film may be decreased. 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 this reason, the content of the structural unit (d) is 0.5 to 8 mole parts with respect to a total of 100 mole parts of the structural units (a), (b) and (c). More preferably, it is more preferably 0.5 to 6 mole parts. For the same reason, the content of the structural unit (d) is desirably determined so that the content of the structural unit (d) contained therein falls within the above range.

[5] Structural unit (e)
Moreover, it is also preferable that the hydroxyl group-containing fluoropolymer further comprises the structural unit (e). The structural unit (e) is a structural unit represented by the following general formula (5).

［一般式（５）において、Ｒ^１８は、下記一般式（６）で表される基を示す。］

[In General Formula (5), R ¹⁸ represents a group represented by the following General Formula (6). ]

［一般式（６）中、ｎは１〜２０の数、ｍは０〜４の数、ｕは３〜５０の数を示す］

[In General Formula (6), n is a number from 1 to 20, m is a number from 0 to 4, and u is a number from 3 to 50]

  The structural unit (e) can be introduced by using a reactive emulsifier as a polymerization component. Examples of such reactive emulsifiers include compounds represented by the following general formula (9).

［一般式（９）中、ｎ、ｍ、及びｕは、上記一般式（６）と同様である］

[In general formula (9), n, m, and u are the same as in general formula (6) above]

In addition, it is preferable that the content rate of a structural unit (e) shall be 0.1-5 mol part with respect to a total of 100 mol parts of the said structural unit (a), (b) and (c). 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 5 mol part or less, the adhesive of the resin composition is improved. This is because the property does not increase excessively, the handling becomes easy, and the moisture resistance does not decrease even when used as a coating material.
For such reasons, the content of the structural unit (e) is more preferably 0.1 to 5 mol parts, based on the total amount of the hydroxyl group-containing fluoropolymer, and 0.5 to 2 More preferably, the molar part.

[6] Molecular Weight The hydroxyl group-containing fluoropolymer has a polystyrene-reduced number average molecular weight of 5,000 measured by gel permeation chromatography (hereinafter referred to as “GPC”) using tetrahydrofuran (hereinafter referred to as “THF”) as a solvent. It is preferably ~ 500,000. 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 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 500,000, and even more preferably 10,000 to 100,000.

  The blending amount of the (A) hydroxyl group-containing fluoropolymer in the resin composition of the present invention is preferably 20 to 70% by mass with respect to the total amount of the composition excluding the organic solvent, and 20 to 65% by mass. Is more preferable, and 20 to 60% by mass is particularly preferable. By being 20-70 mass%, the abrasion resistance of the cured film obtained by hardening | curing the composition of this invention improves.

(B) Thermosetting Compound In the composition of the present invention, the thermosetting compound (hereinafter sometimes referred to as “component (B)”) is heated to react with the compound itself or with another compound to be cured. Is. The thermosetting compound may be included by simply mixing it in the composition, or a reaction product obtained by reacting all of the hydroxyl group-containing fluoropolymer and the thermosetting compound or a state in which only a part thereof is reacted. May be included. However, those in which the reaction site is an ethylenically unsaturated group are not included in the component (B).

  Examples of the thermosetting compound include various amino compounds, various hydroxyl group-containing compounds such as pentaerythritol, polyphenol, and glycol, and others.

  The amino compound used as the thermosetting compound is an amino group capable of reacting with a hydroxyl group present in the fluoropolymer, for example, one or both of a hydroxyalkylamino group and an alkoxyalkylamino group in total of 2 or more. Specific examples 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 in particular, good storage stability can be obtained in the resin composition. In terms of obtaining good reactivity, and alkoxylated methylmelamine is preferable. There are no particular limitations on the methylolated melamine and the alkoxylated methylmelamine used as the thermosetting compound. For example, the method described in the document “Plastic Materials Course [8] Urea Melamine Resin” (Nikkan Kogyo Shimbun) It is also possible to use various resinous materials obtained.

  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.

  The blending amount of the thermosetting compound (B) in the composition of the present invention is preferably in the range of 1 to 50% by mass, more preferably 5 to 45, with the total amount of the composition excluding the organic solvent being 100% by mass. It is the range of 10 mass%, More preferably, it is 10-40 mass%. If the amount of the thermosetting compound used is too small, the durability of the thin film formed from the resulting resin composition may be insufficient, and if it exceeds 50% by mass, the above-mentioned hydroxyl group-containing fluoropolymer In the reaction, it is difficult to avoid gelation, and the cured product may become brittle.

  (A) The reaction between the hydroxyl group-containing fluoropolymer and the (B) thermosetting compound can be achieved, for example, by (B) adding the thermosetting compound to a solution of an organic solvent in which the hydroxyl group-containing fluoropolymer is dissolved. The reaction system may be added while homogenizing the reaction system by heating and stirring 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. If this heating temperature is less than 30 ° C, the reaction proceeds very slowly. If it exceeds 150 ° C, in addition to the intended reaction, (B) due to the reaction between methylol groups and alkoxylated methyl groups in the thermosetting compound. Since a crosslinking reaction occurs and a gel is formed, it is not preferable. 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.

  The reaction between (A) the hydroxyl group-containing fluoropolymer and (B) the thermosetting compound is the same as the organic solvent, for example, the same organic solvent used in the production of (A) the hydroxyl group-containing fluoropolymer. It is preferable to use it. In the present invention, the reaction solution obtained by the above-described (A) hydroxyl group-containing fluoropolymer and (B) thermosetting compound can be used as a resin composition solution as it is, or as necessary. It can also be used after blending various additives.

(C) Compound that generates acid upon irradiation with radiation (C) The compound that generates acid upon irradiation with radiation is a sulfonic acid derivative having high acidity, and radiation, preferably ultraviolet (UV). It is an acid generator that generates organic sulfonic acid, preferably p-toluenesulfonic acid by irradiation (hereinafter sometimes referred to as “photoacid generator”). Since the generated organic sulfonic acid is a strong acid compound, it is effective for the condensation reaction between the melamine compound and the hydroxyl group-containing fluoropolymer, and a cured film having high scratch resistance can be produced.

  Since the photoacid generator does not generate an organic sulfonic acid unless it is irradiated with light of a specific wavelength, the reaction between the (A) hydroxyl group-containing fluoropolymer and the (B) thermosetting compound is allowed to proceed. There is no. Therefore, the composition of the present invention containing (C) the photoacid generator has a long pot life as a composition and is kept in a good state until it is irradiated with radiation.

  (C) Examples of commercially available photoacid generators include p-toluenesulfonic acid derivatives (PAI-101, DPI-105, DPI-109, DPI-201, MPI-105, MPI-106, MPI-109, BBI-105, BBI-106, BBI-109, BBI-201, BBI-301, TPS-105, TPS-109, MDS-105, MDS-109, MDS-205, NAT-105, NDS-105, NDS- 155, NDS-165, MBZ-101, MBZ-201, MBZ-301, PYR-100, DNB-101, NB-101, NB-201, SI-100, SI-101, SI-105, SI-106, PI-105, NDI-101, NDI-105 NAI-100, NAI-1002, NAI-1003, N I-1004, NAI-101, NAI-105, NAI-106, PAI-101: above, manufactured by Midori Chemical Co.), SP-095, SP-080, SP-082, SP-083, SP-084, SP- 090, SP-063, IP-019, N-1919, SP-062 (above, manufactured by Asahi Denka).

  The content of the component (C) photoacid generator in the composition of the present invention is 1 to 10% by mass, preferably 1 to 5% by mass, more preferably 100% by mass of the total composition excluding the organic solvent. 3 to 5% by mass. If it is in the range of 1 to 10% by mass, the resulting cured product exhibits excellent scratch resistance and chemical resistance.

(D) Ethylenically unsaturated group-containing fluoropolymer
The composition of the present invention may contain (D) an ethylenically unsaturated group-containing fluoropolymer, and the ethylenically unsaturated group-containing fluoropolymer used in the present invention cures the curable resin composition. It is used for reducing the refractive index of the resulting cured film and enhancing the scratch resistance of the cured film and the antireflection film laminate using the cured film. The ethylenically unsaturated group-containing fluorine-containing polymer is a fluorine-containing polymer exhibiting radiation curability by having an ethylenically unsaturated group.
The structure is not particularly limited. For example, the (A) hydroxyl group-containing fluoropolymer is reacted with a compound containing one isocyanate group and at least one ethylenically unsaturated group. It is preferable that it is a polymer obtained by making it.

(I) Hydroxyl group-containing fluoropolymer Since it has the same content as the above-mentioned (A) hydroxyl group-containing fluoropolymer, it is not described in detail here. (D) The hydroxyl group-containing fluoropolymer used in the production of the ethylenically unsaturated group-containing fluoropolymer can be the same polymer as the component (A) described above, or has a different composition or molecular weight. Although a polymer can also be used, it is preferable to use the above-mentioned (A) hydroxyl group-containing fluoropolymer.

(Ii) Compound containing one isocyanate group and at least one ethylenically unsaturated group The compound containing one isocyanate group and at least one ethylenically unsaturated group is the above-mentioned (A) hydroxyl group. By reacting with the hydroxyl group of the containing fluoropolymer (the structural unit (c) has a hydroxyl group), (D) an ethylenically unsaturated group-containing fluoropolymer is obtained. In this case, the structural unit (c) of the hydroxyl group-containing fluoropolymer is an ethylenically unsaturated group-containing structural unit in the ethylenically unsaturated group-containing fluoropolymer.
The compound containing one isocyanate group and at least one ethylenically unsaturated group may be a compound containing one isocyanate group and at least one ethylenically unsaturated group in the molecule. There is no particular limitation.
In addition, when two or more isocyanate groups are contained, there is a possibility of causing gelation when reacting with a hydroxyl group-containing fluoropolymer.
Moreover, since the curable resin composition mentioned later can be hardened more easily as said ethylenically unsaturated group, the compound which has a (meth) acryloyl group is more preferable.
As such a compound, 2- (meth) acryloyloxyethyl isocyanate and 2- (meth) acryloyloxypropyl isocyanate may be used singly or in combination of two or more.

Such a compound can also be synthesized by reacting diisocyanate and a hydroxyl group-containing (meth) acrylate.
In this case, examples of the diisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m- Phenylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 3,3′-dimethylphenylene diisocyanate, 4,4′-biphenylene diisocyanate, 1, 6-hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanate ethyl) Malate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diisocyanate, 2,5 (or 6 ) -Bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, or a combination of two or more thereof.
Among these, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), and 1,3-bis (isocyanate methyl) cyclohexane are particularly preferable.

Examples of hydroxyl group-containing (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone (meth) acrylate, polypropylene glycol (meta ) Acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, isocyanuric acid EO-modified di (meth) acrylate, or a combination of two or more Can be mentioned.
Among these, 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are particularly preferable.
In addition, as a commercial item of a hydroxyl-containing polyfunctional (meth) acrylate which has two or more (meth) acryloyl groups, 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, etc. can be obtained.

  When a compound containing one isocyanate group and at least one ethylenically unsaturated group is synthesized from diisocyanate and a hydroxyl group-containing polyfunctional (meth) acrylate, the hydroxyl group-containing polyfunctional group ( The addition amount of (meth) acrylate is preferably 1 to 1.2 mol.

  Examples of the method for synthesizing such a compound include a method in which diisocyanate and a hydroxyl group-containing (meth) acrylate are collectively charged and reacted, a method in which diisocyanate is dropped into a hydroxyl group-containing (meth) acrylate, and a reaction method.

  The blending amount of the (D) ethylenically unsaturated group-containing fluoropolymer in the composition of the present invention is preferably 20 to 70% by mass with respect to the total amount of the composition excluding the organic solvent. 65 mass% is further more preferable, and 20-60 mass% is especially preferable. By being 20-70 mass%, the abrasion resistance of the cured film obtained by hardening | curing the composition of this invention improves.

(E) Compound having two or more (meth) acryloyl groups A compound having two or more (meth) acryloyl groups (hereinafter sometimes referred to as “polyfunctional (meth) acrylate compound”) is a resin composition. In addition, it is a component that imparts radiation curability, and is used to enhance the scratch resistance of a cured film obtained by curing a resin composition and an antireflection film using the cured film.

  The polyfunctional (meth) acrylate compound is not particularly limited as long as it is a compound having at least two (meth) acryloyl groups in the molecule. Examples of the compound having two (meth) acryloyl groups include ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis ( 2-hydroxyethyl) isocyanurate di (meth) acrylate, bis ((meth) acryloyloxymethyl) tricyclo [5.2.1.02,6] decane (also called “tricyclodecanediyldimethanol di (meth) acrylate”) Say), and manufacture these compounds Poly (meth) acrylates of ethylene oxide or propylene oxide adducts of starting alcohols, oligoester (meth) acrylates having two (meth) acryloyl groups in the molecule, oligoether (meth) acrylates, Examples include oligourethane (meth) acrylates and oligoepoxy (meth) acrylates.

The polyfunctional (meth) acrylate compound is preferably a compound having 3 or more polyfunctional (meth) acryloyl groups in the molecule. Examples of such include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, Alkyl modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate , Ditrimethylolpropane tetra (meth) acrylate, Shin-Nakamura Chemical Co., Ltd. U-6HA, U-15HA, and the following formula (10) Alone or in combinations of two or more such are the compounds.
Of these, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) Acrylate, U-6HA, U-15HA, and a compound represented by the following formula (10) are particularly preferred.

［式（１０）中、「Ａｃｒｙｌ」は、アクリロイル基を示す。］

[In the formula (10), “Acryl” represents an acryloyl group. ]

  In the composition of the present invention, (E) the compounding amount of the compound having two or more (meth) acryloyl groups may be 5 to 25% by mass with the total amount of the composition excluding the organic solvent being 100% by mass. Preferably, 5 to 20% by mass is more preferable. By being 5-25 mass%, the abrasion resistance of the cured film obtained by hardening | curing the composition of this invention improves.

(F) Compound that generates active species upon irradiation with radiation In the resin composition of the present invention, a compound that generates active species upon irradiation with radiation (hereinafter referred to as “photopolymerization initiator” or “(F) component”). Is added). Such a compound is used to efficiently cure the composition of the present invention.

Examples of the compound that generates active species upon irradiation with radiation include photo radical generators that generate radical species as active species.
Radiation is defined as energy rays that can decompose active compounds to generate active species. Examples of such radiation include optical energy rays such as visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, and γ rays. However, it is preferable to use ultraviolet rays from the viewpoint of having a certain energy level, a high curing speed, and a relatively inexpensive irradiation apparatus, and a small size.

  Examples of the photo radical generator include acetophenone, acetophenone benzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, carbazole, xanthone, 4-chlorobenzophenone, 4 , 4′-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3′-dimethyl-4-methoxybenzophenone, thioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1- (4-dodecylphenyl) -2 -Hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, triphenylamine, 2,4,6-trimethylbenzoyldiphenyl Phosphine oxide, 1-H Roxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, Michler ketone, 3-methylacetophenone, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone (BTTB), 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl) -1-butanone, 4-benzoyl -4'-methyldiphenyl sulfide, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzyl, or BTTB and xanthene, thioxanthene, coumarin, ketocoumarin, Combination with other dye sensitizer, and the like can be given.

  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, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer and the like are preferable, and 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1 are more preferable. -[4- (Methylthio) phenyl] -2-morpholinopropane-1 ON, 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl) -1-butanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol An oligomer etc. can be mentioned.

The amount of component (F) added in the composition of the present invention is not particularly limited, but the total amount of the composition excluding the organic solvent is preferably 100% by mass, and preferably 0.01 to 10% by mass. . The reason for this is that when the amount added is less than 0.01% by mass, the curing reaction becomes insufficient, and the scratch resistance and the scratch resistance after immersion in an alkaline aqueous solution may decrease. On the other hand, when the addition amount of the photopolymerization initiator exceeds 10% by mass, the refractive index of the cured film increases and the antireflection effect may be lowered.
For these reasons, the addition amount of the photopolymerization initiator is more preferably 0.05 to 10% by mass based on 100% by mass of the total composition excluding the organic solvent, and 0.1 to 7. More preferably, it is 5 mass%.

(G) Organic solvent In the resin composition of the present invention, the components (A) to (F) and the components (H) to (I) are dissolved or dispersed in an organic solvent for the purpose of improving operability. It is preferable.

  Specific examples of the organic solvent are not particularly limited. For example, ketone solvents such as methyl isobutyl ketone (hereinafter sometimes referred to as “MIBK”), methyl ethyl ketone (MEK), and methyl amyl ketone, methanol, Examples include alcohol solvents such as ethanol, isopropanol, and propylene glycol monomethyl ether, and ester solvents such as ether, benzene solvent, and propylene glycol monomethyl ether acetate (PGMEA). These can be used alone or in combination of two or more.

  The organic solvent can be added in an amount of usually 200 to 10,000 parts by mass with respect to 100 parts by mass of the solid content of the composition of the present invention. Here, solid content means the ratio for which all components other than an organic solvent account, when the whole quantity of a resin composition is 100 mass%. The solid content is calculated by calculating the ratio (mass%) between the mass after drying obtained by weighing the resin composition on a hot plate at 120 ° C. for 1 hour and weighing it. Measured.

(H) Silica particles (i) Silica particles Silica particles can be blended with the composition of the present invention for the purpose of improving the scratch resistance of the cured product of the composition, particularly the steel wool resistance. Known silica particles can be used. The shape may be spherical or indefinite, and is not limited to ordinary colloidal silica, and may be hollow particles, porous particles, core-shell type particles, or the like. Silica particles may be surface-treated. The number average particle diameter of the silica particles determined by the dynamic light scattering method is preferably 5 to 100 nm, more preferably 5 to 80 nm, and particularly preferably 5 to 60 nm. The silica particles are preferably colloidal silica having a solid content of 10 to 40% by mass and a pH of 2.0 to 6.5.

The dispersion medium of 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 preferred. These organic solvents can be used alone or in combination of two or more as a dispersion medium.
Examples of commercially available silica particles include Snowtex O (manufactured by Nissan Chemical Industries, Ltd. (number average particle diameter determined by dynamic light scattering method: 7 nm, solid content: 20% by mass, pH 2.7), Snowtex OL) (Number average particle diameter determined by dynamic light scattering method: 15 nm, solid content: 20 mass%, pH 2.5) and the like.

  The silica particles used in the present invention may have an ethylenically unsaturated group (hereinafter referred to as “reactive silica particles”). The method for producing reactive silica particles is not particularly limited. For example, the reactive silica particles can be obtained by reacting the above-described silica particles having a number average particle diameter of 5 to 100 nm with the following organic compound (Hb).

(Ii) Organic compound (Hb)
The organic compound (Hb) used for the production of the reactive silica particles is a compound having an ethylenically unsaturated group, and is preferably an organic compound containing a group represented by the following general formula (11). Further, it includes a [—O—C (═O) —NH—] group, and further includes a [—O—C (═S) —NH—] group and a [—S—C (═O) —NH—] group. It is preferable that at least 1 of these is included. Moreover, it is preferable that this organic compound (Hb) is a compound which has a silanol group in a molecule | numerator, or a compound which produces | generates a silanol group by hydrolysis.

［一般式（１１）中、Ｕは、ＮＨ、Ｏ（酸素原子）又はＳ（イオウ原子）を示し、Ｖは、Ｏ又はＳを示す。］

[In General Formula (11), U represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S. ]

[1] Ethylenically unsaturated group Although there is no restriction | limiting in particular as an ethylenically unsaturated group contained in an organic compound (Hb), For example, an acryloyl group, a methacryloyl group, and a vinyl group can be mentioned as a suitable example.
This ethylenically unsaturated group is a structural unit that undergoes addition polymerization with active radical species.

[2] Group represented by Formula (11) The group [—UC— (V) —NH—] represented by Formula (11) contained in the organic compound is specifically represented by [—O—C ( = O) -NH-], [-O-C (= S) -NH-], [-S-C (= O) -NH-], [-NH-C (= O) -NH-], Six types of [—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 [—UC— (V) —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 and heat resistance to adjacent layers such as materials and high refractive index layers.

[3] Silanol group or group that generates a silanol group by hydrolysis The organic compound (Hb) is preferably a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis. Examples of the compound that generates such a silanol group include compounds in which an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen atom, and the like are bonded to a silicon atom. A compound having a group bonded thereto, that is, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.
The silanol group-generating site of the silanol group or the compound that generates the silanol group is a structural unit that binds to the silica particles by a condensation reaction that occurs following a condensation reaction or hydrolysis.

[4] Preferred Embodiment As a preferred specific example of the organic compound (Hb), for example, a compound represented by the following formula (12) can be mentioned.

In formula (12), R ²¹ and R ²² may be the same or different and each represents a hydrogen atom or an alkyl group or aryl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, Examples thereof include phenyl and xylyl groups. Here, j is an integer of 1 to 3.

^{_{[(R 21 O) j R}} 22 3 - j Si-] The group represented by, for example, trimethoxysilyl groups, triethoxysilyl group, triphenoxysilyl group, methyldimethoxysilyl group, dimethyl methoxy silyl group Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.
R ²³ is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms, and may include a chain, branched, or cyclic structure. Specific examples include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, dodecamethylene and the like.
R ²⁴ 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. Specific examples include a chain polyalkylene group such as hexamethylene, octamethylene, and dodecamethylene; an alicyclic or polycyclic divalent organic group such as cyclohexylene and norbornylene; and 2 such as phenylene, naphthylene, biphenylene, and polyphenylene. Valent aromatic group; and these alkyl group-substituted and aryl group-substituted products. These divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and may contain a polyether bond, a polyester bond, a polyamide bond, and a polycarbonate bond.
R ²⁵ is a (k + 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. K is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5.

  Specific examples of the compound represented by the formula (12) include compounds represented by the following formula (13) or the following formula (14).

［式（１３）及び（１４）中、「Ａｃｒｙｌ」は、アクリロイル基を示す。「Ｍｅ」は、メチル基を示す。］

[In the formulas (13) and (14), “Acryl” represents an acryloyl group. “Me” represents a methyl group. ]

  For the synthesis of the organic compound (Hb) used in the present invention, for example, a method described in JP-A-9-100111 can be used. Preferably, mercaptopropyltrimethoxysilane and isophorone diisocyanate are mixed in the presence of dibutyltin dilaurate and reacted at 60 to 70 ° C. for several hours, then pentaerythritol triacrylate is added, and further at 60 to 70 ° C. for several hours. Produced by reacting to some extent. Typically, a mixture of the compound represented by formula (13) and the compound represented by formula (14) is obtained.

(Iii) Reactive Particles An organic compound (Hb) having a silanol group or a group that generates a silanol group by hydrolysis is mixed with silica particles, hydrolyzed, and bonded together. The ratio of the organic polymer component, that is, the hydrolyzate and condensate of hydrolyzable silane in the obtained reactive particles is usually as a constant value of mass reduction% when the dry powder is completely burned in air. For example, it can be determined by thermal mass spectrometry from room temperature to usually 800 ° C. in air.

  The amount of organic compound (Hb) bound to the silica particles is preferably 0.01% by mass or more, more preferably 0.01% by mass or more, based on 100% by mass of reactive particles (total of silica particles and organic compound (Hb)). 0.1% by mass or more, particularly preferably 1% by mass or more. When the binding amount of the organic compound (Hb) bound to the silica particles is less than 0.01% by mass, the dispersibility of the reactive particles in the composition is not sufficient, and the resulting cured product has transparency and scratch resistance. May not be sufficient. Moreover, the mixing ratio of the silica particles in the raw material during the production of the reactive particles is preferably 5 to 99% by mass, and more preferably 10 to 98% by mass. The content of the silica particles constituting the reactive particles is preferably 65 to 95% by mass of the reactive particles.

  In the composition of the present invention, the blending (content) amount of (H) silica particles and reactive silica particles is 40% by mass or less and 5 to 40% by mass with 100% by mass of the total composition excluding the organic solvent. % Is preferable, and 10 to 40% by mass is more preferable. By containing the component (H) in the range of 5 to 40% by mass, the cured film obtained by curing the resin composition and the scratch resistance of the antireflection film laminate using the cured film can be improved. . As the component (H), silica particles or reactive silica particles can be used alone, or silica particles and reactive silica particles can be mixed and used. In addition, the quantity of a silica particle (H) means solid content, and when the silica particle (H) is used with the form of a dispersion liquid, the quantity of a dispersion medium is not included in the compounding quantity.

(I) Other additives In the range which does not impair the object and effect of the present invention, a compound having one polymerizable unsaturated group in the molecule, an acidic compound (acid catalyst), a compound which generates an acid by heating, a photosensitizer Sensitizer, polymerization inhibitor, polymerization initiator, leveling agent, wettability improver, surfactant, plasticizer, UV absorber, antioxidant, antistatic agent, silane coupling agent, inorganic filler, pigment, It is also preferable to further contain additives such as dyes and slip agents.

(I) Compound having one polymerizable unsaturated group in the molecule For the purpose of improving the adhesion between the cured film and the base, a compound having one polymerizable unsaturated group in the molecule may be optionally added. it can.
Specific examples of such compound (i) include, for example, vinyl group-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam, isobornyl (meth) acrylate, bornyl (meth) acrylate, and tricyclodecanyl (meth). Acrylates, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate and other alicyclic structure-containing (meth) acrylates, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate , Acryloylmorpholine, vinylimidazole, vinylpyridine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate , Ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate , Isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate , Isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isosteary (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol Mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide , N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethyl Ruaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, Examples thereof include hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, and a compound represented by the following formula (15).
_{^{CH 2 = C (R 26)}} -COO (R 27 O) d -Ph-R 28 (15)
Wherein R ²⁶ represents a hydrogen atom or a methyl group, R ²⁷ represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and R ²⁸ represents a hydrogen atom or 1 to 12 carbon atoms, preferably 1 -9 represents an alkyl group, Ph represents a phenylene group, and d represents a number of 0 to 12, preferably 1 to 8.)

  Moreover, as a commercial item of such a compound (i), Aronix M-101, M-102, M-111, M-113, M-114, M-117 (above, Toagosei Co., Ltd. product); Viscoat LA, STA, IBXA, 2-MTA, # 192, # 193 (manufactured by Osaka Organic Chemical Co., Ltd.); NK Ester AMP-10G, AMP-20G, AMP-60G (above, Shin-Nakamura Chemical Co., Ltd.) ); Light acrylate LA, SA, IB-XA, PO-A, PO-200A, NP-4EA, NP-8EA (manufactured by Kyoeisha Chemical Co., Ltd.); FA-511, FA-512A, FA-513A (manufactured by Hitachi Chemical Co., Ltd.) and the like.

(Ii) An acidic compound (acid catalyst) and / or a compound that generates an acid by heating An acidic compound (acid catalyst) and / or a compound that generates an acid by heating functions as a curing catalyst, and (C) radiation irradiation In addition to the compound generating an acid, it can be added as necessary. Acidic compounds are various acids. A compound that generates an acid upon heating is generally referred to as a “thermal acid generator”, and is a salt or ester compound of various acids, which decomposes upon heating to an acidic compound, preferably an organic sulfonic acid, more preferably p- It becomes toluenesulfonic acid. Further, the thermal acid generator is a substance that can accelerate the curing reaction when the coating film of the resin composition is cured by heating, and the heating condition is improved to be milder. It is a substance that can. There is no restriction | limiting in particular as this thermal acid generator, The various acids currently used as a hardening | curing agent for general urea resin, melamine resin, etc. and its salt can be utilized. Specific examples of acidic compounds and thermal acid generators include, for example, various aliphatic sulfonic acids and salts thereof, various aliphatic carboxylic acids and salts thereof such as citric acid, acetic acid, and maleic acid, and various types such as benzoic acid and phthalic acid. Examples thereof include aromatic carboxylic acids and salts thereof, various alkylbenzene sulfonic acids such as p-toluenesulfonic acid and dodecylbenzenesulfonic acid and ammonium salts thereof, various metal salts, phosphoric acid and organic acid phosphates, and the like.

The amount of the component (ii) used in the total solid component amount of 100% by mass excluding the solvent in the resin composition is usually 10% by mass or less, preferably 0.5 to 7% by mass, more preferably 1 It is the range of -5 mass%. If the amount of component (ii) used is too small, sufficient mechanical strength and chemical resistance cannot be obtained. If this ratio is excessive, the component (ii) acts as a plasticizer in the cured film, which is not preferable because the transparency of the coating film is impaired or sufficient mechanical strength cannot be obtained.
In addition, when adding (ii) component, especially an acidic compound, it is preferable to make the composition of this invention into a 2 liquid type. In the case of the one-pack type, the pot life is shortened depending on the storage temperature condition and the like, the applicability may be lowered, and the optical characteristics may be lowered.

(2) Preparation method of curable resin composition The preparation of the composition of the present invention comprises the components (A), (B), (C), (E), (F) and (G) and as necessary. The components (D) and (H) and the component (I) can be added and mixed at room temperature or under heating conditions. Specifically, it can be prepared using a mixer such as a mixer, a kneader, a ball mill, or a three roll. However, when mixing under heating conditions, it is preferable to carry out at or below the decomposition start temperature of the thermal polymerization initiator.

(3) Curing conditions for curable resin composition The composition of the present invention is a combination of a component that is cured by heating and a component that is cured by irradiation with radiation. Accordingly, the curing conditions of the composition can be cured by heating or radiation irradiation, but in order to improve the scratch resistance, which is an effect of the present invention, heating and radiation irradiation can be used in combination. preferable. Furthermore, it is effective to perform radiation irradiation after performing a curing treatment by heating.
Usually, when curing an ethylenically unsaturated group-containing composition by irradiation, it is common to perform irradiation in an inert gas atmosphere such as nitrogen in order to prevent curing inhibition by oxygen, The resin composition of the present invention can give a cured film having excellent scratch resistance even by radiation irradiation in an air atmosphere by performing radiation irradiation after performing a curing treatment by heating.

As conditions for curing by heating, it is preferable to heat at a temperature within a range of 30 to 200 ° C. for 1 to 180 minutes. By heating in this way, an antireflection film having excellent scratch resistance can be obtained more efficiently without damaging the substrate and the like.
For these reasons, it is more preferable to heat at a temperature in the range of 50 to 180 ° C. for 2 to 120 minutes, and further to heat at a temperature in the range of 80 to 150 ° C. for 5 to 60 minutes. preferable.
As for the subsequent irradiation conditions, the exposure dose is preferably set to a value within the range of 0.01 to 10 J / cm ² .
The reason for this is that when the exposure amount is less than 0.01 J / cm ² , curing failure may occur. On the other hand, when the exposure amount exceeds 10 J / cm ² , the curing time may become excessively long. Because there is.
For this reason, the exposure dose is more preferably set to a value in the range of 0.1 to 5 J / cm ² , and more preferably set to a value in the range of 0.3 to 3 J / cm ^2. .

2. Cured film Hereinafter, the cured film of the present invention will be described.
The cured film of the present invention is obtained by curing the resin composition by the above method.
The refractive index of the cured film (the refractive index of Na-D line, measurement temperature 25 ° C.) is preferably 1.45 or less at the wavelength of Na-D line. The refractive index of the cured film may vary depending on the blend amount of the ethylenically unsaturated group-containing fluoropolymer or silica particles, but the refractive index is more preferably 1.44 or less, and 1.43 or less. More preferably. By setting the refractive index of the cured film to 1.45 or less, the reflectance of the antireflection film laminate described later can be reduced.

3. Antireflection Film Laminate Hereinafter, the antireflection film laminate of the present invention (hereinafter sometimes referred to as “antireflection film of the present invention”) will be described.
The antireflection film of the present invention includes a low refractive index layer composed of a cured film obtained by curing the composition of the present invention. Furthermore, the antireflection film of the present invention can typically contain a high refractive index layer, a hard coat layer, an antistatic layer and a substrate under the low refractive index layer.
FIG. 1 shows a schematic diagram of such an antireflection film 10. As shown in FIG. 1, a hard coat layer 14, a high refractive index layer 16, and a low refractive index layer 18 are laminated on a substrate 12.
At this time, the high refractive index layer 16 may be formed directly on the substrate 12 without providing the hard coat layer 14.
Further, an intermediate refractive index layer and an antistatic layer (both not shown) are further provided between the high refractive index layer 16 and the low refractive index layer 18 or between the high refractive index layer 16 and the hard coat layer 14. It may be provided.

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

(I) Refractive index The refractive index of the cured film obtained by curing the resin composition (refractive index of Na-D line, measurement temperature 25 ° C.), that is, the refractive index of the low refractive index film is 1.45 or less. It is preferable. The reason is that when the refractive index of the low refractive index film exceeds 1.45, the antireflection effect may be remarkably lowered.
Therefore, the refractive index of the low refractive index film is more preferably 1.44 or less, and further preferably 1.43 or less.
In the case where a plurality of low refractive index films are provided, at least one of the low refractive index films only needs to have a refractive index value within the above-described range. Therefore, the other low refractive index films exceed 1.45. It may be a value.

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

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

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

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

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

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

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

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to the description of these examples.

(Production Example 1)
Synthesis of hydroxyl-containing fluoropolymer A-1 (component (A)) A stainless steel autoclave with an internal volume of 2.0 L with a magnetic stirrer was sufficiently substituted with nitrogen gas, and then 1200 g of ethyl acetate, perfluoro (propyl vinyl ether) (FPVE) ) 180.8 g, 81.6 g of ethyl vinyl ether (EVE), 99.7 g of hydroxyethyl vinyl ether (HEVE), 3.0 g of lauroyl peroxide, azo group-containing polydimethylsiloxane (VPS1001 (VPS1001 ( (Trade name), 18.0 g manufactured by Wako Pure Chemical Industries, Ltd.) and 120 g nonionic reactive emulsifier (NE-30 (trade name), manufactured by Asahi Denka Kogyo Co., Ltd.), -50 with dry ice-methanol After cooling to 0 ° C., oxygen in the system was removed again with nitrogen gas.
Next, 285.5 g of hexafluoropropylene (HFP) was charged, and the temperature was raised. The pressure when the temperature in the autoclave reached 60 ° C. was 5.6 × 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 30.7%. The obtained polymer solution was poured into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 303 g of a hydroxyl group-containing fluoropolymer A-1. Table 1 shows the charged masses of the monomer and solvent used.
Attached to the obtained hydroxyl group-containing fluoropolymer, the polystyrene-equivalent number average molecular weight by GPC and the fluorine content by the alizarin complexone method were measured. Moreover, the mass ratio and the molar ratio of each monomer component constituting the hydroxyl group-containing fluoropolymer were determined from both ¹ H-NMR and ¹³ C-NMR NMR analysis results, elemental analysis results, and fluorine content. The results are shown in Table 2 together with the correspondence between monomers and structural units. However, the molar ratio made the sum total of structural unit (a)-(c) 100 mol%.

  VPS1001 is an azo group-containing polydimethylsiloxane represented by the above general formula (8) having a number average molecular weight of 70 to 90,000 and a polysiloxane portion having a molecular weight of about 10,000. NE-30 is a nonionic reactive emulsifier wherein n is 9, m is 1 and u is 30 in the general formula (9).

(Production Example 2)
Synthesis of Composition Hb-1 Containing Specific Organic Compound Hb In dry air, 60.0 parts of isophorone diisocyanate was stirred with respect to a solution consisting of 23.0 parts of mercaptopropyltrimethoxysilane and 0.5 parts of dibutyltin dilaurate. However, after dropwise addition at 50 ° C. over 1 hour, the mixture was stirred with heating at 70 ° C. for 3 hours. This is composed of NK ester A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical Co., Ltd.) comprising 60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate. Of these, it is pentaerythritol having a hydroxyl group that is involved in the reaction. After adding 202.0 parts dropwise at 30 ° C. over 1 hour, and stirring with heating at 60 ° C. for 10 hours, an organic compound (Hb) containing a polymerizable unsaturated group was obtained. When the amount of residual isocyanate in the product was analyzed by FT-IR, it was 0.1% or less, indicating that the reaction was almost quantitatively completed. In the infrared absorption spectrum of the product, the 2550 Kaiser absorption peak characteristic of the mercapto group in the raw material and the 2260 Kaiser absorption peak characteristic of the raw material isocyanate compound disappeared, and a new urethane bond and S (C = O) A peak of 1660 Kaiser characteristic of NH-group and a peak of 1720 Kaiser characteristic of acryloxy group were observed, and both an acryloxy group as a polymerizable unsaturated group, -S (C = O) NH-, and a urethane bond were observed. It was shown that an acryloxy group-modified alkoxysilane was produced. As described above, the mixture (Hb-1) containing the compound represented by the formula (13) and the compound represented by the formula (14) contains 285 parts (including 80.8 parts of pentaerythritol tetraacrylate not involved in the reaction). )was gotten.
In the infrared absorption spectrum of the product, the absorption peak of 2550 Kaiser characteristic of the mercapto group in the raw material and the absorption peak of 2260 Kaiser characteristic of the isocyanate group disappeared, and a new [—O—C (═O) A 1660 Kaiser peak characteristic of carbonyl in the —NH—] group and [—S—C (═O) —NH—] group and a 1720 Kaiser peak characteristic of acryloyl group are observed and polymerizable unsaturated. It was shown that a specific organic compound having both an acryloyl group as a group, a [—S—C (═O) —NH—] group, and a [—O—C (═O) —NH—] group was produced. .

(Production Example 3)
Preparation of Reactive Silica Particles 9.0 parts of composition (Hb-1) containing the specific organic compound obtained in Production Example 2, methyl ethyl ketone (MEK) 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), isopropanol 0.2 parts and ion-exchanged water 0.1 parts, After stirring for 3 hours, 1.4 parts of methyl orthoformate was added, and further heated and stirred at the same temperature for 1 hour to obtain a colorless and transparent particle dispersion. 2 g of this particle dispersion was weighed on an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour, and weighed to determine the solid content, which was 35% by mass.
The average particle diameter of the silica-based particles was 20 nm. Here, the average particle diameter was measured with a transmission electron microscope.

(Production Example 4)
Preparation of silica particle-containing composition for hard coat layer In a container shielded from ultraviolet rays, 100 parts (35 parts as solid content) of the reactive silica particle dispersion synthesized in Production Example 3, 65 parts dipentaerythritol hexaacrylate, A composition for a hard coat layer having a uniform solution by stirring 5 parts of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 49 parts of MIBK at 50 ° C. for 2 hours. Got. 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 mass.

(Production Example 5)
Preparation of base material for coating resin composition Single-sided easy-adhesive polyethylene terephthalate (PET) film A4300 (manufactured by Toyobo Co., Ltd., film thickness 188 μm) on the easy-adhesion treated surface of silica-containing hard coat layer prepared in Production Example 4 The composition for coating was applied using a wire bar coater (# 6) and dried in an oven at 80 ° C. for 1 minute to form a coating film. Next, ultraviolet rays were irradiated under a light irradiation condition of 0.9 J / cm ² using a high-pressure mercury lamp in the air to prepare a resin composition coating substrate. When the film thickness of the hard coat layer on this substrate was measured with a stylus type surface shape measuring instrument, it was 3 μm.

(Production Example 6)
Synthesis of Ethylenically Unsaturated Group-Containing Fluoropolymer D-1 (Component (D)) Obtained in Production Example 1 in a 1-liter separable flask equipped with an electromagnetic stirrer, a glass condenser, and a thermometer. 50.0 g of a hydroxyl group-containing fluoropolymer A-1 was charged with 0.01 g of 2,6-di-t-butylmethylphenol and 370 g of methyl isobutyl ketone (MIBK) as a polymerization inhibitor. Stirring was performed until the polymer was dissolved in MIBK and the solution became transparent and uniform.
Next, 14.7 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 D-1 was obtained by maintaining the temperature at 65 ° C. and continuing stirring for 5 hours. 2 g of this solution was weighed in an aluminum dish, dried on a hot plate at 150 ° C. for 5 minutes, and weighed to determine the solid content, which was 15%.

Example 1
(1) Production of curable resin composition As shown in Table 3, 14.0 g of the hydroxyl group-containing fluoropolymer A-1 synthesized in Production Example 1, hexamethoxymethylmelamine (product name: Cymel) as a crosslinkable compound 300, manufactured by Mitsui Cytec) 16.0 g, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate as a polyfunctional (meth) acrylate compound (trade name: NK ester A-TMM-3LM-N, manufactured by Shin-Nakamura Chemical Co., Ltd.) ) 2.80 g, methyl ethyl ketone silica sol (trade name: MEK-ST-L, manufactured by Nissan Chemical Industries, Ltd., silica concentration 30%) 30.7 g (9.20 g as silica particles), methanol dispersion of silica particles (product) Name: methanol silica sol, manufactured by Nissan Chemical Co., Ltd., silica concentration 30%) 3.20 g (as silica particles) 0.96 g), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one as a photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.) .14 g, hydroxyl group-terminated polydimethylsiloxane as an additive (trade name: Silaplane FM0425, manufactured by Chisso Corporation) 0.64 g, MIBK 275.86 g, tert-butanol 190.00 g, glass separable flask equipped with a stirrer And stirred at 23 ° C. for 2 hours. Thereafter, 1.97 g of PAI-101 (manufactured by Midori Kagaku) was added as a photoacid generator, and the mixture was stirred at the same temperature for 30 minutes to obtain a uniform one-pack type resin composition. 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 5%. In addition, 40% of the solvent was tert-butanol, and other than that, MEK brought in from each silica particle dispersion, and MIBK other than methanol were MIBK.

(2) Production of antireflection film laminate On the substrate for coating a resin composition produced in Production Example 5, the curable resin composition obtained in (1) above was applied to a wire bar coater (# 3). It was applied and dried at room temperature (23 ° C.) for 3 minutes. Thereafter, the sample was heated in an oven at 140 ° C. for 1 minute, and then irradiated with ultraviolet rays under a light irradiation condition of 0.6 J / cm 2 in an air atmosphere using a high-pressure mercury lamp to prepare a sample for evaluation. When the film thickness of this cured film layer was estimated by reflectance measurement, it was about 100 nm.

(Examples 2 and 3 and Comparative Examples 1 to 3)
A curable resin composition and a cured film were produced in the same manner as in Example 1 except that the compositions shown in Table 3 were used, and used as evaluation samples.

(Test Example 1): Characteristic evaluation of curable resin composition The pot life of the curable resin composition produced in Example 1 (1) was evaluated as follows. The curable resin composition was stored in a sealed container at 23 ° C. and a relative humidity of 50% for 12 hours. Then, the antireflection film laminated body was produced like Example 1 (2) using the curable resin composition after storage. About the obtained anti-reflective film laminated body, it evaluates similarly to the characteristic evaluation of a cured film which will be described later (Test Example 2), the rate of change in reflectance before and after storage is less than 0.1%, and other than the reflectance The case where the evaluation results of all items in the above were the same as before storage was marked with ◯, and the others were marked with ×.

(Test example 2): Characteristic evaluation of cured film The physical properties of the cured film obtained using the curable resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were measured or evaluated by the measurement methods shown below. did. The obtained results are shown in Table 3.

(A) Appearance The cured films obtained in each of the examples and comparative examples were visually observed to confirm the presence or absence of coating unevenness and repelling, and evaluated according to the following criteria.
○: Coating unevenness and repellency are not recognized.
X: Coating unevenness or repellency is recognized.

(B) Reflectance The back surface of the antireflection film obtained in each Example and Comparative Example was painted with a black spray, and a wavelength of 340 to 700 nm was measured with a spectral reflectance measuring device (MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.). In this range, the reflectance was measured and evaluated from the antireflection film coated surface side. Specifically, the reflectance of the antireflection laminate (antireflection film) at each wavelength was measured using the reflectance of the aluminum deposited film as a reference (100%), and evaluated according to the following criteria.
A: The reflectance is 2.2% or less.
○: Reflectance exceeds 2.2% and is 2.4% or less.
(Triangle | delta): A reflectance exceeds 2.4% and is 2.6% or less.
X: Reflectance exceeds 2.6%.

(C) Scratch resistance test (steel wool resistance test)
The antireflection film produced in each of the examples and comparative examples is made of steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.), Gakushoku type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.). The surface of the cured film was repeatedly abraded under the conditions of a load of 400 g / cm ² and a sliding frequency of 30 times, and the presence or absence of scratches on the surface of the cured film was visually evaluated according to the following criteria.
A: Hardened film peeling or scratches are hardly observed.
○: Slight thin scratches are observed on the cured film.
Δ: Streaky scratches are observed on the entire surface of the cured film.
X: Peeling of the cured film occurs.

(D) Scratch resistance test (eraser resistance test)
The antireflection film produced in each example and comparative example was attached to an eraser testing machine (manufactured by Honko Seisakusho Co., Ltd.) with an eraser (trade name: 1000S, manufactured by Sakura Crepas Co., Ltd.), and the surface of the cured film was loaded. Scratching was repeated under the conditions of 1 kg / cm ² and the number of sliding times of 30, and the presence or absence of scratches on the surface of the cured film was visually evaluated according to the following criteria.
A: Hardened film peeling or scratches are hardly observed.
○: Slight thin scratches are observed on the cured film.
Δ: Streaky scratches are observed on the entire surface of the cured film.
X: Peeling of the cured film occurs.

(E) Chemical resistance test 0.75N sodium hydroxide aqueous solution was dripped on the cured film (sample for evaluation) obtained by each Example and the comparative example in the environment of room temperature 23 degreeC and humidity 50% RH. . After 30 minutes, an aqueous sodium hydroxide solution was blotted using a non-woven fabric made of cellulose (trade name: Bencot S-2, Asahi Kasei Kogyo Co., Ltd.). The coating film after the test was visually evaluated according to the following criteria.
○: No change in the appearance of the coating film.
(Triangle | delta): A dripping trace is seen in a coating-film external appearance.
X: Peeling of the coating film is observed at the dropping point.

The following compounds were used in Table 3.
Hydroxyl group-containing fluoropolymer A-1: Production Example 1
Cymel 300: Hexamethoxymethylmelamine, manufactured by Mitsui Cytec Co., Ltd. Silica particles (MEK-ST-L): Methyl ethyl ketone silica sol, manufactured by Nissan Chemical Industries, Ltd., silica concentration 30%
Silica particles (methanol silica sol): methanol dispersion of silica particles, manufactured by Nissan Chemical Co., Ltd., silica concentration 30%
PAI-101: manufactured by Midori Chemical Co., Ltd., photoacid generator SP-095: manufactured by Asahi Denka Kogyo Co., Ltd., photoacid generator Cat4040 (acid catalyst): isopropanol solution of aromatic sulfonic acid, manufactured by Nippon Cytec Co., Ltd., active ingredient concentration 40%
NACURE 2500: manufactured by Enomoto Kasei Co., Ltd., thermal acid generator Silaplane FM0425: hydroxyl-terminated polydimethylsiloxane, manufactured by Chisso Corporation Ethylenically unsaturated group-containing fluoropolymer D-1: Production Example 6
Pentaerythritol triacrylate and pentaerythritol tetraacrylate: NK ester A-TMM-3LM-N, manufactured by Shin-Nakamura Chemical Co., Ltd., consisting of 60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, manufactured by Ciba Specialty Chemicals

  From the results in Table 3, it can be seen that the curable resin compositions of Examples 1 and 3 containing only the photoacid generator are excellent in pot life and at the same time, the properties of the cured film. In Example 2 in which the photoacid generator and the acid catalyst were used in combination, the pot life was shortened although the properties of the cured film were excellent. On the other hand, in Comparative Example 1 using only the acid catalyst, although the properties of the cured film are not impaired, it can be seen that the pot life is remarkably deteriorated because it contains an acidic compound. In Comparative Example 2 using only the thermal acid generator, the pot life is excellent, but the characteristics of the cured film are not maintained. In Comparative Example 3 containing no curing agent, the pot life is good, but the degree of cure of the cured film does not increase, and it can be seen that the scratch resistance and chemical resistance are reduced.

The curable resin composition of the present invention is excellent in coating property, chemical resistance, refractive index and particularly scratch resistance, and is particularly useful as a material for forming a low refractive index layer of an antireflection film laminate.
The curable resin composition of the present invention can also be used as a surface coating material for various optical materials.
According to the present invention, a one-pack type heat / radiation curable resin composition can be provided.

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

DESCRIPTION OF SYMBOLS 10 Antireflection film 12 Base material 14 Hard-coat layer 16 High refractive index layer 18 Low refractive index layer

Claims (11)

The following ingredients,
(A) Hydroxyl group-containing fluorine-containing polymer (B) Thermosetting compound (C) Compound that generates acid upon irradiation with radiation (E) Compound having two or more (meth) acryloyl groups (F) Upon irradiation with radiation Compound generating active species (G) Organic solvent
(Ii) a curable resin composition containing an acid catalyst and / or a thermal acid generator ,
The (A) hydroxyl group-containing fluoropolymer is represented by the structural unit (a) represented by the following formula (1), the structural unit (b) represented by the following formula (2), and the following formula (3). The structural unit (c) is contained, and the structural units (a), (b) and (c) are added in an amount of (a) 20 to 70 mol% and (b) 5 to 70 mol with respect to 100 mol% in total. % And (c) a hydroxyl group-containing fluoropolymer contained in a proportion of 5 to 70 mol%,
The (B) thermosetting compound is one or more compounds selected from an amino compound and a hydroxyl group-containing compound,
The content of the compound that generates an acid upon irradiation with the (C) radiation is 1 to 10% by mass when the total amount of the composition excluding the organic solvent (G) is 100% by mass,
(Ii) A curable resin composition in which the content of the acid catalyst and / or the thermal acid generator is 0 to 5% by mass when the total amount of the composition excluding the organic solvent (G) is 100% by mass.

[In General Formula (1), R ¹ represents a fluorine atom, a fluoroalkyl group, or a group represented by —OR ² (R ² represents an alkyl group or a fluoroalkyl group)]

[In General Formula (2), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, a group represented by — (CH ₂ ) x —OR ⁵ or —OCOR ⁵ (R ⁵ represents an alkyl group, or A glycidyl group, x represents a number of 0 or 1), a carboxyl group, or an alkoxycarbonyl group]

[In General Formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a hydroxyalkyl group, and v represents a number of 0 or 1] The (B) thermosetting compound is at least one selected from melamine, alkylated melamine, methylolated melamine, and alkoxylated methylmelamine; urea, polymethylolated urea, alkoxylated methylurea, methylolated 2. The curable resin composition according to claim 1, wherein the curable resin composition is one or more selected from ureon and one or more urea compounds selected from alkoxylated methyluron; benzoguanamine compounds; and glycoluril compounds. The (A) hydroxyl group-containing fluoropolymer contains 0.1 to 10 mole parts of the following structural unit (d) with respect to 100 mole parts in total of the structural units (a), (b) and (c). The curable resin composition according to claim 1 or 2 .
(D) Structural unit represented by the following general formula (4)

[In General Formula (4), R ^{10 to} R ¹³ represent a hydrogen atom, an alkyl group, or a cyano group, R ^{14 to} R ¹⁷ represent a hydrogen atom or an alkyl group, and p and q are numbers of 1 to 6, s and t are numbers from 0 to 6, and y is a number from 1 to 200. ] The (A) hydroxyl group-containing fluoropolymer contains 0.1 to 5 mole parts of the following structural unit (e) with respect to 100 mole parts in total of the structural units (a), (b) and (c). Curable resin composition in any one of Claims 1-3 .
(E) Structural unit represented by the following general formula (5)

[In General Formula (5), R ¹⁸ represents a group represented by the following Formula (6)]

[In General Formula (6), n is a number from 1 to 20, m is a number from 0 to 4, and u is a number from 3 to 50] The curable resin composition according to any one of claims 1 to 4, wherein the compound (C) that generates an acid upon irradiation with radiation is an acid generator that generates an organic sulfonic acid upon irradiation with UV. The (E) a compound having two or more (meth) acryloyl group is a compound having three or more (meth) acryloyl group, the curable resin composition according to any one of claims 1 to 5 object. Furthermore, (H) The curable resin composition of any one of Claims 1-6 containing a silica particle. The curable resin composition according to claim 7 , wherein the (H) silica particles have an ethylenically unsaturated group. A cured film having a refractive index of Na-D line of 1.45 or less, obtained by curing the curable resin composition according to any one of claims 1 to 8 . The manufacturing method of the cured film which hardens the coating film of the curable resin composition of any one of Claims 1-8 by the process of heating and then irradiating a radiation. An antireflection film laminate comprising the cured film according to claim 9 .

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