JP2007182530A - Curable composition, cured film, reflection-preventing laminate film and method for producing the cured film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition giving a cured film excellent in scratch resistance and chemical resistance, and cured film and reflection-preventing film obtained by curing the composition. <P>SOLUTION: This curable composition containing the following components: (A) a hydroxy and/or ethylenically unsaturated group-containing and fluorine-containing polymer, (B) a thermosetting compound, (C) an acidic compound or a compound forming an acid by heating, (E) a compound having ≥2 (meth)acryloyl groups, (F) a compound forming an active species by the irradiation of an active energy beam and (G) an organic solvent is provided by containing ≥3 wt.% component (B) and ≥3 wt.% component (E) based on the total of components by excluding the component (G), as 100 wt.%. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a curable composition, a cured film made of a cured product of the curable composition, and an antireflection film including a low refractive index layer made of the cured 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, coating properties, 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 it is bonded to the polarizing plate. It is necessary to saponify with an aqueous solution.
Accordingly, in applications of liquid crystal display panels, there is a demand for an antireflection film excellent in alkali resistance, particularly in 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 weather resistance, there was a problem that scar resistance and durability were poor.

  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 fluorine-containing vinyl polymer, an amount of isocyanate sufficient to react all the hydroxyl groups of the hydroxyl group-containing fluorine-containing polymer. An unreacted hydroxyl group was positively left in the polymer without using a group-containing unsaturated compound.
For this reason, the 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 the scratch resistance were not sufficient.
In addition, curing of a composition containing a compound having an ethylenically unsaturated group by irradiation with radiation does not provide sufficient scratch resistance unless performed under an inert gas atmosphere such as nitrogen gas. In curing, it was necessary to install a device for supplying an inert gas to the radiation irradiation part.

  In view of the above situation, the present invention provides a curable composition that provides a cured film excellent in scratch resistance and chemical resistance, a cured film obtained by curing the cured composition, an antireflection film, and a method for producing the cured film. For the purpose.

  In order to achieve the above object, the present inventors have conducted intensive research, a fluorine-containing polymer having an ethylenically unsaturated group and / or a fluorine-containing polymer having a hydroxyl group, a thermosetting compound, a curing catalyst, A cured film obtained by curing a curable composition containing a (meth) acrylate compound containing two or more (meth) acryloyl groups, a radical photopolymerization initiator, and an organic solvent has a scratch resistance, The present invention has been completed by finding that it is excellent in workability and durability.

［一般式（１）中、Ｒ¹はフッ素原子、フルオロアルキル基、又は−ＯＲ²で表される基（Ｒ²はアルキル基、又はフルオロアルキル基を示す）を示す］

［一般式（２）中、Ｒ³は水素原子又はメチル基を、Ｒ⁴はアルキル基、−(ＣＨ₂)_x−ＯＲ⁵若しくは−ＯＣＯＲ⁵で表される基（Ｒ⁵はアルキル基、又はグリシジル基を、ｘは０又は１の数を示す）、カルボキシル基、又はアルコキシカルボニル基を示す］

［一般式（３）中、Ｒ⁶は水素原子、又はメチル基を、Ｒ⁷は水素原子、又はヒドロキシアルキル基を、ｖは０又は１の数を示す］
３．前記（Ａ）水酸基含有含フッ素共重合体が、上記構造単位（ａ）、（ｂ）及び（ｃ）の合計１００重量部に対して、下記構造単位（ｄ）０．１〜１０重量部を含むことを特徴とする上記２に記載の硬化性組成物。
（ｄ）下記一般式（４）で表される構造単位。

［一般式（４）中、Ｒ¹⁰〜Ｒ¹³は水素原子、アルキル基、又はシアノ基を示し、Ｒ¹⁴〜Ｒ¹⁷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、上記構造単位（ａ）、（ｂ）及び（ｃ）の合計１００重量部に対して、下記構造単位（ｅ）０．１〜３０重量部を含む上記２又は３に記載の硬化性組成物。
（ｅ）下記一般式（５）で表される構造単位。

［一般式（５）中、Ｒ¹⁸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（Ａ）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、
前記水酸基含有含フッ素重合体と、
を反応させて得られるものである、上記１〜４のいずれかに記載の硬化性組成物。
６．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５に記載の硬化性組成物。
７．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１〜６のいずれかに記載の硬化性組成物。
８．さらに、（Ｈ）シリカ粒子を含有する、上記１〜７のいずれかに記載の硬化性組成物。
９．前記（Ｈ）シリカ粒子が、エチレン性不飽和基を有する、上記８に記載の硬化性組成物。
１０．上記１〜９のいずれかに記載の硬化性組成物を硬化させてなる硬化膜。
１１．上記１〜９のいずれかに記載の硬化性組成物の塗布膜を、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。
１２．上記１０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 composition, a cured film comprising the same, and an antireflection film laminate are provided.
1. The following ingredients,
(A) a fluorine-containing polymer containing a hydroxyl group and / or an ethylenically unsaturated group,
(B) a thermosetting compound,
(C) an acidic compound and / or a compound that generates an acid by heating,
(E) a compound having two or more (meth) acryloyl groups,
(F) a curable composition containing a compound that generates active species upon irradiation with active energy rays, and (G) an organic solvent,
When the total of the components excluding the component (G) is 100% by weight,
A curable composition containing 3% by weight or more of the component (B) and 3% by weight or more of the component (E).
2. The (A) hydroxyl group-containing fluoropolymer has the following structural units (a), (b) and (c) as a total of 100 mol%: (a) 20 to 70 mol%, (b) 5 Comprising -70 mol% and (c) 5-70 mol%, and
The curable composition according to 1 above, wherein the polystyrene-reduced number average molecular weight measured by gel permeation chromatography is 10,000 to 500,000.
(A) A structural unit represented by the following general formula (1).
(B) A structural unit represented by the following general formula (2).
(C) A 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 is a hydrogen atom or a methyl group, R ⁴ is an alkyl group, a group represented by — (CH ₂ ) _x —OR ⁵ or —OCOR ⁵ (R ⁵ is 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 fluorine-containing copolymer contains 0.1 to 10 parts by weight of the following structural unit (d) with respect to 100 parts by weight of the total of the structural units (a), (b) and (c). 3. The curable composition as described in 2 above, which comprises the curable composition.
(D) A structural unit represented by the following general formula (4).

[In the general formula (4), R ¹⁰ ~R ¹³ represents a hydrogen atom, an alkyl group, or a cyano group, R ¹⁴ to R ¹⁷ represents a hydrogen atom or an alkyl group, p, q is a number from 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 30 parts by weight of the following structural unit (e) with respect to a total of 100 parts by weight of the structural units (a), (b) and (c). 4. The curable composition according to 2 or 3 above.
(E) A 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. The (A) ethylenically unsaturated group-containing fluoropolymer is
A compound containing one isocyanate group and at least one ethylenically unsaturated group;
The hydroxyl group-containing fluoropolymer,
The curable composition according to any one of 1 to 4 above, which is obtained by reacting.
6). 6. The curable composition according to 5 above, wherein the compound containing one isocyanate group and at least one ethylenically unsaturated group is 2- (meth) acryloyloxyethyl isocyanate.
7). The curable composition according to any one of 1 to 6 above, wherein the compound (E) having two or more (meth) acryloyl groups is a compound having three or more (meth) acryloyl groups.
8). Furthermore, (H) The curable composition in any one of said 1-7 containing a silica particle.
9. 9. The curable composition according to 8 above, wherein the (H) silica particles have an ethylenically unsaturated group.
10. The cured film formed by hardening | curing the curable composition in any one of said 1-9.
11. The manufacturing method of a cured film which hardens the coating film of the curable composition in any one of said 1-9 by the process of heating and then irradiating a radiation.
12 11. An antireflection film laminate comprising the cured film as described in 10 above.

According to the curable composition of the present invention, a curable composition that provides a cured film having excellent scratch resistance and chemical resistance can be obtained.
The curable 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.
The curable composition of the present invention uses a hydroxyl group-containing fluorine-containing copolymer and / or an ethylenically unsaturated group-containing fluorine-containing polymer, so that it can be cured at a low temperature in a short time, and radiation in the atmosphere. Curing by irradiation is possible.
According to the present invention, an antireflection laminate having a cured film having excellent scratch resistance and chemical resistance can be obtained.

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

1. Curable composition The curable composition of the present invention (hereinafter sometimes referred to as the composition of the present invention) is (A) a hydroxyl group-containing fluoropolymer and / or an ethylenically unsaturated group-containing fluoropolymer, (B) a thermosetting compound, (C) an acidic compound and / or a compound that generates an acid upon heating, (E) a compound having two or more (meth) acryloyl groups, (F) activated by irradiation with active energy rays A seed generating compound, and (G) an organic solvent.

(1) Component of curable composition (A) Hydroxyl group-containing fluoropolymer and / or ethylenically unsaturated group-containing fluoropolymer A fluoropolymer is a polymer having a carbon-fluorine bond in the molecule. The fluorine content is preferably 30% by weight or more. Here, the fluorine content is a value measured by the alizarin complexone method.
The hydroxyl group-containing fluoropolymer (A1) is a fluoropolymer having a hydroxyl group in the molecule, and the ethylenically unsaturated group-containing fluoropolymer (A2) is an ethylenically unsaturated group in the molecule. It is a fluorine-containing polymer.

(A1) Hydroxyl group-containing fluoropolymer The (A1) hydroxyl group-containing fluoropolymer used in the present invention is preferably a copolymer of at least the following structural units (a), (b), and (c). Further, the total amount of the structural units (a), (b) and (c) in the weight of the copolymer is preferably 70% by weight or more.

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

［一般式（１）中、Ｒ¹はフッ素原子、フルオロアルキル基、又は−ＯＲ²で表される基（Ｒ²はアルキル基、又はフルオロアルキル基を示す）を示す］
上記一般式（１）において、Ｒ¹及びＲ²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、Ｒ²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 represented by 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 C 1-6 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), (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether); Perfluoro (alkoxyalkyl vinyl ether) s such as perfluoro (propoxypropyl vinyl ether) These may be used alone or in combination of two or more.
Among these, hexafluoropropylene and perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether) are more preferable, and a combination of these is more preferable.

The content of the structural unit (a) is 20 to 70 mol% when the total of the structural units (a), (b) and (c) in the hydroxyl group-containing fluoropolymer is 100 mol%. is there. The reason for this is that when the content is less than 20 mol%, it may be 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. If the ratio exceeds 70 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent, transparency, or adhesion to the substrate may be lowered.
For this reason, the content of the structural unit (a) is 25 to 65 mol% when the total of the structural units (a), (b) and (c) is 100 mol%. Is more preferable, and it is more preferable to set it as 30 to 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、Ｒ³は水素原子又はメチル基を、Ｒ⁴はアルキル基、−(ＣＨ₂)_x−ＯＲ⁵若しくは−ＯＣＯＲ⁵で表される基（Ｒ⁵はアルキル基、又はグリシジル基を、ｘは０又は１の数を示す）、カルボキシル基、又はアルコキシカルボニル基を示す］
一般式（２）において、Ｒ⁴又はＲ⁵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 is a hydrogen atom or a methyl group, R ⁴ is an alkyl group, a group represented by — (CH ₂ ) _x —OR ⁵ or —OCOR ⁵ (R ⁵ is 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% when the sum total of the structural units (a), (b), and (c) in a hydroxyl-containing fluoropolymer is 100 mol%. is there. This is because when the content is less than 5 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced, whereas when 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 this reason, when the content of the structural unit (b) is 100 mol% in the total of the structural units (a), (b) and (c) in the hydroxyl group-containing fluoropolymer, It is more preferable to set it as 5-65 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、Ｒ⁶は水素原子、又はメチル基を、Ｒ⁷は水素原子、又はヒドロキシアルキル基を、ｖは０又は１の数を示す］
一般式（３）において、Ｒ⁷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.
In addition to the above, the hydroxyl group-containing vinyl monomer includes 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone (meth) acrylate, and polypropylene. Glycol (meth) acrylate or the like can be used.

The content of the structural unit (c) is 5 to 70 mol% when the total of the structural units (a), (b) and (c) in the hydroxyl group-containing fluoropolymer is 100 mol%. It is preferable to do. This is because when the content is less than 5 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced, whereas when 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 this reason, when the content of the structural unit (c) is 100 mol% when the total of the structural units (a), (b) and (c) in the hydroxyl group-containing fluoropolymer is 100 mol%, It is more preferable to set it as 5-65 mol%, and it is still more preferable to set it as 5-60 mol%.

[4] Structural unit (d)
Further, the hydroxyl group-containing fluoropolymer preferably further comprises the above structural unit (d). The structural unit (d) is a structural unit represented by the following general formula (4).

[In the general formula (4), R ¹⁰ ~R ¹³ represents a hydrogen atom, an alkyl group, or a cyano group, R ¹⁴ to R ¹⁷ represents a hydrogen atom or an alkyl group, p, q is a number from 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、Ｒ¹⁰〜Ｒ¹³、Ｒ¹⁴〜Ｒ¹⁷、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). ]

The content of the structural unit (d) is 0.1 to 10 parts by weight with respect to a total of 100 parts by weight of the structural units (a), (b) and (c) in the hydroxyl group-containing fluoropolymer. It is preferable to do. The reason for this is that when the content is less than 0.1 parts by weight, the surface slipperiness of the cured coating film is reduced, and the scratch resistance of the coating film may be reduced. When the amount exceeds 10 parts by weight, 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 set to 0. 0 with respect to 100 parts by weight of the total of the structural units (a), (b) and (c) in the hydroxyl group-containing fluoropolymer. 5-8 parts by weight is more preferable, and 0.5-6 parts by weight is even more preferable.

[5] Structural unit (e)
Moreover, it is 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、Ｒ¹⁸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 those in general formula (6) above]

The content of the structural unit (e) is 0.1 to 30 parts by weight with respect to a total of 100 parts by weight of the structural units (a), (b) and (c) in the hydroxyl group-containing fluoropolymer. It is preferable to do. The reason for this is that when the content is 0.1 parts by weight or more, the solubility of the hydroxyl group-containing fluoropolymer in the solvent is improved, while if the content is 30 parts by weight or less, the curable composition This is because the adhesiveness does not increase excessively, the handling becomes easy, and the moisture resistance does not deteriorate even when used as a coating material.
For this reason, the content of the structural unit (e) is set to 0.1% relative to the total of 100 parts by weight of the structural units (a), (b) and (c) in the hydroxyl group-containing fluoropolymer. The amount is more preferably 5 to 25 parts by weight, and further preferably 1 to 20 parts by weight.

[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. -500,000 are preferred. The reason for this is that when the number average molecular weight is less than 5,000, the mechanical strength of the hydroxyl group-containing fluoropolymer may be lowered. On the other hand, when the number average molecular weight exceeds 500,000, it will be described later. This is because the viscosity of the curable 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.

(A2) Ethylenically unsaturated group-containing fluoropolymer The ethylenically unsaturated group-containing fluoropolymer used in the present invention reduces the refractive index of a cured film obtained by curing a curable composition, and the cured It is used for enhancing the scratch resistance of the film and the antireflection film laminate using the 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 (A1) 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 contents as the above-mentioned (A1) hydroxyl group-containing fluoropolymer, it is not described in detail here. As the hydroxyl group-containing fluoropolymer used for the production of (A2), the same polymer as the component (A1) can be used, or polymers having different compositions and molecular weights can be used.

(Ii) A compound containing one isocyanate group and at least one ethylenically unsaturated group A compound containing one isocyanate group and at least one ethylenically unsaturated group is a hydroxyl group-containing fluorine-containing compound. By reacting with a hydroxyl group of the polymer (the structural unit (c) has a hydroxyl group), (A2) 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 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-isocyanatoethyl) fumarate, 6- Sopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, tetramethylxylylene diisocyanate, 2,5 (or 6) -bis ( One type alone or a combination of two or more types such as isocyanatomethyl) -bicyclo [2.2.1] heptane may be mentioned.
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. trade name HEA, Nippon Kayaku Co., Ltd. trade name KAYARAD DPHA, PET-30, manufactured by Toagosei Co., Ltd. Product names 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.

In the composition of the present invention, the blending amount of the (A) fluoropolymer (component (A1) and / or (A2)) is 10 to 75% by weight based on the total amount of the composition excluding the organic solvent. It is preferably 20 to 65% by weight, more preferably 25 to 60% by weight. By being 10 to 75% by weight, the scratch resistance of the cured film obtained by curing the composition of the present invention is improved.
In addition, the compounding quantity of a component (A), when using either a hydroxyl-containing fluorine-containing polymer (A1) or an ethylenically unsaturated group-containing fluorine-containing polymer (A2), the amount of either This means that when the hydroxyl group-containing fluoropolymer (A1) and the ethylenically unsaturated group-containing fluoropolymer (A2) are used in combination, the total amount thereof is meant.

(B) Thermosetting Compound In the composition of the present invention, the thermosetting compound (hereinafter sometimes referred to as “component (B)”) is heated in the presence of an acidic catalyst, whereby the compound itself or other It reacts with the compound and cures. The thermosetting component may be included by simply mixing in the curable composition, or the reaction product obtained by reacting all of the hydroxyl group-containing fluoropolymer and the thermosetting compound or only a part of them may be reacted. You may include the thing of the state. 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 particularly, good storage stability is obtained in the curable composition. In view of the point and good reactivity, alkoxylated methylmelamine is preferable. There are no particular restrictions on the methylolated melamine and 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 3 to 40% by weight, more preferably 5 to 40%, based on 100% by weight of the total composition excluding the organic solvent. The range is 10% by weight, more preferably 10 to 40% by weight. If the amount of the thermosetting compound used is too small, the durability of the thin film formed from the resulting curable composition may be insufficient. If the amount exceeds 40% by weight, the above-mentioned hydroxyl group-containing fluorine-containing weight is insufficient. In the reaction with the coalescence, it is difficult to avoid gelation, and the cured product may become brittle.

  The reaction between the fluoropolymer and the thermosetting compound can be achieved, for example, by adding the thermosetting compound to an organic solvent solution in which the fluoropolymer is dissolved, and uniformizing the reaction system by heating, stirring, etc. for an appropriate time. Just do it. 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 the heating temperature is less than 30 ° C, the reaction proceeds very slowly. If the heating temperature exceeds 150 ° C, in addition to the intended reaction, a crosslinking reaction is caused by the reaction between methylol groups and alkoxylated methyl groups in the thermosetting compound. Is generated and a gel is formed, which 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.

  For the reaction between the fluoropolymer and the thermosetting compound, it is preferable to use an organic solvent, for example, the same organic solvent used in the production of the fluoropolymer. In the present invention, the reaction solution obtained with the fluoropolymer and the thermosetting compound thus obtained can be used as it is as the solution of the curable composition, and various additives are blended as necessary. It can also be used.

(C) An acidic compound and / or a compound that generates an acid upon heating An acidic compound used in the present invention and / or a compound that generates an acid upon heating (hereinafter sometimes referred to as “component (C)”) is used as a curing catalyst. Function. Acidic compounds are various acids. A compound that generates an acid by heating is generally called a “thermal acid generator”, and is a salt or ester compound of various acids, which decomposes to become an acidic compound by heating. The thermal acid generator is a substance that can accelerate the curing reaction when the coating film of the curable composition is heated and cured, and the heating condition is improved to be milder. It is a substance that can do. 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 alkylbenzenesulfonic 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 component (C) in the composition of the present invention is usually in the range of 0.1 to 10% by weight, preferably 0.5 to 7% by weight, with the total solid content excluding the solvent being 100% by weight. %, More preferably in the range of 1 to 5% by weight. If the amount of component (C) used is too small, it is not preferable because sufficient mechanical strength and chemical resistance cannot be obtained. When this ratio is excessive, the component (C) acts as a plasticizer in the cured film, which is not preferable because transparency of the coating film is impaired or sufficient mechanical strength cannot be obtained.

(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 curable composition. It is a component that imparts radiation curability to a product, and is used for enhancing the scratch resistance of a cured film obtained by curing a curable 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 two or more (meth) acryloyl groups in the molecule. Examples of this include neopentyl glycol di (meth) acrylate, 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, U made by Shin-Nakamura Chemical Co., Ltd. 6HA, U-15HA, as well as alone or in combinations of two or more such compounds represented by the following formula (10).
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. ]

  The polyfunctional (meth) acrylate compound is preferably a (meth) acrylate compound having three or more (meth) acryloyl groups. By setting it as such an aspect, the abrasion resistance of the cured film obtained by hardening | curing a curable composition and an antireflection film laminated body using the same can be improved especially.

  The amount of component (E) in the composition of the present invention is preferably 3 to 25% by weight, more preferably 5 to 20% by weight, with the total amount of the composition excluding the organic solvent being 100% by weight. By being 3 to 25% by weight, the scratch resistance of the cured film obtained by curing the composition of the present invention is improved.

(F) Compound that generates active species upon irradiation with active energy rays In the curable composition of the present invention, a compound that generates active species upon irradiation with active energy rays (hereinafter sometimes referred to as “component (F)”). .) Is added. Such a compound is used for efficiently curing the curable composition.

Examples of the compound that generates active species upon irradiation with active energy rays (hereinafter sometimes referred to as “photopolymerization initiator”) include photo radical generators that generate radical species as active species.
The active energy ray is defined as an energy ray capable of decomposing a compound that generates active species to generate active species. Examples of such active energy rays include optical energy rays such as visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, and γ rays. However, it is preferable to use ultraviolet rays 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.

Although the compounding quantity of (F) component in the composition of this invention is not restrict | limited in particular, It is preferable to set it as 0.01-10 weight% by making the composition whole quantity except an organic solvent into 100 weight%. This is because when the amount added is less than 0.01% by weight, 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 weight, the refractive index of the cured film increases and the antireflection effect may be lowered.
For these reasons, the blending amount of the photopolymerization initiator is more preferably 0.05 to 10% by weight, with the total amount of the composition excluding the organic solvent being 100% by weight. More preferably, it is 5% by weight.

(G) Organic solvent The curable composition of the present invention preferably has the components (A) to (F) dissolved or dispersed in an organic solvent for the purpose of improving operability. Moreover, it is preferable that the below-mentioned (H) silica particle which can be added arbitrarily is melt | dissolved or disperse | distributed to the organic solvent.

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

Hereafter, the component added to the composition of this invention as needed is demonstrated.
(H) Silica Particles Silica particles can be added to the curable composition of the present invention for the purpose of improving the scratch resistance of the cured product of the curable composition, particularly the steel wool resistance.
(I) Silica particles As the silica particles, known particles can be used, and the shape thereof is not limited to a spherical shape, and may be an irregular particle. Also, the form is not particularly limited, and may be hollow particles, porous particles, core-shell type particles, or the like, as long as it is spherical, without being limited to ordinary colloidal silica. Further, 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 weight and a pH of 2.0 to 6.5.

The dispersion medium for 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, dimethyl Examples include amides such as acetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and γ-butyrolactone; and organic solvents such as ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in admixture of two or more as a dispersion medium.
As a commercial product of particles mainly composed of silica, for example, Snowtex O (manufactured by Nissan Chemical Industries, Ltd.) (number average particle diameter determined by dynamic light scattering method 7 nm, solid content 20% by weight, pH 2.7) ), Snowtex OL (number average particle diameter determined by dynamic light scattering method: 15 nm, solid content: 20% by weight, 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.

Examples of the group represented by [(R ²¹ O) _j R ²² _3-j Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.
R 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 hydrolyzate and condensate of the organic polymer component, ie hydrolyzable silane, in the resulting reactive particles is usually as a constant value of weight loss% when the dry powder is completely burned in air. For example, it can be determined by thermogravimetric analysis from room temperature to usually 800 ° C. in air.

  The amount of the organic compound (Hb) bound to the silica particles is preferably 0.01% by weight or more, more preferably 0.01% by weight or more, based on 100% by weight of the reactive particles (total of silica particles and organic compound (Hb)). 0.1% by weight or more, particularly preferably 1% by weight or more. When the amount of the organic compound (Hb) bonded to the silica particles is less than 0.01% by weight, 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. Further, the blending ratio of the silica particles in the raw material during the production of the reactive particles is preferably 5 to 99% by weight, and more preferably 10 to 98% by weight. The content of the silica particles constituting the reactive particles is preferably 65 to 95% by weight of the reactive particles.

  The compounding amount of the component (H) (silica particles and / or reactive silica particles) in the composition of the present invention is preferably 10 to 40% by weight, with the total amount of the composition excluding the organic solvent being 100% by weight, More preferred is 25% by weight. By being 10 to 40 weight%, the scratch resistance of the cured film obtained by curing the curable composition and 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 used in combination. In addition, the compounding quantity of (H) component means solid content, and when the (H) component is used with the form of a dispersion liquid, the quantity of a dispersion medium is not included in the compounding quantity.

(I) Compound having one polymerizable unsaturated group in the molecule For the purpose of improving the adhesion between the cured film and the substrate, a compound having one polymerizable unsaturated group in the molecule (hereinafter referred to as “(I) In some cases, “component” may be optionally added.
Specific examples of component (I) include, for example, vinyl group-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam, isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, Cyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate and other alicyclic structure-containing (meth) acrylate, 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 ( 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, isostearyl (meth) acrylate Relate, 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, dimethylaminoethyl (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.)

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

The blending amount of the component (I) in the composition of the present invention is not particularly limited, but is preferably 10% by weight or less based on 100% by weight of the total composition excluding the organic solvent. The reason for this is that if the amount of component (I) exceeds 10% by weight, the refractive index of the cured film increases and the antireflection effect may decrease, or the strength of the cured film may decrease. .
For these reasons, the amount of component (I) added is more preferably 7.5% by weight or less, with the total amount of the composition excluding the organic solvent being 100% by weight, more preferably 5% by weight or less. Is more preferable.

(J) Other additives As long as the object and effect of the present invention are not impaired, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, a surfactant, a plasticizer, and an ultraviolet absorber It is also preferable to further contain additives such as an agent, an antioxidant, an antistatic agent, a silane coupling agent, an inorganic filler, a pigment, and a dye.

(2) Preparation method of curable composition The curable composition of this invention is the composition containing the said (A)-(C) component, said (D)-(F) component, and as needed ( Each of the compositions containing the component H) may be prepared and mixed, or the components (A) to (F) and the component (H), component (I) and / or addition as necessary. It can also be prepared by adding each agent and mixing 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 component (C).

  In the composition of the present invention, (B) the thermosetting compound and (E) the polyfunctional (meth) acrylate compound must be blended in an amount of 3% by weight or more, with the total amount of the composition excluding the solvent being 100% by weight. is there. When the blending amount of these components is 3% by weight or more, both the scratch resistance and chemical resistance characteristics of the resulting cured film are good.

(3) Curing conditions for curable 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 active energy rays (radiation). Accordingly, the curing conditions of the curable 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 are used in combination. It is 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 curable 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 .
This is because when the exposure dose is less than 0.01 J / cm ² , curing failure may occur. On the other hand, when the exposure dose exceeds 10 J / cm ² , the curing time may become excessively long. Because there is.
Moreover, such a reason, the exposure amount is more preferably within a range of 0.1~5J / cm ^2, further preferably a value within the range of 0.3~3J / 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 curable 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. Hereinafter, the antireflection film laminate of the present invention (hereinafter sometimes referred to as “antireflection film”) 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 curable composition. 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 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 curable composition of this invention. Since the configuration and the like of the curable 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 curable composition of the present invention (the refractive index of Na-D line, measurement temperature 25 ° C.), that is, the refractive index of the low refractive index film is 1. 50 or less is preferable. This is because when the refractive index of the low refractive index film exceeds 1.50, the antireflection effect may be significantly reduced.
Therefore, the refractive index of the low refractive index film is more preferably 1.45 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 them should have a refractive index value within the above-mentioned range. Therefore, the other low refractive index films exceed 1.50. 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 with a high refractive index layer into the value of 0.05 or more. The reason for this is that when the difference in refractive index 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. 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 resins, cyanate resins, acrylic resins, polyester resins, urethane resins, siloxane resins and the like. This is because these resins can form a strong thin film 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.
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 for 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 fields of antireflection films such as color filters in camera lens units, television (CRT) screen display units, and 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. “Part” and “%” mean parts by weight and% by weight unless otherwise specified.

(Production Example 1)
Synthesis of hydroxyl group-containing fluoropolymer A1-1 (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 400 g of ethyl acetate, perfluoro (propyl vinyl ether) (FPVE) ) 92.3 g, ethyl vinyl ether (EVE) 25 g, hydroxyethyl vinyl ether (HEVE) 30.6 g, lauroyl peroxide 1.00 g, azo group-containing polydimethylsiloxane represented by the above general formula (8) (VPS1001 (trade name) ), 6.0 g of Wako Pure Chemical Industries, Ltd.) and 40 g of nonionic reactive emulsifier (NE-30 (trade name), manufactured by Asahi Denka Kogyo Co., Ltd.), and dry ice-methanol up to −50 ° C. After cooling, oxygen in the system was removed again with nitrogen gas.
Next, 52.1 g of hexafluoropropylene (HFP) was charged and the temperature increase was started. The pressure when the temperature in the autoclave reached 60 ° C. was 5.3 × 10 ⁵ Pa. Thereafter, the reaction was continued with stirring at 70 ° C. for 20 hours. When the pressure dropped to 1.7 × 10 ⁵ Pa, the autoclave was cooled with water to stop the reaction. After reaching room temperature, the unreacted monomer was released and the autoclave was opened to obtain a polymer solution having a solid content concentration of 26.4%. The obtained polymer solution was put into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 220 g of a hydroxyl group-containing fluoropolymer A1-1. Table 1 shows the monomers and solvents used.
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 moiety having a molecular weight of about 10,000. NE-30 is a nonionic reactive emulsifier wherein n is 9, m is 1 and u is 30 in the general formula (9).

Attached to the obtained hydroxyl group-containing fluoropolymer A1-1, the number average molecular weight in terms of polystyrene by GPC and the fluorine content by the alizarin complexone method were measured. Moreover, the ratio of each monomer component which comprises a hydroxyl-containing fluoropolymer was determined from both NMR analysis results of ¹ H-NMR and ¹³ C-NMR, elemental analysis results, and fluorine content. The results are shown in Table 2 together with the correspondence between monomers and structural units.

(Production Example 2)
Synthesis of Ethylenically Unsaturated Group-Containing Fluoropolymer A2-1 (Component (A)) 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 the hydroxyl group-containing fluoropolymer A1-1, 0.01 g of 2,6-di-t-butylmethylphenol and 370 g of methyl isobutyl ketone (MIBK) were charged as a polymerization inhibitor, and the hydroxyl group-containing fluorine-containing polymer at 20 ° C. 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 A2-1 was obtained by maintaining at 65 ° C. and continuing stirring for 5 hours. 2 g of this solution was weighed in an aluminum dish, dried on a hot plate at 150 ° C. for 5 minutes, and weighed to determine the solid content, which was 15%. The compounds used, solvent and solid content are shown in Table 3.

(Production Example 3)
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, the mixture was added dropwise at 50 ° C. over 1 hour, and then stirred at 70 ° C. for 3 hours. NK ester A-TMM-3LM-N (60% by weight of pentaerythritol triacrylate and 40% by weight of pentaerythritol tetraacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. 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. Thus, 285 parts of a mixture (Hb-1) containing the compound represented by the formula (13) and the compound represented by the formula (14) (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 4)
Preparation of acrylic-modified silica particles H-1 (component (H)) 9.0 parts of composition (Hb-1) synthesized in Production Example 3, methyl ethyl ketone silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-ST) -L (number average particle diameter 50 nm, silica concentration 30%)) 92.3 parts (solid content 27.4 parts), ion-exchanged water 0.1 parts, orthoformate methyl ester 1.4 parts H-1 was obtained. The solid content of H-1 was determined to be 35% by weight.
The average particle diameter of the silica-based particles was 50 nm. Here, the average particle diameter was measured with a transmission electron microscope.

(Production Example 5)
Preparation of silica particle-containing hard coat layer composition In a container shielded from ultraviolet rays, 86 parts of acrylic-modified silica particles H-1 synthesized in Production Example 4 (30 parts as a solid content) and 65 parts of dipentaerythritol hexaacrylate , 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 5 parts and MIBK 44 parts are stirred at 50 ° C. for 2 hours to form a uniform solution for a hard coat layer 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 weight.

(Production Example 6)
Preparation of substrate for coating curable composition Silica-containing hard coat prepared in Production Example 5 on the easy-adhesion treated surface of single-sided easy-adhesive polyethylene terephthalate (PET) film A4100 (manufactured by Toyobo Co., Ltd., film thickness 188 μm) The layer composition was applied using a wire bar coater (# 7) 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 curable composition coating substrate. The film thickness of the hard coat layer on this substrate was measured with a stylus type surface shape measuring instrument and found to be 3 μm.

Example 1
(1) Production of curable composition As shown in Table 4, 35.0 g of the hydroxyl group-containing fluoropolymer A1-1 synthesized in Production Example 1 and the ethylenically unsaturated group-containing fluorine synthesized in Production Example 2 200.0 g of MIBK solution of polymer A2-1 (30.0 g as a fluorine-containing polymer containing an ethylenically unsaturated group), cross-linked compound methoxymethyl methylamine “Cymel 300” (product name, manufactured by Mitsui Cytec) 13 .5 g, 3.5 g of dipentaerythritol pentaacrylate (SR399E, manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional (meth) acrylate compound, 56.0 g of MEK solution of acrylic-modified silica particles produced in Production Example 4 (solid content) 14.0 g), Catalyst 4050 as an acid catalyst (aromatic sulfonic acid amine salt, manufactured by Nippon Cytec) 1.5 g, E as a photopolymerization initiator Sacure Kip150 (2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, 2.5 g of Nippon Siebel Hegner), MIBK 988 g, methoxypropyl acetate (PGMEA) 1200 g, made of glass with a stirrer The mixture was charged into a separable flask and stirred at 23 ° C. for 1 hour to obtain a uniform curable composition. Moreover, it was 4% when solid content of the obtained curable composition was calculated | required similarly to manufacture example 2. In addition, 50% of the solvent was PGMEA, and other than that, it was MIBK except for MEK brought in from the acrylic modified silica particle dispersion H-1.
(2) Production of antireflection film On the curable composition coating substrate produced in Production Example 6, the curable composition obtained in (1) above was used using a wire bar coater (# 3). Coated and dried at room temperature for 5 minutes. Thereafter, the sample was heated in an oven at 140 ° C. for 2 minutes, and then irradiated with ultraviolet rays under a light irradiation condition of 1 J / cm ² using a high-pressure mercury lamp in an air atmosphere 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 2-4, Comparative Examples 1-3)
A curable composition and a cured film were produced in the same manner as in Example 1 except that the composition shown in Table 4 was used. In both examples and comparative examples, compositions were prepared so that the refractive index (n _D ²⁵ ) at 589 nm of the cured film was 1.43.

(Reference example)
The curable composition produced in Example 2 was coated on the curable composition coated substrate produced in Production Example 6 using a wire bar coater (# 3) and dried at room temperature for 5 minutes. . In an air atmosphere, ultraviolet rays were irradiated under a light irradiation condition of 1 J / cm ² using a high-pressure mercury lamp, and then heated in an oven at 140 ° C. for 2 minutes 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.

(Test Example 1)
The physical properties of the cured films obtained using the curable compositions obtained in Examples 1 to 4, Comparative Examples 1 to 3 and Reference Examples were measured or evaluated by the measurement methods shown below. Table 4 shows the obtained results.

(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 repellency, and evaluated according to the following criteria.
○: Coating unevenness and repellency are not recognized.
X: Coating unevenness or repellency is recognized.

(B) Refractive index Each curable composition was applied onto a silicon wafer by a spin coater so that the thickness after drying was about 0.1 μm, heated in an oven at 140 ° C. for 2 minutes, and then in an air atmosphere. Using a high-pressure mercury lamp, it was cured by irradiating with ultraviolet rays under a light irradiation condition of 1 J / cm ² . The obtained cured film was measured refractive index at a wavelength of 589nm at 25 ° C. using an ellipsometer to ^{_(n D 25).}

(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 cured film occurs.

(D) Chemical resistance test The cured film (sample for evaluation) obtained in each Example and Comparative Example was attached to an eraser testing machine (manufactured by Honko Seisakusho Co., Ltd.) with a cheesecloth infused with ethanol, and 1.5 kg By repeatedly rubbing under the conditions of load and number of sliding times of 50, the presence or absence of scratches on the surface of the cured film was visually evaluated according to the following criteria.
○: The sample surface for evaluation is intact.
Δ: The surface of the evaluation sample is scratched.
X: Peeling of the coating film is observed.

The components in Table 4 represent the following.
Hydroxyl group-containing fluoropolymer A1-1: produced in Production Example 1 Cymel 300: Methoxylated methyl melamine, manufactured by Mitsui Cytec, Inc.
Cat 4050: Aromatic sulfonic acid amine salt, manufactured by Nippon Cytec Co., Ltd. Ethylenically unsaturated group-containing fluoropolymer A2-1: manufactured in Preparation Example 2 dipentaerythritol pentaacrylate: SR399E, manufactured by Nippon Kayaku Co., Ltd. acrylic modified silica particles H-1 : Manufactured in Production Example 4 Kip150: 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, manufactured by Nippon Siebel Hegner, Esacure Kip150

  From the results of Table 4, it can be seen that the cured films of the examples are excellent in coating property, scratch resistance and chemical resistance. Moreover, even if it compares with the case where the order of a hardening process (thermal curing, radiation curing) is reversed from the result of a reference example, it turns out that the manufacturing method of the cured film in this invention is excellent.

(Production Example 7)
Synthesis of hydroxyl group-containing fluoropolymer A1-2 (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, ethyl vinyl ether (EVE) 81.6 g, hydroxyethyl vinyl ether (HEVE) 99.7 g, lauroyl peroxide 3.0 g, azo group-containing polydimethylsiloxane represented by the above general formula (8) (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, and 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 put 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 A1-2. Table 5 shows the charged weights of monomers and solvents used.
Attached to the obtained hydroxyl group-containing fluoropolymer A1-2, the polystyrene-equivalent number average molecular weight by GPC and the fluorine content by the alizarin complexone method were measured. Further, the weight ratio and molar ratio of each monomer component constituting the hydroxyl group-containing fluoropolymer A1-2 are determined from both ¹ H-NMR and ¹³ C-NMR NMR analysis results, elemental analysis results, and fluorine content. did. The results are shown in Table 6 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 8)
Preparation of Reactive Silica Particle H-2 (Component (H)) 9.0 parts of composition (Hb-1) containing the specific organic compound obtained in Production Example 3, methyl ethyl ketone (MEK) silica sol (Nissan Chemical Industry ( Product name: MEK-ST (number average particle diameter 0.022 μm, silica concentration 30%)) 91.3 parts (solid content 27.4 parts), isopropanol 0.2 parts and ion-exchanged water 0.1 After stirring the mixture of 80 parts at 80 ° C. for 3 hours, 1.4 parts of orthoformate methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain a colorless transparent particle dispersion D-1. After weighing 2 g of D-1 in an aluminum dish, it was dried on a hot plate at 120 ° C. for 1 hour and weighed to determine the solid content, which was 35% by weight.
The average particle diameter of the silica-based particles was 20 nm. Here, the average particle diameter was measured with a transmission electron microscope.

(Production Example 9)
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 reactive silica particles H-2 synthesized in Production Example 8 and 65 parts of dipentaerythritol hexaacrylate , 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 5 parts and MIBK 49 parts are stirred at 50 ° C. for 2 hours to form a uniform solution for the hard coat layer I got a thing. 2 g of this composition was weighed in an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour, and weighed to determine the solid content, which was 50% by weight.

(Production Example 10)
Preparation of substrate for coating curable composition Silica-containing hard coat prepared in Production Example 9 on the easy-adhesion treated surface of single-sided easy-adhesive polyethylene terephthalate (PET) film A4300 (manufactured by Toyobo Co., Ltd., film thickness 188 μm) The layer composition 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 curable composition coating substrate. The film thickness of the hard coat layer on this substrate was measured with a stylus type surface shape measuring instrument and found to be 3 μm.

(Production Example 11)
Synthesis of Ethylenically Unsaturated Group-Containing Fluoropolymer A2-2 (Component (A)) Obtained in Production Example 7 in a 1-liter separable flask equipped with an electromagnetic stirrer, a glass condenser, and a thermometer. Hydroxyl group-containing fluorine-containing polymer A1-2 was charged with 50.0 g, 2,6-di-t-butylmethylphenol 0.01 g and methyl isobutyl ketone (MIBK) 370 g as a polymerization inhibitor, and hydroxyl group-containing fluorine-containing polymer at 20 ° C. 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 A2-2 was obtained by maintaining at 65 ° C. and continuing stirring for 5 hours. 2 g of this solution was weighed in an aluminum dish, dried on a hot plate at 150 ° C. for 5 minutes, and weighed to determine the solid content, which was 15%. The compounds used, solvent and solid content are shown in Table 7.

(Example 5)
(1) Production of curable composition As shown in Table 8-1, 14.0 g of the hydroxyl group-containing fluoropolymer A1-2 synthesized in Production Example 7, hexamethoxymethylmelamine (product name: Cymel 300, manufactured by Mitsui Cytec) 3.50 g, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate as a polyfunctional (meth) acrylate compound (trade name: NK ester A-TMM-3LM-N, 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%) 9.80 g (2.94 g as silica particles), methanol dispersion of silica particles ( Product name: methanol silica sol, manufactured by Nissan Chemical Co., Ltd., silica concentration 30%) 3.27 g (as silica particles) .98 g), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator 0.14 g As an additive, 0.64 g of hydroxyl group-terminated polydimethylsiloxane (trade name: Silaplane FM0425, manufactured by Chisso Corporation), MIBK275.86 g, 190.00 g of tert-butanol, charged into a glass separable flask equipped with a stirrer. The mixture was stirred at 23 ° C. for 2 hours. Thereafter, 2.8 g of catalyst 4040 (Cat 4040; isopropanol solution of aromatic sulfonic acid, manufactured by Nippon Cytec Co., Ltd., active ingredient concentration: 40%) was added as an acid catalyst, and the mixture was stirred at the same temperature for 30 minutes to obtain a uniform curable composition. Got. 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 the others were MEK brought in from each silica particle dispersion and MIBK other than methanol.

(2) Production of antireflection laminate On the curable composition coating substrate produced in Production Example 10, the curable composition obtained in (1) above was used using a wire bar coater (# 3). And then dried at room temperature (23 ° C.) for 5 minutes. Thereafter, the sample was heated in an oven at 140 ° C. for 2 minutes, and then irradiated with ultraviolet rays under a light irradiation condition of 1 J / cm ² using a high-pressure mercury lamp in an air atmosphere 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 6 to 20, Comparative Example 4)
A curable composition and a cured film were produced in the same manner as in Example 5 except that the compositions shown in Tables 8-1 and 8-2 were used. However, in Examples 15, 17 and 19, the curable composition was coated on the curable composition coating substrate prepared in Production Example 10 using a wire bar coater (# 3) and room temperature ( 23 ° C.) for 5 minutes. Thereafter, ultraviolet rays were irradiated under a light irradiation condition of 1 J / cm ^{2 in} an air atmosphere using a high pressure mercury lamp, and then heated in an oven at 140 ° C. for 2 minutes to prepare a sample for evaluation.

(Test Example 2)
The physical properties of the cured films obtained using the curable compositions obtained in Examples 5 to 20 and Comparative Example 4 were measured or evaluated by the measurement methods shown below. The obtained results are shown in Tables 8-1 and 8-2.

(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 repellency, 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 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 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 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 sucked up 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 as compounds in Tables 8-1 and 8-2.
Hydroxyl group-containing fluoropolymer A1-2: Production Example 7
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%
Silaplane FM0425: hydroxyl group terminal polydimethylsiloxane, manufactured by Chisso Corporation Silaplane FM0725: methacryloxy group terminal polydimethylsiloxane, manufactured by Chisso Corporation Cat 4040 (acid catalyst): isopropanol solution of aromatic sulfonic acid, manufactured by Nippon Cytec Co., Ltd. , Active ingredient concentration 40%
Ethylenically unsaturated group-containing fluoropolymer A2-2: Production Example 11
Pentaerythritol triacrylate and pentaerythritol tetraacrylate: NK ester A-TMM-3LM-N, manufactured by Shin-Nakamura Chemical Co., Ltd. Dipentaerythritol hexaacrylate comprising 60% by weight of pentaerythritol triacrylate and 40% by weight of pentaerythritol tetraacrylate Acrylate: Trade name KAYARAD DPHA, Nippon Kayaku Co., Ltd. 2-ethylhexyl acrylate: Trade name 2-ethylhexyl acrylate, Nippon Shokubai Co., Ltd. N-Vinyl-2-pyrrolidone: Trade name V-PYROL Acrylic modified silica particles H-2 manufactured by Japan: Production Example 8
Irgacure 907: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, manufactured by Ciba Specialty Chemicals

  From the results of Tables 8-1 and 8-2, it can be seen that the cured films of the examples are excellent in coating property, scratch resistance, chemical resistance and refractive index.

  The curable 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.

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

Explanation of symbols

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

Claims (12)

The following ingredients,
(A) a fluorine-containing polymer containing a hydroxyl group and / or an ethylenically unsaturated group,
(B) a thermosetting compound,
(C) an acidic compound and / or a compound that generates an acid by heating,
(E) a compound having two or more (meth) acryloyl groups,
(F) a curable composition containing a compound that generates active species upon irradiation with active energy rays, and (G) an organic solvent,
When the total of the components excluding the component (G) is 100% by weight,
A curable composition containing 3% by weight or more of the component (B) and 3% by weight or more of the component (E). The (A) hydroxyl group-containing fluoropolymer has the following structural units (a), (b) and (c) as a total of 100 mol%: (a) 20 to 70 mol%, (b) 5 Comprising -70 mol% and (c) 5-70 mol%, and
The curable composition of Claim 1 whose polystyrene conversion number average molecular weights measured by the gel permeation chromatography are 10,000-500,000.
(A) A structural unit represented by the following general formula (1).
(B) A structural unit represented by the following general formula (2).
(C) A 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 is a hydrogen atom or a methyl group, R ⁴ is an alkyl group, a group represented by — (CH ₂ ) _x —OR ⁵ or —OCOR ⁵ (R ⁵ is 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 (A) hydroxyl group-containing fluorine-containing copolymer contains 0.1 to 10 parts by weight of the following structural unit (d) with respect to 100 parts by weight of the total of the structural units (a), (b) and (c). The curable composition according to claim 2, which is contained.
(D) A structural unit represented by the following general formula (4).

[In the general formula (4), R ¹⁰ ~R ¹³ represents a hydrogen atom, an alkyl group, or a cyano group, R ¹⁴ to R ¹⁷ represents a hydrogen atom or an alkyl group, p, q is a number from 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 30 parts by weight of the following structural unit (e) with respect to a total of 100 parts by weight of the structural units (a), (b) and (c). The curable composition according to claim 2 or 3.
(E) A 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 (A) ethylenically unsaturated group-containing fluoropolymer is
A compound containing one isocyanate group and at least one ethylenically unsaturated group;
The hydroxyl group-containing fluoropolymer,
The curable composition as described in any one of Claims 1-4 which is obtained by making this react.   The curable composition according to claim 5, wherein the compound containing one isocyanate group and at least one ethylenically unsaturated group is 2- (meth) acryloyloxyethyl isocyanate.   The curable composition according to any one of claims 1 to 6, wherein the compound (E) having two or more (meth) acryloyl groups is a compound having three or more (meth) acryloyl groups.   Furthermore, (H) The curable composition as described in any one of Claims 1-7 containing a silica particle.   The curable composition according to claim 8, wherein the (H) silica particles have an ethylenically unsaturated group.   The cured film formed by hardening the curable composition as described in any one of Claims 1-9.   The manufacturing method of the cured film which hardens the coating film of the curable composition as described in any one of Claims 1-9 by the process of heating and then irradiating with a radiation. An antireflection film laminate comprising the cured film according to claim 10.

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