JP2007277504A - Curable resin composition and antireflection film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition to give a cured product which is excellent in the mar resistance, coatability and durability and also lower refractive index and to provide a cured film and an antireflection film. <P>SOLUTION: The curable resin composition, containing (A) an ethylenically unsaturated group-containing fluorocopolymer, (B) a compound excepting component (A) and having two or more (meth)acryloyl groups and (C) a compound to generate an active species by means of the active energy ray irradiation, is characterized in that (A) the ethylenically unsaturated group-containing fluorocopolymer contains the specific structural unit (a), structural unit (b') and structural unit (c), and the sum total amount of the structural unit (a), (b') and (c) occupied in (A) the ethylenically unsaturated group-containing fluorocopolymer is 80% by mass or more, and also the curable resin composition contains, on the basis of 100% by mole of the sum total of the structural units of (a), (b') and (c), (a) of 40-55% by mole, (b') of 2-60% by mole, and (c) of less than 10% by mole. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an ethylenically unsaturated group-containing fluorine-containing copolymer, a curable resin composition using the same, and an antireflection film. More specifically, it contains an ethylenically unsaturated group-containing fluorine-containing copolymer, and when this ethylenically unsaturated group-containing fluorine-containing copolymer is cured and cured, it has scratch resistance, coating property, and durability. The present invention relates to a curable resin composition capable of obtaining a cured product excellent in, and an antireflection film including a low refractive index layer composed of such a cured product.

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

  As a material for a low refractive index layer of an antireflection film, for example, thermosetting fluororesin-based paints containing a hydroxyl group-containing fluorine-containing copolymer are known (Patent Documents 1 to 3). However, in such a fluororesin-based paint, it is necessary to heat and crosslink a hydroxyl group-containing fluorine-containing copolymer and a curing agent such as melamine resin under an acid catalyst in order to cure the coating film, 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 unsaturated group-containing fluorine-containing copolymer obtained by reacting a compound having an isocyanate group and an addition polymerizable unsaturated group with a hydroxyl group-containing fluorine-containing copolymer is included. Active energy ray-curable coating compositions have been proposed (Patent Documents 4 and 5).

JP 57-34107 A JP 59-189108 A JP 60-67518 A Japanese Patent Publication No. 6-35559 JP 2003-183322 A

  According to the ethylenically unsaturated group-containing fluorine-containing copolymer described in Patent Document 5, the above-described low refractive index property and durability can be achieved, but a material having a lower refractive index is demanded. When attempting to increase the fluorine content in order to reduce the refractive index, depending on the method for producing the ethylenically unsaturated group-containing fluorine-containing copolymer described in Patent Document 5, the ethylenically unsaturated group-containing content can be obtained. It has been found that the fluorine content of the fluorine copolymer has certain limits.

That is, in the production method described in Patent Document 5, the hydroxyl group-containing fluorine-containing copolymer is once solidified by vacuum drying or the like and redissolved in another solvent, and then the one isocyanate group and at least one It reacts with the compound containing the ethylenically unsaturated group of (refer patent document 5, an Example). However, in the case of a hydroxyl group-containing fluorine-containing copolymer having a high fluorine content, once this is solidified, it cannot be redissolved in the solvent, and one isocyanate group and at least one ethylenically unsaturated group It is not possible to carry out a reaction with a compound containing, and an ethylenically unsaturated group-containing fluorine-containing copolymer cannot be obtained.
The reason why the hydroxyl group-containing fluorine-containing copolymer was once solidified and redissolved in the solvent was that gelation occurred when the unreacted polymerization initiator and monomer were removed and the ethylenically unsaturated group-containing isocyanate compound was reacted. In addition, this is to suppress the generation of impurities.

  Therefore, the present invention provides a cured product having a lower refractive index by using an ethylenically unsaturated group-containing fluorine-containing copolymer having excellent scratch resistance, coating property and durability and having a high fluorine content. It aims at providing the curable resin composition to give, the cured film obtained by hardening | curing this composition, and an anti-reflective film.

［式中、Ｒ^１はフッ素原子、フルオロアルキル基又は−ＯＲ^２で表される基（Ｒ^２はアルキル基又はフルオロアルキル基を示す）を示す］
構造単位（ｂ’）：

［式中、Ｒ^３は水素原子又はメチル基であり、Ｒ^２４は、下記式（６）又は（７）

又は

（式中、Ｒは、水素原子又はメチル基であり、ｘは０〜２である）で示される基を示す］
構造単位（ｃ）：

［式中、Ｒ^６は水素原子又はメチル基を示し、Ｒ^７は−Ｏ（ＣＨ_２）_ｘＲ^８で表される基（Ｒ^８はフルオロアルキル基を示し、ｘは０〜２である）を示す］
２．前記（Ａ）エチレン性不飽和基含有含フッ素共重合体が、該共重合体中に、下記式（４）で表される構造単位（ｄ）を０．１〜１０質量％含有する、上記１に記載の硬化性樹脂組成物。
構造単位（ｄ）：

［式中、Ｒ^９及びＲ^１０は、同一でも異なっていてもよく、水素原子、アルキル基、ハロゲン化アルキル基又はアリール基を示す］
３．前記（Ａ）エチレン性不飽和基含有含フッ素共重合体が、該共重合体中に、下記式（５）で表される構造単位（ｅ）を１〜１５質量％含有する、上記１又は２に記載の硬化性樹脂組成物。
構造単位（ｅ）：

［式中、Ｒ^１９は乳化作用を有する基を示す］
４．シリカを主成分とする粒子を含有する、上記１〜３のいずれかに記載の硬化性樹脂組成物。
５．上記１〜４のいずれかに記載の硬化性樹脂組成物を硬化させて得られる硬化膜。
６．上記５に記載の硬化膜からなる層を有する、反射防止膜。 The present invention provides the following curable resin composition, cured film and antireflection film.
1. (A) an ethylenically unsaturated group-containing fluorine-containing copolymer;
(B) a compound containing two or more (meth) acryloyl groups other than component (A);
(C) A curable resin composition containing a compound that generates active species upon irradiation with active energy rays,
The (A) ethylenically unsaturated group-containing fluorine-containing copolymer comprises a structural unit (a) represented by the following formula (1), a structural unit (b ′) represented by the following formula (2 ′), and the following: Containing a structural unit (c) represented by formula (3),
The total amount of structural units (a), (b ′) and (c) in the (A) ethylenically unsaturated group-containing fluorine-containing copolymer is 80% by mass or more, and
The structural units (a), (b ′) and (c) are based on a total of 100 mol%,
(A) 40-55 mol%,
(B ') 2-60 mol% and (c) It contains in the ratio of less than 10 mol%, The curable resin composition characterized by the above-mentioned.
Structural unit (a):

[Wherein, 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)]
Structural unit (b ′):

[In the formula, R ³ represents a hydrogen atom or a methyl group, and R ²⁴ represents the following formula (6) or (7)

Or

(In the formula, R represents a hydrogen atom or a methyl group, and x represents 0 to 2).]
Structural unit (c):

[In the formula, R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a group represented by —O (CH ₂ ) _x R ⁸ (R ⁸ represents a fluoroalkyl group, and x is 0 to 2). Show]
2. Said (A) ethylenically unsaturated group containing fluorine-containing copolymer contains 0.1-10 mass% of structural units (d) represented by following formula (4) in this copolymer, The curable resin composition according to 1.
Structural unit (d):

[Wherein R ⁹ and R ¹⁰ may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group]
3. Said (1) or (A) said fluorine-containing copolymer containing an ethylenically unsaturated group contains 1-15 mass% of structural units (e) represented by following formula (5) in this copolymer 2. The curable resin composition according to 2.
Structural unit (e):

[Wherein R ¹⁹ represents a group having an emulsifying action]
4). The curable resin composition according to any one of the above 1 to 3, comprising particles containing silica as a main component.
5). The cured film obtained by hardening the curable resin composition in any one of said 1-4.
6). 6. An antireflection film having a layer comprising the cured film as described in 5 above.

  According to the curable resin composition of the present invention, since the refractive index value is low, a cured film having an excellent antireflection effect and excellent in coating property and durability can be obtained. The antireflection film of the present invention has an excellent antireflection effect and also has excellent scratch resistance.

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

I. Curable resin composition

2. Curable resin assembly The curable resin composition of this invention contains the following (A)-(G) component. Among these components, the components (A) to (C) are essential components, and preferably include the component (D).
(A) Ethylenically unsaturated group-containing fluorine-containing copolymer (B) Compound containing two or more (meth) acryloyl groups other than component (A) (C) Active species generated by irradiation with active energy rays (D) Particles mainly composed of silica (E) Compound that generates active species by heat (F) Organic solvent (G) Fluorine-containing compound having one or more (meth) acryloyl groups Hereinafter, each component explain.

1. (A) Ethylenically unsaturated group-containing fluorine-containing copolymer The ethylenically unsaturated group-containing fluorine-containing copolymer of the present invention includes a hydroxyl group-containing fluorine-containing copolymer described below and acrylic acid or a halogen salt of acrylic acid. It is obtained by reacting.

1-1. Hydroxyl group-containing fluorine-containing copolymer The hydroxyl group-containing fluorine-containing copolymer is a hydroxyl group-containing fluorine-containing copolymer containing the following structural units (a), (b) and (c), and the mass of the copolymer: The total amount of the structural units (a), (b) and (c) is 80% by mass or more, and the structural units (a), (b) and (c) The structural unit (a) is contained in a proportion of 40 to 55 mol%, the structural unit (b) is contained in a proportion of 30 to 60 mol%, and the structural unit (c) is contained in a proportion of 0 to 20 mol%. To do.

［式中、Ｒ^１はフッ素原子、フルオロアルキル基又は−ＯＲ^２で表される基（Ｒ^２はアルキル基又はフルオロアルキル基を示す）を示す］ The structural unit (a) is represented by the following formula (1).

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

［式中、Ｒ^３は水素原子又はメチル基であり、Ｒ^４は、−Ｏ（ＣＨ_２）_ｘＯＨ又は−ＯＣＯ（ＣＨ_２）_ｘＯＨであり、ｘは０〜２である。］ The structural unit (b) is represented by the following formula (2).

[Wherein, R ³ is a hydrogen atom or a methyl group, R ⁴ is —O (CH ₂ ) _x OH or —OCO (CH ₂ ) _x OH, and x is 0 to 2. ]

［式中、Ｒ^６は水素原子又はメチル基を示し、Ｒ^７は−Ｏ（ＣＨ_２）_ｘＲ^８で表される基（Ｒ^８はフルオロアルキル基を示し、ｘは０〜２の数を示す）を示す］ The structural unit (c) is represented by the following formula (3).

[Wherein R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a group represented by —O (CH ₂ ) _x R ⁸ (R ⁸ represents a fluoroalkyl group, x represents a number of 0 to 2; Show)]

  The fluorine content of the hydroxyl group-containing fluorine-containing copolymer is usually 50% by mass or more, and has a solubility of 5% by mass or more at 25 ° C. with respect to MIBK. Here, the fluorine content refers to the ratio (% by mass) of fluorine atoms to the mass of the entire polymer. Further, the hydroxyl group-containing fluorine-containing copolymer preferably has a polystyrene-equivalent number average molecular weight of 5,000 to 500,000 as measured by gel permeation chromatography.

Hereinafter, each structural unit of the hydroxyl group-containing fluorine-containing copolymer will be described.
(1) Structural unit (a)
In the formula (1), as the fluoroalkyl group of R ¹ and R ² , carbon such as trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluorohexyl group, perfluorocyclohexyl group, etc. The fluoroalkyl group of number 1-6 is mentioned. The alkyl group R ^2, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an alkyl group having 1 to 6 carbon atoms such as a cyclohexyl group.

The structural unit (a) can be introduced by using a fluorine-containing vinyl monomer as a polymerization component. Such a fluorine-containing vinyl monomer is not particularly limited as long as it is a compound having at least one polymerizable unsaturated double bond and at least one fluorine atom. Examples thereof include fluororefines such as tetrafluoroethylene, hexafluoropropylene and 3,3,3-trifluoropropylene; alkyl perfluorovinyl ethers or alkoxyalkyl perfluorovinyl ethers; perfluoro (methyl vinyl ether), perfluoro Perfluoro (alkyl vinyl ethers) such as (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether); perfluoro (alkoxyalkyl vinyl ether) such as perfluoro (propoxypropyl vinyl ether) ) Class of single species or a combination of two or more species.
Among these, hexafluoropropylene and perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether) are more preferable, perfluoro (alkyl vinyl ether) is more preferable, and perfluoro (propyl vinyl ether) is particularly preferable.

In addition, the content rate of structural unit (a) is 40-55 mol% with respect to a total of 100 mol% of structural units (a), (b), and (c). This is because when the content is less than 40 mol%, the fluorine content of the fluorine-containing copolymer is less than 40% by mass, which is an optical characteristic of the fluorine-containing material intended by the present invention. This is because it may be difficult to express the refractive index. On the other hand, the hydroxyl group-containing fluorine-containing copolymer having a content ratio of more than 55 mol% is basically composed of the structural units (a). However, when this content is exceeded, the solubility of the hydroxyl-containing fluorine-containing copolymer in an organic solvent, transparency, or adhesion to a substrate may be reduced. .
For this reason, the content of the structural unit (a) is further set to 45 to 50 mol% with respect to 100 mol% in total of the structural units (a), (b) and (c). preferable.

(2) Structural unit (b)
The structural unit (b) can be introduced by using a hydroxyl group-containing vinyl monomer represented by the formula (2) 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.

In addition, the content rate of a structural unit (b) is 30-60 mol% with respect to a total of 100 mol% of structural units (a), (b), and (c). The reason for this is that when the content rate is less than 30 mol%, the solubility of the hydroxyl group-containing fluorine-containing copolymer in the organic solvent may decrease, whereas when the content rate exceeds 60 mol%, This is because the optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluorine-containing copolymer may deteriorate.
For this reason, the content of the structural unit (b) is more preferably 40 to 50 mol% with respect to the total of 100 mol% of the structural units (a), (b) and (c). preferable.

（式中、Ｒ^２０は水素原子又はメチル基であり、ｘは０〜２である。また、上記式中、芳香環の中にＦと記した基は、５つの水素の全てがフッ素原子で置換されていることを示す。） (3) Structural unit (c)
The structural unit (c) can be introduced by using a vinyl monomer represented by the formula (3) as a polymerization component. Specific examples of such vinyl monomers include those having the following structural formula.

(In the formula, R ²⁰ is a hydrogen atom or a methyl group, and x is 0 to 2. Also, in the above formula, the group denoted by F in the aromatic ring is all five hydrogen atoms are fluorine atoms. Indicates that it has been replaced.)

In addition, the content rate of a structural unit (c) is 0-20 mol% with respect to a total of 100 mol% of structural units (a), (b), and (c). This is because, when the content of the structural unit (c) is 20 mol% or more, it is difficult to dissolve in an organic solvent, and it becomes difficult to produce an ethylenically unsaturated group-containing fluorine-containing copolymer described later. It is.
For this reason, the content of the structural unit (c) is further set to 0 to 10 mol% with respect to a total of 100 mol% of the structural units (a), (b) and (c). preferable.

  The total content of the structural units (a), (b) and (c) in the hydroxyl group-containing fluorine-containing copolymer is 80% by mass or more of the mass of the copolymer. This is because when the content is less than 80% by mass, the fluorine content of the hydroxyl group-containing fluorine-containing copolymer is lowered, and thus optical properties such as low reflectivity may be lowered.

(4) Structural unit (d)
The hydroxyl group-containing fluorine-containing copolymer preferably contains the following structural unit (d) derived from an azo group-containing polysiloxane compound. By including the structural unit (d), the scratch resistance is improved.

(D) A structural unit represented by the following formula (4).

[In formula (4), R ⁹ and R ¹⁰ may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group, or an aryl group]
By including the structural unit (d), the scratch resistance is improved.

  Moreover, in a hydroxyl-containing fluorine-containing copolymer, it is preferable that the said structural unit (d) is included as a part of structural unit (d-1) shown by following formula (4-1).

Structural unit (d-1):

[In Formula (4-1), R ^{11 to} R ¹⁴ may be the same or different and each represents a hydrogen atom, an alkyl group, or a cyano group, and R ^{15 to} R ¹⁸ may be the same or different. , A hydrogen atom or an alkyl group, a halogenated alkyl group, or an aryl group, p and q are numbers from 1 to 6, s and t are numbers from 0 to 6, and y is a number from 1 to 200. ]
Hereinafter, the structural units (d) and (d-1) will be described.

In the formula (4), the alkyl group of R ⁹ or R ^{10 is} an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group, and the halogenated alkyl group is a trifluoromethyl group or perfluoro group. C1-C4 fluoroalkyl groups, such as an ethyl group, a perfluoropropyl group, a perfluorobutyl group, etc., A phenyl group, a benzyl group, a naphthyl group etc. are each mentioned as an aryl group.

  The structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the formula (4). Examples of such azo group-containing polysiloxane compounds include compounds represented by the following formula (4-2).

[In the formula (4-2), R ^{11 to} R ¹⁴ , R ^{15 to} R ¹⁸ , p, q, s, t, and y are the same as those in the above formula (4-1), and z is 1 to 20 Is the number of ]

When the compound represented by the formula (4-2) is used, the structural unit (d) is included in the hydroxyl group-containing fluorine-containing copolymer as a part of the structural unit (d-1). In this case, in the formula (4-1), examples of the alkyl group represented by R ^{11 to} R ¹⁴ include an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, and a cyclohexyl group. Examples of the alkyl group of R ^{15 to} R ¹⁸ include an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group.

  In the present invention, the azo group-containing polysiloxane compound represented by the above formula (4-2) is particularly preferably a compound represented by the following formula (4-3).

[In formula (4-3), y and z are the same as those in formula (4-2). ]
As a commercial item of the compound represented by the formula (4-3), for example, VPS1001 (Wako Junshaku Kogyo Co., Ltd.) can be mentioned. VPS1001 is an azo group-containing polydimethylsiloxane represented by the above formula (4-3) having a number average molecular weight of 70 to 90,000 and a polysiloxane moiety having a molecular weight of about 10,000.

The content of the structural unit (d) in the hydroxyl group-containing fluorine-containing copolymer is preferably 0.1 to 10% by mass in the copolymer. The reason for this is that when the content exceeds 10% by mass, the transparency of the hydroxyl group-containing fluorine-containing copolymer is inferior, and when used as a coating material, repelling or the like may easily occur during coating. . Moreover, it is preferable for the content rate to be 0.1% by mass or more for improving scratch resistance.
For this reason, the content of the structural unit (d) is more preferably 0.5 to 5% by mass in the copolymer. For the same reason, the content of the structural unit (e) is desirably determined so that the content of the structural unit (d) contained therein is in the above range.

(5) Structural unit (e)
Furthermore, it is preferable that the said hydroxyl-containing fluorine-containing copolymer contains the following structural unit (e).
(E) A structural unit represented by the following formula (5).

[In formula (5), R ¹⁹ represents a group having an emulsifying action]

By including the structural unit (e), coatability is improved.
Hereinafter, the structural unit (e) will be described.

In the formula (5), the group having an emulsifying action of R ¹⁹ includes a group having both a hydrophobic group and a hydrophilic group, and the hydrophilic group having a polyether structure such as polyethylene oxide and polypropylene oxide. preferable.

  Examples of the group having such an emulsifying action include a group represented by the following formula (5-1).

[In Formula (5-1), n is a number from 1 to 20, m is a number from 0 to 4, and u is a number from 3 to 50]

  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 formula (5-2).

[In Formula (5-2), n, m, and u are the same as those in Formula (5-1) above]
As a commercial item of the compound represented by Formula (5-2), NE-30 (Asahi Denka Kogyo Co., Ltd.) is mentioned, for example. NE-30 is a nonionic reactive emulsifier in which n is 9, m is 1, and u is 30 in the above formula (5-2).

In addition, it is preferable that the content rate of a structural unit (e) shall be 1-15 mass% in this copolymer. The reason for this is that when the content is 1% by mass or more, the solubility of the hydroxyl group-containing fluorine-containing copolymer in the solvent is improved. On the other hand, if the content is within 15% by mass, the curable resin composition has This is because the tackiness does not increase excessively, the handling becomes easy, and the moisture resistance does not decrease even when used as a coating material.
For such reasons, the content of the structural unit (e) is more preferably 1 to 10% by mass, and further preferably 3 to 7% by mass in the copolymer.

  The hydroxyl group-containing fluorine-containing copolymer is a copolymer of monomers containing various functional groups in addition to the structural units (a) to (e) as long as the properties intended by the present invention are not impaired. By doing so, a fluorine-containing copolymer having a functional group can be obtained. As the functional group of the monomer to be copolymerized, a hydroxyl group and an epoxy group are particularly preferable. Examples of the hydroxyl group-containing monomer include hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether; allyl alcohol; hydroxyethyl (meth) acrylate Can be mentioned. Examples of the monomer containing an epoxy group include vinyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate, glycidyl crotonic acid, and methyl glycidyl maleate. These other monomers may be used alone or in combination of two or more.

  Among the other copolymerizable monomers, alkyl vinyl ethers, cycloalkyl vinyl ethers, and carboxylic acid vinyl esters are preferably used in order to increase the yield in the polymerization reaction of the fluorine-containing copolymer of the present invention. Is done. In particular, for example, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, etc. Molecular weight monomers are preferred.

  Furthermore, the use of branched monomers such as isopropyl vinyl ether, tert-butyl vinyl ether, and vinyl pivalate is effective for increasing the hardness and lowering the refractive index of the coating film after curing of the curable resin composition. is there.

(6) Molecular Weight The hydroxyl group-containing fluorine-containing copolymer has a polystyrene-reduced number average molecular weight of 5, measured by gel permeation chromatography (hereinafter referred to as “GPC”) using tetrahydrofuran (hereinafter referred to as “THF”) as a solvent. It is preferable that it is 000-500,000. The reason for this is that when the number average molecular weight is less than 5,000, the mechanical strength of the hydroxyl group-containing fluorine-containing copolymer may be reduced. On the other hand, when the number average molecular weight exceeds 500,000, This is because the viscosity of the curable resin composition produced by using the resin 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 fluorine-containing copolymer is more preferably 10,000 to 300,000, and even more preferably 10,000 to 100,000.

(7) Fluorine content The fluorine content of the hydroxyl group-containing fluorine-containing copolymer is preferably 45% by mass or more, and more preferably 50% by mass or more. When the fluorine content is 45% by mass or more, optical characteristics such as low reflectivity are improved.

1-2. Ethylenically unsaturated group-containing fluorine-containing copolymer The ethylenically unsaturated group-containing fluorine-containing copolymer of the present invention is an ethylenically unsaturated group containing the following structural units (a), (b ′) and (c). The total amount of structural units (a), (b ′) and (c) in the fluorine-containing copolymer containing the ethylenically unsaturated group is 80% by mass or more. And 40 to 50 mol% of structural unit (a) and 2 to 60 mol of structural unit (b ′) with respect to 100 mol% of the total of structural units (a), (b ′) and (c). % And the structural unit (c) in a proportion of less than 10 mol%.
Among these, the structural units (a) and (c) are the same as the structural units (a) and (c) of the above-mentioned hydroxyl group-containing fluorocopolymer, but the content of the structural unit (c) is the above. It is necessary to be less than 10 mol% on the basis. This is because a hydroxyl group-containing fluorine-containing copolymer having a structural unit (c) content of 10 mol% or more is difficult to dissolve in an organic solvent. This is because it becomes difficult to produce the polymer.

［式中、Ｒ^３は水素原子又はメチル基であり、Ｒ^２４は、下記式（６）又は（７）

又は

（Ｒは、水素原子又はメチル基であり、ｘは０〜２である）で示される基を示す］ The structural unit (b ′) is represented by the following formula (2 ′). The structural unit (b ′) is a structural unit obtained by reacting the structural unit (b) of the above-mentioned hydroxyl group-containing fluorine-containing copolymer with acrylic acid or the like in the steps described later.

[In the formula, R ³ represents a hydrogen atom or a methyl group, and R ²⁴ represents the following formula (6) or (7)

Or

(R represents a hydrogen atom or a methyl group, and x represents 0 to 2).

The content of the structural unit (b ′) in the ethylenically unsaturated group-containing fluorine-containing copolymer of the present invention is based on a total of 100 mol% of the structural units (a), (b ′) and (c). It is preferable to set it as 2-60 mol%. The content of the structural unit (b ′) in the ethylenically unsaturated group-containing fluorine-containing copolymer is different from the content of the structural unit (b) in the hydroxyl group-containing fluorine-containing copolymer. This is because ') is formed by the reaction of the structural unit (b) with acrylic acid or the like, and the impossibility of acrylic acid or the like due to the reaction is not necessarily 100 mol% as described later.
For these reasons, the content of the structural unit (b ′) is further set to 2 to 50 mol% with respect to the total of 100 mol% of the structural units (a), (b ′) and (c). preferable.

  The ethylenically unsaturated group-containing fluorine-containing copolymer of the present invention can contain the above-mentioned structural units (d) and / or (e) in the same manner as the above-mentioned hydroxyl-containing fluorine-containing copolymer. The contents of the structural units (d) and (e) in the ethylenically unsaturated group-containing fluorine-containing copolymer are the same as in the above-mentioned hydroxyl group-containing fluorine-containing copolymer.

  In addition, the ethylenically unsaturated group containing fluorine-containing copolymer of this invention can contain arbitrary structural units other than the said structural unit in the range which does not impair the characteristic which this invention aims. Since the ethylenically unsaturated group-containing fluorine-containing copolymer of the present invention is produced by introducing an ethylenically unsaturated group into a hydroxyl group-containing fluorine-containing copolymer, as described later, these arbitrary configurations The unit is as described above for the hydroxyl group-containing fluorine-containing copolymer.

1-3. Method for producing ethylenically unsaturated group-containing fluorine-containing copolymer The method for producing an ethylenically unsaturated group-containing fluorine-containing copolymer of the present invention (hereinafter referred to as the production method of the present invention) is the above-mentioned hydroxyl-containing fluorine-containing copolymer. The polymer is dissolved in an organic solvent and reacted with acrylic acid or a halogen salt of acrylic acid in the presence of a basic compound.

More specifically,
(1) The above-mentioned hydroxyl group-containing fluorine-containing copolymer (however, the proportion of the structural unit (c) relative to the total of 100 mol% of the structural units (a), (b) and (c) is less than 10 mol%) )) In an organic solvent to obtain a solution of the hydroxyl group-containing fluorine-containing copolymer having a concentration of 5% by mass or more, and (2) a solution of the hydroxyl group-containing fluorine-containing copolymer and acrylic acid or The method includes a step of synthesizing the aforementioned ethylenically unsaturated group-containing fluorine-containing copolymer by mixing a halogen salt of acrylic acid in the presence of a basic compound.

  The above-mentioned production method for producing the ethylenically unsaturated group-containing fluorine-containing copolymer of the present invention particularly comprises using an ethylenically unsaturated group-containing fluorine-containing copolymer having a fluorine content of 50% by mass or more. Although it is suitable for producing a fluorine copolymer, it can also be applied to the case of using a hydroxyl group-containing fluorine-containing copolymer having a fluorine content of less than 50% by mass.

Hereinafter, each step will be described.
Step (1):
The organic solvent (hereinafter referred to as “organic solvent 1”) used in the step (1) has a property that does not affect the reaction of the hydroxyl group-containing fluorine-containing copolymer with acrylic acid and a halide of acrylic acid. Although not particularly limited, methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), methyl amyl ketone, acetone, butyl acetate, and ethyl acetate are preferable. These organic solvents 1 can be used individually by 1 type or in mixture of 2 or more types.

  The concentration of the hydroxyl group-containing fluorine-containing copolymer in the solution is preferably 5% by mass or more. The reason is that if it is less than 5% by mass, the reactivity with acrylic acid or the like is lowered in the step (2) described later. The upper limit of the concentration is determined by the solubility of the hydroxyl group-containing fluorine-containing copolymer, but is usually about 30% by mass.

  Therefore, the hydroxyl group-containing fluorine-containing copolymer needs to have a solubility of 5% by mass or more at room temperature with respect to any one of the organic solvents 1 described above. This solubility is less than 10 mol% with respect to the total of 100 mol% of the structural units (a), (b) and (c) in the proportion of the structural unit (c) in the hydroxyl group-containing fluorine-containing copolymer. Can be obtained.

Step (2):
This is a step of reacting a hydroxyl group-containing fluorine-containing copolymer with acrylic acid or a halogen salt of acrylic acid (also referred to herein as “acrylic acid or the like”). Specifically, the hydroxyl group of the structural unit (b) in the hydroxyl group-containing fluorine-containing copolymer reacts with acrylic acid or a halogen salt of acrylic acid to form the structural unit (b ′). As the halogen salt of acrylic acid, acrylic acid chloride is preferred.
This reaction is performed using a basic compound as a catalyst. Specific examples of basic compounds include strong acids such as sulfuric acid and p-toluenesulfonic acid in the case of reaction with acrylic acid, and dimethylaniline and diethylamine in the case of reaction with a halogen salt of acrylic acid. Is preferred.

Specifically, acrylic acid or the like and a basic compound are added to the solution of the hydroxyl group-containing fluorine-containing copolymer obtained in the step (1), and the reaction is performed while stirring at 120 to 130 ° C. for 4 to 8 hours. . During the reaction, it is preferable to dehydrate using, for example, a Dean-Stark tube.
The addition amount of acrylic acid or the like is 5 to 120 mol parts with respect to 100 mol parts of the structural unit (b) contained in the hydroxyl group-containing fluorine-containing copolymer, and the addition amount of the basic compound is a hydroxyl group-containing amount. The amount is 5 to 120 mol parts relative to 100 mol parts of the structural unit (b) contained in the fluorinated copolymer.

  In the case of acrylic acid, the addition rate of acrylic acid or the like in the conditions of the step (2) is usually 5 to 60 mol%, preferably 30 to 60 mol%. In the case of the halogen salt of acrylic acid, it is usually 5 to 100 mol%, preferably 30 to 95 mol%. Here, the addition rate of acrylic acid or the like refers to the structural unit (b ′) obtained by reaction with acrylic acid or the like with the total amount of the structural unit (b) in the hydroxyl group-containing fluorine-containing copolymer being 100 mol%. Of mol%. When the addition rate is less than 5 mol%, the amount of acryloyl groups in the ethylenically unsaturated group-containing fluorine-containing copolymer is low, so the photocurability is lowered, and consequently the scratch resistance as a low refractive index material is lowered. There is a case. On the other hand, the upper limit of the addition rate is determined as the limit value of each method using acrylic acid or a halogen salt of acrylic acid.

Step (3):
After completion of the reaction, a base such as ammonia is added to make the pH of the reaction solution almost neutral. For example, pH 6-7 is preferable.

Step (4):
The reaction solution in which the ethylenically unsaturated group-containing fluorine-containing copolymer is generated is added to an organic solvent 2 that is different from the organic solvent 1 and has low compatibility with the organic solvent 1, and contains an ethylenically unsaturated group. The fluorine-containing copolymer is precipitated and the precipitate is collected. Furthermore, the obtained ethylenically unsaturated group-containing fluorine-containing copolymer may be dissolved in the organic solvent 1 again. At this time, it is preferable to remove moisture in the solution using a dehydrating agent such as magnesium sulfate.

  According to the production method of the present invention, an ethylenically unsaturated group-containing fluorine-containing copolymer having a fluorine content of 45% by mass or more, more preferably 47% by mass or more is obtained.

  The amount of the component (A) added is not particularly limited, but is usually 3 to 95% by mass with respect to the total amount of the composition other than the organic solvent. The reason for this is that when the addition amount is less than 3% by mass, the refractive index of the cured coating film of the curable resin composition becomes high, and a sufficient antireflection effect may not be obtained. This is because if the amount exceeds 95% by mass, the scratch resistance of the cured coating film of the curable resin composition may not be obtained. For this reason, the amount of component (A) added is more preferably 10 to 90% by mass, and still more preferably 30 to 80% by mass.

2. (B) Compound containing two or more (meth) acryloyl groups other than component (A) (hereinafter referred to as “polyfunctional (meth) acrylate compound”) containing two or more (meth) acryloyl groups. ) Is used to increase the scratch resistance of a cured product obtained by curing a curable resin composition and an antireflection film using the cured product.

  The polyfunctional (meth) acrylate compound is not particularly limited as long as it is a compound containing at least two (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-15HA” Product name, include alone or in a combination of two or more of Shin-Nakamura Chemical Co., Ltd.), and the like. Of these, neopentyl glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) Acrylate is particularly preferred.

  Although it does not restrict | limit especially about the addition amount of (B) component, It is 1-95 mass% normally with respect to composition whole quantity other than an organic solvent. The reason for this is that when the addition amount is less than 1% by mass, the scratch resistance of the cured coating film of the curable resin composition may not be obtained. On the other hand, when the addition amount exceeds 95% by mass, This is because the refractive index of the cured coating film of the curable resin composition becomes high and a sufficient antireflection effect may not be obtained. For this reason, the amount of component (B) added is more preferably 3 to 80% by mass, and even more preferably 5 to 60% by mass.

4). (D) Particles mainly composed of silica (1) Particles mainly composed of silica The curable resin composition of the present invention has the scratch resistance of the cured product of the curable resin composition, particularly steel wool resistance. In order to improve, particles containing silica as a main component are blended. As the particles containing silica as a main component, known particles can be used, and as long as the shape is spherical, not only ordinary colloidal silica but also hollow particles, porous particles, and core / shell type particles. From the viewpoint of reducing the refractive index of the composition, hollow particles and porous particles are preferable, and hollow particles are particularly preferable. Moreover, it is not limited to a spherical shape, and may be an irregularly shaped particle. Colloidal silica having a number average particle diameter determined by a dynamic light scattering method of 1 to 100 nm, a solid content of 10 to 40% by mass, and a pH of 2.0 to 6.5 is preferable.

  The dispersion medium is preferably water or an organic solvent. Examples of organic solvents include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol and ethylene glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethylformamide and dimethyl Examples include amides such as acetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and γ-butyrolactone; and organic solvents such as ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in combination of two or more as a dispersion medium.

  As a commercial 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 mass%, pH 2.7) ), Snowtex OL (number average particle diameter determined by dynamic light scattering method: 15 nm, solid content: 20% by mass, pH 2.5), and the like.

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

  The particles containing silica as a main component are preferably those which have been surface-treated with an organic compound containing a polymerizable unsaturated group (hereinafter sometimes referred to as “specific organic compound”). By such surface treatment, the scratch resistance of the cured product obtained by curing the composition of the present invention is hardly deteriorated even after being immersed in an alkaline aqueous solution.

(2) Specific organic compound The specific organic compound used in the present invention is a polymerizable compound containing a polymerizable unsaturated group in the molecule. This compound is a compound further containing a group represented by the following formula (11) in the molecule, and a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis. preferable.

［式（１１）中、ＸはＮＨ、Ｏ（酸素原子）又はＳ（イオウ原子）を示し、ＹはＯ又はＳを示す。］

[In the formula (11), X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]

(I) Polymerizable unsaturated group The polymerizable unsaturated group contained in the specific organic compound is not particularly limited. For example, acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, A cinnamoyl group, a maleate group, and an acrylamide group can be mentioned as preferred examples.

(Ii) Group represented by Formula (11) The specific organic compound preferably further includes a group represented by Formula (11) in the molecule. Specific examples of the group [—X—C (═Y) —NH—] represented by the formula (11) include [—O—C (═O) —NH—], [—O—C (═S). ) —NH—], [—S—C (═O) —NH—], [—NH—C (═O) —NH—], [—NH—C (═S) —NH—], and [ -S-C (= S) -NH-]. These groups can be used singly or in combination of two or more. 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.

(Iii) A silanol group or a group that generates a silanol group by hydrolysis The specific organic compound is a compound having a silanol group in the molecule (hereinafter sometimes referred to as “silanol group-containing compound”) or by hydrolysis. A compound that generates a silanol group (hereinafter sometimes referred to as a “silanol group-generating compound”) is preferable. Examples of such a silanol group-forming compound include compounds having an alkoxy group, aryloxy group, acetoxy group, amino group, halogen atom, etc. on the silicon atom, but an alkoxy group or aryloxy group on the silicon atom. In other words, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.

(Iv) Preferred Embodiment Specific examples of the specific organic compound include compounds represented by the following formula (12).

R ¹⁹ and R ²⁰ may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and a represents a number of 1, 2 or 3.
Examples of R ¹⁹ and R ²⁰ include methyl, ethyl, propyl, butyl, octyl, phenyl, xylyl groups and the like.

Examples of the group represented by [(R ¹⁹ O) _a R ²⁰ _3-a Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, a dimethylmethoxysilyl group, and the like. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.

R ²¹ is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms and may contain a chain, branched or cyclic structure. Examples of such an organic group include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, and dodecamethylene. Among these, preferred examples are methylene, propylene, cyclohexylene, phenylene and the like.

R ²² is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500. For example, chain polyalkylene groups such as hexamethylene, octamethylene, dodecamethylene; alicyclic or polycyclic divalent organic groups such as cyclohexylene and norbornylene; divalent groups such as phenylene, naphthylene, biphenylene and polyphenylene Aromatic group; and these alkyl group-substituted and aryl group-substituted products. Further, these divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and include a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, and a group represented by the formula (11). Can also be included.

R ²³ is a (b + 1) -valent organic group, preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.

  Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species. For example, acryloyl (oxy) group, methacryloyl (oxy) group, vinyl (oxy) group, propenyl (oxy) group, butadienyl (oxy) group, styryl (oxy) group, ethynyl (oxy) group, cinnamoyl (oxy) group , Maleate group, acrylamide group, methacrylamide group and the like. Among these, an acryloyl (oxy) group and a methacryloyl (oxy) group are preferable. Further, b is preferably a positive integer of 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5.

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

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

Hereinafter, the surface treatment method will be described in more detail using the alkoxysilyl group-containing compound (alkoxysilane compound) represented by the formula (12) as an example of the specific organic compound.
The amount of water consumed by hydrolysis of the alkoxysilane compound during the surface treatment may be an amount that allows at least one alkoxy group on silicon in one molecule to be hydrolyzed. Preferably, the amount of water added or present during hydrolysis is at least one third of the number of moles of all alkoxy groups on the silicon, more preferably one half of the number of moles of all alkoxy groups. It is less than 3 times.

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

  When a solvent-dispersed sol is used as the particles, it can be produced by mixing at least a solvent-dispersed sol and a specific organic compound. Here, an organic solvent which is uniformly compatible with water may be added for the purpose of ensuring the uniformity at the initial stage of the reaction and allowing the reaction to proceed smoothly.

  The amount of alkoxysilane compound bonded to the particles is usually a thermogravimetric analysis from 110 ° C. to 800 ° C. in air as a constant value of mass reduction% when the dry powder is completely burned in air. It can ask for.

  (D) The compounding quantity in the resin composition of the particle | grains which have silica as a main component is 1-90 mass% normally with respect to composition whole quantity other than an organic solvent, 5-80 mass% is preferable, and 10-70. % By weight is more preferable, and 20 to 60% by weight is particularly preferable. When it is less than 5% by mass, the hardness when cured is sometimes insufficient, and when it exceeds 90% by mass, it may not be cured (not formed into a film). The amount of particles means solid content, and when the particles are used in the form of a solvent-dispersed sol, the amount of the solvent does not include the amount of solvent.

3. (C) Compound that generates active species upon irradiation with active energy rays A compound that generates active species upon irradiation with active energy rays is used to cure the curable resin composition.

  Compounds that generate active species upon irradiation with active energy rays Compounds that generate active species upon irradiation with active energy rays (hereinafter referred to as "photopolymerization initiator") include photo radical generators that generate radicals as active species. Etc. 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 photopolymerization initiators 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-hydro Cycyclohexyl 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, benzyl, or a combination of BTTB and xanthene, thioxanthene, coumarin, ketocoumarin, and other dye sensitizers. Among these photopolymerization initiators, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4,6- Trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2 -Phenylmethyl) -1-butanone and the like are preferable, and 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (Dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl ) -1-butanone, and the like.

  The addition amount of the photopolymerization initiator is not particularly limited, but is usually preferably 0.01 to 20% by mass with respect to the total amount of the composition excluding the organic solvent. The reason for this is that when the amount added is less than 0.01% by mass, the curing reaction becomes insufficient, and the scratch resistance and the scratch resistance after immersion in an alkaline aqueous solution may decrease. On the other hand, when the addition amount of the photopolymerization initiator exceeds 20% by mass, the refractive index of the cured product increases and the antireflection effect may be lowered. For this reason, the amount of photopolymerization initiator added is more preferably 0.01 to 15% by mass with respect to the total amount of the composition excluding the organic solvent, and 0.1 to 10% by mass. More preferably.

5). (E) Compound that generates active species by heat In addition to the photopolymerization initiator of component (C), the curable resin composition of the present invention includes a compound that generates active species by heat (hereinafter “thermal polymerization”). Initiator ")) may be used in combination. Examples of the thermal polymerization initiator include a thermal radical generator that generates radicals as active species.

  Examples of thermal radical generators include benzoyl peroxide, tert-butyl-oxybenzoate, azobisisobutyronitrile, acetyl peroxide, lauryl peroxide, tert-butyl peracetate, cumyl peroxide, tert-butyl peroxide , Tert-butyl hydroperoxide, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc. The combination of the above can be mentioned.

  The addition amount of the thermal polymerization initiator is not particularly limited, but is preferably 0.01 to 20% by mass with respect to the total amount of the composition excluding the organic solvent. The reason for this is that when the amount added is less than 0.01% by mass, the curing reaction becomes insufficient, and the scratch resistance and the scratch resistance after immersion in an alkaline aqueous solution may decrease. On the other hand, when the addition amount of the photopolymerization initiator exceeds 20% by mass, the refractive index of the cured product increases and the antireflection effect may be lowered. For this reason, it is more preferable that the addition amount of the thermal polymerization initiator is 0.05 to 15% by mass with respect to 100% by mass of the ethylenically unsaturated group-containing fluorine-containing copolymer. More preferably, the value is in the range of ˜15% by mass.

6). (F) Organic solvent Moreover, it is preferable to add an organic solvent further in curable resin composition. Thus, by adding an organic solvent, the antireflection film of the thin film obtained by hardening the curable resin composition of this invention can be formed uniformly. Examples of such an organic solvent include one type of methyl isobutyl ketone (hereinafter sometimes referred to as “MIBK”), methyl ethyl ketone, methanol, ethanol, t-butanol, and isopropanol, or a combination of two or more types.

  The addition amount of the organic solvent is not particularly limited, but is preferably 100 to 100,000 parts by mass with respect to 100 parts by mass of the total composition excluding the organic solvent. This is because when the addition amount is less than 100 parts by mass, it may be difficult to adjust the viscosity of the curable resin composition. On the other hand, when the addition amount exceeds 100,000 parts by mass, the curable resin composition may be difficult to adjust. This is because the storage stability of the composition may decrease, or the viscosity may decrease excessively, making handling difficult.

7). (G) Fluorine-containing compound having one or more (meth) acryloyl groups The curable resin composition of the present invention further includes a fluorine-containing compound having one or more (meth) acryloyl groups (hereinafter referred to as “fluorine-containing compounds”). (Meth) acrylate compound ”) can also be added. The fluorine-containing (meth) acrylate compound is used for reducing the refractive index of the curable resin composition. Examples of the fluorine-containing (meth) acrylate compound include a fluorine-containing (meth) acrylate monomer and a fluorine-containing copolymer containing an ethylenically unsaturated group other than the component (A).
Specific examples of the fluorine-containing (meth) acrylate monomer include perfluorooctylethyl (meth) acrylate, octafluoropentyl (meth) acrylate, trifluoroethyl (meth) acrylate, and the like alone or in combination of two or more. It is done.

  The ethylenically unsaturated group-containing fluorine-containing copolymer other than the component (A) is not particularly limited as long as it does not correspond to the component (A) and has solubility in the above solvent. (Propylene vinyl ether) (FPVE), ethyl vinyl ether (EVE) and hydroxyethyl vinyl ether (HEVE) containing ethylenically unsaturated group-containing fluorine-containing copolymer obtained by reacting a copolymer with 2-methacryloyloxyethyl isocyanate A coalescence etc. can be mentioned. As the component (G), an ethylenically unsaturated group-containing fluorine-containing copolymer obtained by reacting a hydroxyl group-containing fluorine-containing copolymer used to produce the component (A) with 2-methacryloyloxyethyl isocyanate. By blending, the scratch resistance can be improved. In this case, particularly when the ethylenically unsaturated group-containing fluorine-containing copolymer (A) does not contain the structural units (d) and (e), the scratch resistance is remarkably improved. can do. Here, the hydroxyl group-containing fluorine-containing copolymer used for producing the component (A) is a hydroxyl group-containing fluorine-containing copolymer containing the structural units (a), (b), and (c). The total amount of the structural units (a), (b) and (c) in the mass of the copolymer is 80% by mass or more, and the structural units (a), (b) and (c) The proportion of the structural unit (a) is 40 to 55 mol%, the structural unit (b) is 30 to 60 mol%, and the structural unit (c) is 0 to 20 mol% with respect to 100 mol% in total. Is a hydroxyl group-containing fluorine-containing copolymer.

  (G) Although the compounding quantity of a fluorine-containing (meth) acrylate compound is not restrict | limited in particular, it is 0-40 mass% normally with respect to the composition whole quantity except an organic solvent, Preferably, it is 0-30. % By mass. If it exceeds 40% by mass, the compounding amount of the component (A) decreases, so the refractive index of the cured film may increase.

8). (H) Additive In the curable resin composition of the present invention, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, as long as the purpose and effect of the present invention are not impaired. It is also preferable to further contain additives such as a surfactant, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a silane coupling agent, an inorganic filler, a pigment, and a dye.

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

10. Curing conditions for the curable resin composition The curing conditions for the curable resin composition of the present invention are not particularly limited. For example, when active energy rays are used, the exposure dose is 0.01 to 10 J / cm ^2. It is preferable to set the value within the range. 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. For these reasons, the exposure dose is more preferably set to a value in the range of 0.1 to 5 J / cm ² , and more preferably set to a value in the range of 0.3 to 3 J / cm ^2. .

  Moreover, when making a curable resin composition heat and harden | cure, it is preferable to heat for 1 to 180 minutes at the temperature within the range of 30-200 degreeC. 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.

II. Antireflection film Hereinafter, the antireflection film of the present invention will be described. The antireflection film of the present invention includes a low refractive index layer made of a cured product obtained by curing the curable resin composition. Furthermore, the antireflection film of the present invention can comprise a high refractive index layer, a hard coat layer, and a substrate under the low refractive index layer. FIG. 1 shows 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 (not shown) may be further provided between the high refractive index layer 16 and the low refractive index layer 18 or between the high refractive index layer 16 and the hard coat layer 14.

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

  The refractive index of the cured product obtained by curing the curable resin composition (the refractive index of Na-D line, measurement temperature 25 ° C.), that is, the refractive index of the low refractive index film is preferably 1.41 or less. . The reason for this is that when the refractive index of the low refractive index film exceeds 1.45, the antireflection effect may be significantly reduced when combined with a high refractive index film. Therefore, the refractive index of the low refractive index film is more preferably 1.40 or less, and further preferably 1.39 or less. In the case where a plurality of low refractive index films are provided, at least one of the low refractive index films only needs to have a refractive index value within the above-described range. Therefore, the other low refractive index films exceed 1.45. It may be a value.

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

  Moreover, although it does not restrict | limit especially also about the thickness of a low-refractive-index layer, For example, it is preferable that it is 50-300 nm. The reason for this is that when the thickness of the low refractive index layer is less than 50 nm, the adhesion to the high refractive index film as the base may be reduced. On the other hand, when the thickness exceeds 300 nm, optical interference occurs. This is because the antireflection effect may be reduced. Therefore, the thickness of the low refractive index layer is more preferably 50 to 250 nm, and further preferably 60 to 200 nm. In order to obtain higher antireflection properties, when a plurality of low refractive index layers are provided to form a multilayer structure, the total thickness may be set to 50 to 300 nm.

(2) High refractive index layer Although it does not restrict | limit especially as a curable composition for forming a high refractive index layer, As a film formation component, epoxy-type resin, phenol-type resin, melamine-type resin, It is preferable to include one kind or a combination of two or more kinds of alkyd resins, cyanate resins, acrylic resins, polyester resins, urethane resins, siloxane resins and the like. 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. Further, in order to obtain higher antireflection properties, when a plurality of high refractive index layers are provided to form a multilayer structure, the total thickness may be set to 50 to 30,000 nm. In addition, when providing a hard-coat layer between a high refractive index layer and a base material, the thickness of a high refractive index layer can be 50-300 nm.

(3) Hard coat layer The constituent material of the hard coat layer used 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.

(5) Substrate The type of the substrate used in 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.

(Production Example 1) Production of hydroxyl group-containing fluorine-containing copolymer (a-1) A stainless steel autoclave with an internal volume of 3.0 L with a magnetic stirrer was sufficiently replaced with nitrogen gas, and then 1500 g of ethyl acetate and perfluoro (propyl vinyl ether) (FPVE) 506.1 g, (perfluorooctyl) ethyl vinyl ether 93.3 g, hydroxyethyl vinyl ether (HEVE) 150.7 g, and lauroyl peroxide 3.8 g were charged, and oxygen in the system was again removed with nitrogen gas. Next, the temperature was raised and the reaction was continued with stirring at 70 ° C. for 20 hours. Then, the autoclave was cooled with water to stop the reaction. After the temperature of the reaction solution reached room temperature, the autoclave was opened, the reaction solution was recovered, and then the reaction solution was added dropwise to 30 kg of a methanol / water mixed solution (mixed mass ratio 80/20). The precipitate was taken out and dried under reduced pressure at 40 ° C. to obtain a hydroxyl group-containing fluorine-containing copolymer (a-1).

(Production Example 2) Production of hydroxyl-containing fluorine-containing copolymer (a-2) A stainless steel autoclave with an internal volume of 3.0 L with a magnetic stirrer was sufficiently substituted with nitrogen gas, and then 1500 g of ethyl acetate and perfluoro (propyl vinyl ether) (FPVE) 506.1 g, (perfluorooctyl) ethyl vinyl ether 93.2 g, hydroxyethyl vinyl ether (HEVE) 150.7 g, lauroyl peroxide 4 g, VPS 1001 22.5 g, NE-30 37.5 g were charged again. The oxygen in the system was removed with nitrogen gas. Next, the temperature was raised and the reaction was continued with stirring at 70 ° C. for 20 hours. Then, the autoclave was cooled with water to stop the reaction. After the temperature of the reaction solution reached room temperature, the autoclave was opened, the reaction solution was recovered, and then the reaction solution was added dropwise to 30 kg of a methanol / water mixed solution (mixing mass ratio 95/5). The precipitate was taken out and dried under reduced pressure at 40 ° C. to obtain a hydroxyl group-containing fluorine-containing copolymer (a-2).

(Production Example 3): Production of hydroxyl-containing fluorine-containing copolymer (a-3) A stainless steel autoclave with an internal volume of 3.0 L with a magnetic stirrer was sufficiently substituted with nitrogen gas, and then 1500 g of ethyl acetate and perfluoro (propyl vinyl ether) ) (FPVE) 563.6 g, hydroxyethyl vinyl ether (HEVE) 186.5 g, lauroyl peroxide 3.8 g were charged, and oxygen in the system was again removed with nitrogen gas. Next, the temperature was raised and the reaction was continued with stirring at 70 ° C. for 20 hours. Then, the autoclave was cooled with water to stop the reaction. After the temperature of the reaction solution reached room temperature, the autoclave was opened, the reaction solution was recovered, and then the reaction solution was added dropwise to 30 kg of a methanol / water mixed solution (mixed mass ratio 80/20). The precipitate was taken out and dried under reduced pressure at 40 ° C. to obtain a hydroxyl group-containing fluorine-containing copolymer (a-3).

(Production Example 4) Production of hydroxyl-containing fluorine-containing copolymer (a-4) A stainless steel autoclave with an internal volume of 3.0 L with a magnetic stirrer was sufficiently replaced with nitrogen gas, and then 1500 g of ethyl acetate and perfluoro (propyl vinyl ether) (FPVE) 506.1 g, (perfluorooctyl) ethyl vinyl ether 93.3 g, hydroxyethyl vinyl ether (HEVE) 150.7 g, lauroyl peroxide 4 g, VPS 1001 22.5 g, NE-30 75.0 g were charged again. The oxygen in the system was removed with nitrogen gas. Next, the temperature was raised and the reaction was continued with stirring at 70 ° C. for 20 hours. Then, the autoclave was cooled with water to stop the reaction. After the temperature of the reaction solution reached room temperature, the autoclave was opened, the reaction solution was recovered, and then the reaction solution was added dropwise to 30 kg of a methanol / water mixed solution (mixing mass ratio 95/5). The precipitate was taken out and dried under reduced pressure at 40 ° C. to obtain a hydroxyl group-containing fluorine-containing copolymer (a-4).

(Production Example 5): Production of ethylenically unsaturated group-containing fluorine-containing copolymer solution (A-1) Capacity equipped with electromagnetic stirrer, glass cooling tube, glass Dean-Stark tube, glass dropping funnel and thermometer A 5-liter separable flask was charged with 400 g of the hydroxyl group-containing fluorine-containing copolymer (a-1) obtained in Production Example 1 and 1040 g of methyl isobutyl ketone (MIBK) as a solvent, and stirred at room temperature. The fluorine-containing copolymer was dissolved in a solvent. Next, 64.0 g of acrylic acid was added and stirred at room temperature to visually confirm that the solution was uniform. A solution obtained by dissolving 8.8 g of sulfuric acid in 160 g of MIBK was added dropwise while stirring at room temperature using a glass dropping funnel. After completion of the dropwise addition, the system was heated using an oil bath under dry air so that the temperature of the system became 120 to 127 ° C., and stirred for 5 hours while removing water accumulated in the Dean-Stark tube. After cooling to room temperature, 32 g of 10% aqueous ammonia solution was added, and it was confirmed using a pH indicator that the pH of the reaction solution was 6-7. The obtained reaction solution was added dropwise to 20 kg of a methanol / water (mixed mass ratio 80/20) mixed solution to precipitate a polymer. The precipitated polymer was dissolved in MIBK to a solid content concentration of 20% by mass, and then water was removed from the system with anhydrous magnesium sulfate, followed by filtration to contain an ethylenically unsaturated group containing solid content concentration of 20% by mass. A fluorine copolymer solution (A-1) was obtained. Composition analysis of the obtained ethylenically unsaturated group-containing fluorine-containing copolymer (A-1) was conducted by ¹³ C-NMR, the addition rate of acrylic acid was 55 mol%, and the fluorine content determined from the composition was 52 It was mass%.

(Production Example 6): Production of ethylenically unsaturated group-containing fluorine-containing copolymer solution (A-2) A 5-liter separable flask equipped with a magnetic stirrer, a glass condenser, a glass dropping funnel and a thermometer. Into this, 400 g of the hydroxyl group-containing fluorine-containing copolymer (a-2) obtained in Production Example 2 and 3600 g of methyl isobutyl ketone (MIBK) as a solvent were added and stirred at room temperature to obtain a hydroxyl group-containing fluorine-containing copolymer. Dissolved in solvent. Next, 89.0 g of dimethylaniline was charged and stirred at room temperature to confirm that the solution was uniform. Next, using a glass dropping funnel, 60.2 g of acrylic acid chloride was dropped while stirring at room temperature. After completion of the dropwise addition, the mixture was reacted at room temperature for 6 hours under dry air, and then heated using an oil bath so that the temperature inside the system became 40 ° C., and further stirred for 5 hours. After cooling to room temperature, the system was neutralized using a 10% aqueous ammonia solution, and it was confirmed using a pH indicator that the pH of the reaction solution was 6-7. The obtained reaction solution was added dropwise to 30 kg of a methanol / water (mixed mass ratio 95/5) mixed solution to precipitate a polymer. The precipitated polymer was dissolved in MIBK to a solid content concentration of 20% by mass, and then water was removed from the system with anhydrous magnesium sulfate, followed by filtration to obtain a fluorine-containing ethylenically unsaturated group having a solid content concentration of 20%. A copolymer solution (A-2) was obtained. The composition analysis of the obtained ethylenically unsaturated group-containing fluorine-containing copolymer was conducted by ¹³ C-NMR, the addition rate of acrylic acid chloride was 91 mol%, and the fluorine content determined from the composition was 47 mass%. It was.

(Production Example 7): Production of ethylenically unsaturated group-containing fluorine-containing copolymer solution (A-3) Capacity equipped with electromagnetic stirrer, glass cooling tube, glass Dean-Stark tube, glass dropping funnel and thermometer A 5-liter separable flask was charged with 400 g of the hydroxyl group-containing fluorine-containing copolymer (a-3) obtained in Production Example 3 and 1040 g of methyl isobutyl ketone (MIBK) as a solvent, and stirred at room temperature to contain a hydroxyl group. The fluorine-containing copolymer was dissolved in a solvent. Next, 78.6 g of acrylic acid was added and stirred at room temperature to visually confirm that the solution was uniform. A solution obtained by dissolving 10.7 g of sulfuric acid in 160 g of MIBK was dropped while stirring at room temperature using a glass dropping funnel. After completion of dropping, the system was heated using an oil bath under dry air so that the temperature of the system became 120 to 127 ° C., and stirred for 5 hours while removing water accumulated in the Dean-Stark tube. After cooling to room temperature, 37 g of 10% aqueous ammonia solution was added, and it was confirmed using a pH indicator that the pH of the reaction solution was 6-7. The obtained reaction solution was added dropwise to 20 kg of a methanol / water (mixed mass ratio 80/20) mixed solution to precipitate a polymer. The precipitated polymer was dissolved in MIBK to a solid content concentration of 20% by mass, and then water was removed from the system with anhydrous magnesium sulfate, followed by filtration to obtain a fluorine-containing ethylenically unsaturated group having a solid content concentration of 20%. A copolymer solution (A-3) was obtained. Composition analysis of the obtained ethylenically unsaturated group-containing fluorine-containing copolymer (A-3) was conducted by ¹³ C-NMR, the addition rate of acrylic acid was 54 mol%, and the fluorine content determined from the composition was 48 It was mass%.

(Production Example 8): Production of ethylenically unsaturated group-containing fluorine-containing copolymer solution (A-4) A 5-liter separable flask equipped with a magnetic stirrer, a glass condenser, a glass dropping funnel and a thermometer. Into this, 400 g of the hydroxyl group-containing fluorine-containing copolymer (a-4) obtained in Production Example 4 and 3600 g of methyl isobutyl ketone (MIBK) as a solvent were added and stirred at room temperature to obtain a hydroxyl group-containing fluorine-containing copolymer. Dissolved in solvent. Next, 89.0 g of dimethylaniline was charged and stirred at room temperature to confirm that the solution was uniform. Next, using a glass dropping funnel, 60.2 g of acrylic acid chloride was dropped while stirring at room temperature. After completion of the dropwise addition, the mixture was reacted at room temperature for 6 hours under dry air, and then heated using an oil bath so that the temperature inside the system became 40 ° C., and further stirred for 5 hours. After cooling to room temperature, the system was neutralized using a 10% aqueous ammonia solution, and it was confirmed using a pH indicator that the pH of the reaction solution was 6-7. The obtained reaction solution was added dropwise to 30 kg of a methanol / water (mixed mass ratio 95/5) mixed solution to precipitate a polymer. The precipitated polymer was dissolved in MIBK to a solid content concentration of 20% by mass, and then water was removed from the system with anhydrous magnesium sulfate, followed by filtration to contain an ethylenically unsaturated group-containing solid content concentration of 20%. A fluorine copolymer solution (A-4) was obtained. The composition analysis of the obtained ethylenically unsaturated group-containing fluorine copolymer was conducted by ¹³ C-NMR, the addition rate of acrylic acid chloride was 94 mol%, and the fluorine content determined from the composition was 46 mass%. .

(Comparative Production Example 1): Production of ethylenically unsaturated group-containing fluorine-containing copolymer solution (A'-1) Production into a 3 liter separable flask equipped with a magnetic stirrer, a glass condenser, and a thermometer. 100 g of the hydroxyl group-containing fluorine-containing copolymer (a-2) obtained in Example 2, 0.02 g of 2,6-di-t-butylmethylphenol as a polymerization inhibitor, 766.2 g of MIBK as a solvent, and After adding 35.2 g of 2-methacryloyloxyethyl isocyanate and stirring until the solution is uniform, 0.3 g of dibutyltin dilaurate is added to start the reaction, and the temperature of the system is maintained at 55 to 65 ° C. Stirring was continued for 5 hours under dry air to obtain an ethylenically unsaturated group-containing fluorine-containing copolymer solution (A′-1) (solid content concentration: 20% by weight). The composition analysis of the obtained ethylenically unsaturated group-containing fluorine-containing copolymer was conducted by ¹³ C-NMR, and the fluorine content determined from the composition was 42% by weight.

(Comparative Production Example 2): Production of hydroxyl-containing fluorine-containing copolymer (a'-1) After a 2.0-liter stainless steel autoclave with an electromagnetic stirrer was sufficiently substituted with nitrogen gas, 400 g of ethyl acetate, perfluoro ( Propyl vinyl ether) (FPVE) 53.2 g, ethyl vinyl ether (EVE) 64.9 g, hydroxyethyl vinyl ether (HEVE) 8.8 g, lauroyl peroxide 1.00 g, azo group-containing poly (8) 6.0 g of dimethylsiloxane (VPS1001 (trade name), manufactured by Wako Pure Chemical Industries, Ltd.) and 20.0 g of nonionic reactive emulsifier (NE-30 (trade name), manufactured by Asahi Denka Kogyo Co., Ltd.) The oxygen in the system was removed again with nitrogen gas.
Next, the temperature was raised and the reaction was continued with stirring at 70 ° C. for 20 hours. Then, the autoclave was cooled with water to stop the reaction.
After the temperature of the reaction solution reached room temperature, the autoclave was opened, the reaction solution was recovered, and then the reaction solution was added dropwise to 30 kg of a methanol / water mixed solution (mixing weight ratio 95/5). The precipitate was taken out and dried under reduced pressure at 40 ° C. to obtain a hydroxyl group-containing fluorine-containing copolymer (a′-1).

(Comparative Production Example 3): Synthesis of Ethylenically Unsaturated Group-Containing Fluoropolymer (A′-2) Comparative Production Example to a 1-liter separable flask equipped with a magnetic stirrer, a glass condenser, and a thermometer 50.0 g of the hydroxyl group-containing fluoropolymer (a′-1) obtained in 2 and 0.01 g of 2,6-di-t-butylmethylphenol and 370 g of MIBK as a polymerization inhibitor were added, and the hydroxyl group was contained at 20 ° C. Stirring was performed until the fluoropolymer 1 was dissolved in MIBK and the solution became transparent and uniform. Next, 15.1 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. The MIBK solution of the ethylenically unsaturated group-containing fluoropolymer (A′-2) was obtained by maintaining at −65 ° C. and continuing stirring for 5 hours.

(Production Example 9): Preparation of hard coat layer composition Phosphorus-containing tin oxide dispersion (ELCOM JX-1001 PTV manufactured by Catalyst Chemical Industry Co., Ltd., dispersion solvent: propylene glycol monomethyl ether, phosphorus-containing) 80 parts by weight of tin oxide 30% by weight, average primary particle size 20 nm, dispersant 2.17% by weight), dipentaerythritol hexaacrylate (trade name KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) ) 15.6 parts, bis (acryloyloxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-DCP: “Tricyclodecanediyldimethanol diacrylate”, Hereinafter may be referred to as B-2.) 15.6 parts, 1-hydroxycyclohexyl phenyl ketone (Ciba Specialty Chemicals Co., Ltd. Irgacure 184, molar absorption coefficient at 313 nm: 80 L / mol · cm, hereinafter sometimes referred to as C-1) 4.5 parts, and propylene glycol monomethyl ether 50 parts, Was stirred at 50 ° C. for 2 hours to obtain a uniform hard coat layer composition. When 2 g of this hard coat layer composition was weighed on an aluminum dish, dried on a hot plate at 140 ° C. for 1 hour and weighed to determine the solid content, it was 35% by weight.

(Manufacture example 10): Manufacture of base film with a hard coat layer for evaluation of cured film physical properties The composition for hard coat layer obtained in manufacture example 9 was used with an ARTON film G7810 (JSR ( Co., Ltd., norbornene resin film, film thickness 188 μm), and dried in an oven at 80 ° C. for 3 minutes. Subsequently, the coating film was UV-cured under a light irradiation condition of 1 J / cm ² using a metal halide lamp in the atmosphere to prepare a base film with a hard coat layer. It was 3 micrometers when the film thickness of the hard-coat layer was measured with the stylus type surface shape measuring device.

(Production Example 11): Production of alkoxysilane (1) In a dry air, 20.6 parts of isophorone diisocyanate was stirred with respect to a solution consisting of 7.8 parts of mercaptopropyltrimethoxysilane and 0.2 parts of dibutyltin dilaurate. After dropwise addition at 1 ° C over 1 hour, the mixture was stirred at 60 ° C for 3 hours. To this was added dropwise 71.4 parts of pentaerythritol triacrylate at 30 ° C. over 1 hour, and then heated and stirred at 60 ° C. for 3 hours to obtain alkoxysilane (1).
In the infrared absorption spectrum of the product, the absorption peak of 2550 Kaiser characteristic of the mercapto group and the absorption peak of 2260 Kaiser characteristic of the isocyanate group disappeared. Characteristic 1720 Kaiser peak and acryloyl group characteristic of carbonyl in —O—C (═O) —NH—] and [—S—C (═O) —NH—] groups A peak of Kaiser was observed, and an acryloyl group, a [—S—C (═O) —NH—] group, and a [—O—C (═O) —NH—] group as polymerizable unsaturated groups were observed. It was shown that the alkoxysilane (1) having both was produced.

(Production Example 12): Production of reactive silica particle sol (D-1) bonded with an organic compound having a polymerizable unsaturated group Silica particle sol (methyl ethyl ketone silica sol, MEK-ST-L, manufactured by Nissan Chemical Industries, Ltd.) Number average particle size 0.05 μm, silica concentration 30%) 143 g (43 g as silica particles), solution 2.8 g of alkoxysilane (1) prepared in Production Example 11, distilled water 0.1 g, p-hydroquinone monomethyl ether 0 .01g was mixed and heated and stirred at 65 ° C. After 4 hours, 1.0 g of orthoformate methyl ester was added and the mixture was further heated for 1 hour to obtain a reactive silica particle sol (D-1) having a solid content of 31%.

(Production Example 13): Production of reactive silica particle sol (D-2) bonded with an organic compound having a polymerizable unsaturated group Silica particle sol (methyl ethyl ketone silica sol, MEK-ST manufactured by Nissan Chemical Industries, Ltd., number average) 143 g (particle size 10 μm, silica concentration 30%) 143 g (43 g as silica particles), 2.8 g of alkoxysilane (1) solution prepared in Production Example 11, 0.1 g distilled water, 0.01 g p-hydroquinone monomethyl ether are mixed And heated and stirred at 65 ° C. After 4 hours, 1.0 g of orthoformate methyl ester was added and the mixture was further heated for 1 hour to obtain a reactive silica particle sol (D-2) having a solid content of 31%.

［式（１７）中、「Ａｃｒｙｌ」は、アクリロイル基を示す。］ (Production Example 14): Production of a compound represented by the following formula (17) (component (B))

[In the formula (17), “Acryl” represents an acryloyl group. ]

To a solution consisting of 18.8 parts of isophorone diisocyanate and 0.2 part of dibutyltin dilaurate in a container equipped with a stirrer, NK ester A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd. 93 parts) was added dropwise at 10 ° C. for 1 hour, and then stirred at 60 ° C. for 6 hours to obtain a reaction solution.
When the amount of residual isocyanate in this reaction liquid was measured by FT-IR in the same manner as in Production Example 3, it was 0.1% by weight or less, and it was confirmed that the reaction was carried out almost quantitatively. Moreover, it confirmed that a urethane bond and an acryloyl group (polymerizable unsaturated group) were included in the molecule | numerator.
As a result, 75 parts of the compound represented by the formula (17) was obtained, and 37 parts of pentaerythritol tetraacrylate which was not involved in the reaction were mixed.

Hereinafter, preparation examples of the curable resin composition are shown in Examples 1 to 7 and Comparative Examples 1 and 2.
Example 1
As shown in Table 1, 365 g of the ethylenically unsaturated group-containing fluorine-containing copolymer (A-1) synthesized in Production Example 5, a polyfunctional (meth) acrylate containing at least two (meth) acryloyl groups 25 g of dipentaerythritol pentaacrylate as a compound (hereinafter referred to as “polyfunctional (meth) acrylate compound”) and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 as a photopolymerization initiator -2g of ON (Irgacure 907, manufactured by Ciba Specialty Chemicals) and 2108g of MIBK were charged into a glass separable flask equipped with a stirrer and stirred at 23 ° C for 1 hour to obtain a uniform curable resin composition. Moreover, it carried out similarly to manufacture example 9, and calculated | required solid content.

(Examples 2-7 and Comparative Examples 1-2)
Except having set it as the composition shown in Table 1, it carried out similarly to Example 1, and obtained each curable resin composition.

(Test example)
The refractive index, scratch resistance, and coatability of the cured products obtained by curing the curable resin compositions obtained in the respective Examples and Comparative Examples were measured by the following measuring methods. The obtained results are shown in Table 1.

(1) [Evaluation of cured film]
(1-1) Refractive index Each curable resin composition was applied onto a silicon wafer by a spin coater so that the thickness after drying was about 0.1 μm, and then 0% using a high-pressure mercury lamp under nitrogen. It was cured by irradiating with ultraviolet rays under a light irradiation condition of 5 J / cm ² . The obtained cured product was measured refractive index at a wavelength of 589nm at 25 ° C. using an ellipsometer to ^{_(n D 25).}

(2) [Evaluation of antireflection film]
(2-1) Reflectance The reflectance of each of the obtained samples for evaluation was measured using a spectral reflectance measuring device (a self-recording spectrophotometer U-3410 incorporating a large sample chamber integrating sphere attachment device 150-09090, Hitachi, Ltd. )), The reflectance was measured and evaluated in the wavelength range of 340 to 700 nm. 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 evaluation criteria.
A: The reflectance is less than 1.5%.
X: Reflectance is 1.5% or more.

(2-2) Scratch resistance 1 (steel wool resistance)
Steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) is attached to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of each evaluation sample is loaded with 200 g. Under the above conditions, rubbing was repeated 10 times, and the presence or absence of scratches on the surface of the cured film was visually confirmed and evaluated according to the following table.
A: Hardened film peeling or scratches are hardly observed.
○: A thin scratch is observed in the cured film.
Δ Scratches are observed in the cured film.
X: Peeling is recognized in a part of the cured film.

(2-3) Scratch resistance 2 (cloth abrasion resistance)
Each curable resin composition was applied on the film with a hard coat obtained in Production Example 10 using a wire bar coater # 3, and dried in an oven at 80 ° C. for 1 minute. Next, using a metal halide lamp in a nitrogen atmosphere, the coating film was UV-cured under a light irradiation condition of 1 J / cm ² to form a low refractive index layer, thereby producing an antireflection laminate.

The surface of the prepared sample for evaluation was rubbed with a cellulose nonwoven fabric soaked in ethanol (trade name Bencott, Asahi Kasei Kogyo Co., Ltd.) 200 times by hand, and the scratch resistance of the evaluation sample surface was visually observed. Confirmed and evaluated according to the following table or criteria.
A: The sample surface for evaluation is intact.
○: The surface of the sample for evaluation has fine scratches.
Δ: The surface of the evaluation sample is scratched.
X: Peeling of the coating film is observed.

(2-4) Scratch resistance after storage in wet heat environment (cloth rubbing resistance)
The sample for evaluation was allowed to stand for 1 week under conditions of 80 ° C. and 95% RH, and then the surface was reciprocated using a cellulose nonwoven fabric impregnated with ethanol (trade name Bencott, Asahi Kasei Kogyo Co., Ltd.). By rubbing by hand 200 times, the durability of the sample surface for evaluation was visually confirmed and evaluated according to the following table or criteria.
A: The sample surface for evaluation is intact.
○: The surface of the sample for evaluation has fine scratches.
Δ: The surface of the evaluation sample is scratched.
X: Peeling of the coating film is observed.

(2-5) Scratch resistance after immersion in aqueous alkali solution (cloth rubbing resistance)
The sample for evaluation described above was immersed in a 2N aqueous sodium hydroxide solution at 25 ° C. for 2 minutes, washed with distilled water and air-dried, and then the cellulose nonwoven fabric impregnated with ethanol (trade name Bencott, Asahi Kasei Kogyo ( The surface of the sample for evaluation was visually checked for scratch resistance after immersion in an aqueous alkaline solution and evaluated according to the following evaluation criteria.
A: The sample surface for evaluation is intact.
○: The surface of the sample for evaluation has fine scratches.
Δ: The surface of the evaluation sample is scratched.
X: Peeling of the coating film is observed.

(3) [Evaluation of composition]
(3-1) Coatability Each curable resin composition was coated on the curable resin composition coating substrate prepared in Production Example 10 using a wire bar coater (# 3), and then an oven. Medium was dried at 80 ° C. for 1 minute to form a coating film. Next, ultraviolet rays were irradiated under a light irradiation condition of 1 J / cm ² using a high-pressure mercury lamp under nitrogen to prepare a sample for evaluation. The surface of the obtained coating film was visually confirmed and evaluated according to the following evaluation criteria.
◎: Uniform coating without defects in the entire coating film ○: Defects are observed in a part of the coating film, but almost uniform coating film △: Defects are observed in a part of the coating film, and coating film unevenness X seen: Defects are found on one side of the coating

The component names in Table 1 are as follows.
Irgacure 907; 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one: FM0725 manufactured by Ciba Specialty Chemicals Co., Ltd .; acryloyl-modified polydimethylsiloxane: Chisso Corporation Floren AC901; acrylic Mixture of vinyl ether polymer and polyalkylsiloxane: Kyoeisha Chemical Co., Ltd. MIBK; methyl isobutyl ketone

According to the present invention, a cured product having a lower refractive index can be obtained by using an ethylenically-unsaturated-group-containing fluorine-containing copolymer having excellent scratch resistance, coating properties, and durability and having a high fluorine content. Provided are a curable resin composition to be applied, and a cured film obtained by curing the composition.
ADVANTAGE OF THE INVENTION According to this invention, the antireflection film which was excellent in the antireflection characteristic and was excellent in abrasion resistance, coating property, and durability is provided.

It is a schematic diagram which shows one Embodiment of the anti-reflective film 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 (6)

(A) an ethylenically unsaturated group-containing fluorine-containing copolymer;
(B) a compound containing two or more (meth) acryloyl groups other than component (A);
(C) A curable resin composition containing a compound that generates active species upon irradiation with active energy rays,
The (A) ethylenically unsaturated group-containing fluorine-containing copolymer comprises a structural unit (a) represented by the following formula (1), a structural unit (b ′) represented by the following formula (2 ′), and the following: Containing a structural unit (c) represented by formula (3),
The total amount of structural units (a), (b ′) and (c) in the (A) ethylenically unsaturated group-containing fluorine-containing copolymer is 80% by mass or more, and
The structural units (a), (b ′) and (c) are based on a total of 100 mol%,
(A) 40-55 mol%,
(B ') 2-60 mol% and (c) It contains in the ratio of less than 10 mol%, The curable resin composition characterized by the above-mentioned.
Structural unit (a):

[Wherein, 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)]
Structural unit (b ′):

[In the formula, R ³ represents a hydrogen atom or a methyl group, and R ²⁴ represents the following formula (6) or (7)

Or

(In the formula, R represents a hydrogen atom or a methyl group, and x represents 0 to 2).]
Structural unit (c):

[In the formula, R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a group represented by —O (CH ₂ ) _x R ⁸ (R ⁸ represents a fluoroalkyl group, and x is 0 to 2). Show] The said (A) ethylenically unsaturated group containing fluorine-containing copolymer contains 0.1-10 mass% of structural units (d) represented by following formula (4) in this copolymer. Item 2. A curable resin composition according to Item 1.
Structural unit (d):

[Wherein R ⁹ and R ¹⁰ may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group] The said (A) ethylenically unsaturated group containing fluorine-containing copolymer contains 1-15 mass% of structural units (e) represented by following formula (5) in this copolymer. Or the curable resin composition of 2.
Structural unit (e):

[Wherein R ¹⁹ represents a group having an emulsifying action]   The curable resin composition as described in any one of Claims 1-3 containing the particle | grains which have a silica as a main component.   The cured film obtained by hardening the curable resin composition as described in any one of Claims 1-4. An antireflection film having a layer comprising the cured film according to claim 5.

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