JP5572297B2 - Polymerizable fluorine-containing compound, antireflection film, antireflection film, image display device and fluorine-containing alcohol using the same - Google Patents

Description

  The present invention relates to a polymerizable fluorine-containing compound, an antireflection film, an antireflection film and an image display device using the same. More specifically, the present invention relates to a polymerizable fluorine-containing compound suitable for forming a low refractive index layer excellent in scratch resistance, an antireflection film, an antireflection film and an image display device using the same. Moreover, this invention relates to the fluorine-containing alcohol used as these raw materials.

  The fluorine-containing polyfunctional monomer gives a polymer having a low refractive index and a high hardness by using it as a polymer crosslinking agent or by polymerizing itself. Such fluoropolymers are excellent in antifouling properties and are used in fields such as antireflection films, optical fiber cladding materials and paints. As fluorine-containing polyfunctional monomers, 2 to 4 and 6 functional fluorine-containing polyfunctional (meth) acrylic acid esters have been known so far (see, for example, Patent Documents 1 to 6). However, these fluorine-containing polyfunctional monomers have a high refractive index, and if the fluorine content is increased to improve the refractive index, the scratch resistance is lowered. Further, in the conventional method for producing a fluorine-containing polymer, it has been difficult to selectively obtain a desired compound in high yield in the synthesis of a fluorine-containing intermediate before introducing a polymerizable group (Patent Document 7). On the other hand, attempts have been made to efficiently synthesize desired fluorine-containing intermediates using a liquid phase fluorination technique, thereby improving the above problems (Patent Documents 8 and 9). However, there is still room for improvement in the refractive index and scratch resistance. In particular, there has been a demand for further lowering the refractive index of the fluorine-containing polyfunctional monomer described in Patent Document 9.

JP 2001-330706 A JP 2001-262011 A JP 2001-40249 A JP 2000-1111716 A Japanese Patent Laid-Open No. 11-60637 Japanese Patent Laid-Open No. 10-182746 JP-A 63-265920 JP 2006-28280 A JP 2008-106036 A

  An object of the present invention is to provide a polymerizable fluorine-containing compound which has a low refractive index and a high hardness and gives a polymer which is stable against external stimuli such as contamination and shearing. Further, the present invention is a coating-type antireflection film suitable for mass production, having a low refractive index layer having a low reflectance, high hardness, and excellent scratch resistance, using the polymerizable fluorine-containing compound described above. An object is to provide an antireflection film and an image display device. Furthermore, this invention aims at provision of the polyhydric fluorine-containing alcohol used as the said raw material.

［一般式（Ｉ）中、Ｒｆは下記構造式Ｒｆ−１〜Ｒｆ−１１のいずれかの有機基を表す。Ｒｆ_１は炭素数１〜２０の直鎖または分岐のペルフルオロアルキル基または炭素数３〜１２のペルフルオロシクロアルキル基を表す。複数存在するＲｆ_１は各々同一でも異なっていても良い。Ｒｆ_２は炭素数１〜２０の直鎖または分岐のペルフルオロアルキル基、炭素数３〜１２のペルフルオロシクロアルキル基またはフッ素原子を表す。複数存在するＲｆ_２は各々同一でも異なっていても良い。ただし、一般式（Ｉ）におけるａ個存在するユニットのうち少なくとも１つのユニットにおけるＲｆ_１とＲｆ_２の炭素数の合計は３以上である。Ａは単結合または上記一般式（ＩＩ）で表される２価の連結基を表す。複数存在するＡは各々同一でも異なっていても良い。一般式（Ｉ）および一般式（ＩＩ）において、Ｑは水素原子、−ＣＯＣ（Ｒ_０）＝ＣＨ_２、アリル基、エポキシアルキレン基、−（ＣＨ_２）_ＸＳｉ（Ｗ）_３、−（ＣＨ_２）_ｙＮＣＯまたは−（ＣＨ_２）_ｚＣＮ（ここで、Ｒ_０は水素原子、フッ素原子、メチル基またはトリフルオロメチル基を表す。Ｗはアルコキシ基または水酸基を表す。ｘ、ｙおよびｚはそれぞれ１以上の整数を表す。３個のＷは互いに同一でも異なってもよい。）を表す。複数存在するＱは各々同一でも異なっていても良い。ただし、一般式（Ｉ）および一般式（ＩＩ）におけるＱのうち少なくとも１つは−ＣＯＣ（Ｒ_０）＝ＣＨ_２、アリル基、エポキシアルキレン基、−（ＣＨ_２）_ＸＳｉ（Ｗ）_３、−（ＣＨ_２）_ｙＮＣＯまたは−（ＣＨ_２）_ｚＣＮを表す。ａは３〜６の整数を表し、ｂ、ｃはそれぞれ独立に０〜１００の整数を表す。］

＜２＞
前記一般式（Ｉ）において、前記Ｑが−ＣＯＣ（Ｒ）＝ＣＨ_２（ここで、Ｒは水素原子、フッ素原子、メチル基またはトリフルオロメチル基を表す。）であることを特徴とする＜１＞に記載の重合性含フッ素化合物。
＜３＞
前記一般式（Ｉ）において、全てのＡが単結合であることを特徴とする＜１＞または＜２＞に記載の重合性含フッ素化合物。
＜４＞
前記一般式（Ｉ）において、前記Ｒｆ_１が炭素数３以上のペルフルオロアルキル基であり、前記Ｒｆ_２がフッ素原子であることを特徴とする＜１＞〜＜３＞のいずれか１項に記載の重合性含フッ素化合物。
＜５＞
下記一般式（ＩＩＩ）で表されることを特徴とする重合性含フッ素化合物。

［一般式（ＩＩＩ）中、Ｒｆ’は、炭素原子とフッ素原子とのみから、または炭素原子とフッ素原子と酸素原子とのみから構成される鎖状または環状の、炭素数５〜５０のａ’価の有機基であり、Ｒｆ_１’は炭素数３以上のペルフルオロアルキル基であり、Ｒは水素原子、フッ素原子、メチル基またはトリフルオロメチル基であり、ａ’は３から６の整数を表す。］
＜６＞
＜１＞〜＜５＞のいずれか１項に記載の重合性含フッ素化合物を少なくとも１種含有する硬化性樹脂組成物を硬化した低屈折率層を有することを特徴とする反射防止膜。
＜７＞
＜１＞〜＜５＞のいずれか１項に記載の重合性含フッ素化合物および無機酸化物微粒子を含有する硬化性樹脂組成物を硬化した低屈折率層を有することを特徴とする反射防止膜。
＜８＞
前記無機酸化物微粒子が中空シリカ微粒子であることを特徴とする＜７＞に記載の反射防止膜。
＜９＞
透明支持体上に＜６＞〜＜８＞のいずれか１項に記載の反射防止膜が設けられたことを特徴とする反射防止フィルム。
＜１０＞
＜９＞に記載の反射防止フィルムを備えたことを特徴とする画像表示装置。
＜１１＞
下記一般式（ＩＶ）で表されることを特徴とする含フッ素アルコール。

［一般式（ＩＶ）中、Ｒｆは下記構造式Ｒｆ−１〜Ｒｆ−１１のいずれかの有機基を表す。Ｒｆ_１は炭素数１〜２０の直鎖または分岐のペルフルオロアルキル基または炭素数３〜１２のペルフルオロシクロアルキル基を表す。複数存在するＲｆ_１は各々同一でも異なっていてもよい。Ｒｆ_２は炭素数１〜２０の直鎖または分岐のペルフルオロアルキル基、炭素数３〜１２のペルフルオロシクロアルキル基またはフッ素原子を表す。複数存在するＲｆ_２は各々同一でも異なっていてもよい。ただし、一般式（ＩＶ）におけるａ個存在するユニットのうち少なくとも１つのユニットにおけるＲｆ_１とＲｆ_２の炭素数の合計は３以上である。Ａは単結合または上記一般式（Ｖ）で表される２価の連結基を表す。複数存在するＡは各々同一でも異なっていてもよい。ａは３〜６の整数を表し、一般式（Ｖ）中、ｂ、ｃはそれぞれ独立に０〜１００の整数を表す。］

＜１２＞
下記一般式（ＶＩ）で表されることを特徴とする含フッ素アルコール。

［一般式（ＶＩ）中、Ｒｆ’ は、炭素原子とフッ素原子とのみから、または炭素原子とフッ素原子と酸素原子とのみから構成される鎖状または環状の、炭素数５〜５０のａ’価の有機基であり、Ｒｆ_１’は炭素数３以上のペルフルオロアルキル基であり、複数存在するＲｆ_１’は各々同一でも異なっていてもよい。ａ’は３〜６の整数を表す。］
本発明は、前記＜１＞〜＜１２＞に係る発明であるが、以下、それ以外の事項（例えば、下記１〜１５の事項など）についても記載している。
１． 下記一般式（Ｉ）で表されることを特徴とする重合性含フッ素化合物。 As a result of intensive studies to solve the above problems, it has been found that the object can be achieved by the following means.
<1>
A polymerizable fluorine-containing compound represented by the following general formula (I):

[In General Formula (I), Rf represents any organic group of the following structural formulas Rf-1 to Rf-11 . Rf ₁ represents a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms or a perfluorocycloalkyl group having 3 to 12 carbon atoms. A plurality of Rf ₁ may be the same or different. Rf ₂ represents a linear or branched perfluoroalkyl group, perfluorocycloalkyl group or a fluorine atom having 3 to 12 carbon atoms having 1 to 20 carbon atoms. A plurality of Rf ₂ may be the same or different. However, the total number of carbon atoms of Rf ₁ and Rf ₂ in at least one unit among the a units present in the general formula (I) is 3 or more. A represents a single bond or a divalent linking group represented by the general formula (II). A plurality of A may be the same or different. In the general formula (I) and general formula (II), Q is a hydrogen _{atom, -COC (R 0) = CH} 2, allyl, epoxy alkylene _{group, - (CH 2) X Si} (W) 3, - (CH ₂ ) _y NCO or — (CH ₂ ) _z CN (where R ₀ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, W represents an alkoxy group or a hydroxyl group, x, y and z are Each represents an integer greater than or equal to 1. Three W may mutually be same or different. Plural Qs may be the same or different. However, at least one of Q in the general formula (I) and the general formula (II) is —COC (R ₀ ) ═CH ₂ , an allyl group, an epoxyalkylene group, — (CH ₂ ) _X Si (W) ₃ , - _{(CH 2)} y NCO or - represents a _{(CH 2)} z CN. a represents an integer of 3 to 6, and b and c each independently represents an integer of 0 to 100. ]

<2>
In the general formula (I), the Q is —COC (R) ═CH ₂ (wherein R represents a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group). The polymerizable fluorine-containing compound according to 1>.
<3>
The polymerizable fluorine-containing compound according to <1> or <2>, wherein in the general formula (I), all A are single bonds.
<4>
In formula (I), wherein Rf ₁ is the number 3 or more perfluoroalkyl group having a carbon according to any one of <1> to <3>, wherein the Rf ₂ is a fluorine atom Polymerizable fluorine-containing compound.
< 5 >
A polymerizable fluorine-containing compound represented by the following general formula (III):

[In the general formula (III), Rf ′ is a chain or cyclic a ′ having 5 to 50 carbon atoms composed of only carbon atoms and fluorine atoms, or composed of only carbon atoms, fluorine atoms and oxygen atoms. Rf ₁ ′ is a perfluoroalkyl group having 3 or more carbon atoms, R is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and a ′ represents an integer of 3 to 6 . ]
< 6 >
An antireflection film comprising a low refractive index layer obtained by curing a curable resin composition containing at least one polymerizable fluorine-containing compound according to any one of <1> to < 5 >.
< 7 >
An antireflection film comprising a low refractive index layer obtained by curing a curable resin composition containing the polymerizable fluorine-containing compound and inorganic oxide fine particles according to any one of <1> to < 5 > .
< 8 >
< 7 > The antireflection film according to < 7 >, wherein the inorganic oxide fine particles are hollow silica fine particles.
< 9 >
An antireflection film, wherein the antireflection film according to any one of < 6 > to < 8 > is provided on a transparent support.
<1 0 >
< 9 > The image display apparatus provided with the antireflection film as described in < 9 >.
<1 1 >
A fluorine-containing alcohol represented by the following general formula (IV).

[In General Formula (IV), Rf represents any organic group of the following structural formulas Rf-1 to Rf-11 . Rf ₁ represents a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms or a perfluorocycloalkyl group having 3 to 12 carbon atoms. A plurality of Rf ₁ may be the same or different. Rf ₂ represents a linear or branched perfluoroalkyl group, perfluorocycloalkyl group or a fluorine atom having 3 to 12 carbon atoms having 1 to 20 carbon atoms. A plurality of Rf ₂ may be the same or different. However, the total number of carbon atoms of Rf ₁ and Rf ₂ in at least one unit among the a units present in the general formula (IV) is 3 or more. A represents a single bond or a divalent linking group represented by the general formula (V). A plurality of A may be the same or different. a represents an integer of 3 to 6, and in the general formula (V), b and c each independently represents an integer of 0 to 100. ]

<1 2 >
A fluorine-containing alcohol represented by the following general formula (VI):

[In the general formula (VI), Rf ′ is a chain or cyclic a ′ having 5 to 50 carbon atoms composed of only carbon atoms and fluorine atoms, or composed of only carbon atoms, fluorine atoms and oxygen atoms. Rf ₁ ′ is a perfluoroalkyl group having 3 or more carbon atoms, and a plurality of Rf ₁ ′ may be the same or different from each other. a ′ represents an integer of 3 to 6. ]
The present invention is an invention according to the above <1> to <1 2 >, but hereinafter, other matters (for example, items 1 to 15 below) are also described.
1. A polymerizable fluorine-containing compound represented by the following general formula (I):

[In general formula (I), Rf represents a chain or cyclic a-valent organic group containing at least a carbon atom and a fluorine atom and optionally containing at least one of an oxygen atom and a hydrogen atom. Rf ₁ represents a chain or cyclic monovalent organic group which contains at least a carbon atom and a fluorine atom, and may contain at least one of an oxygen atom and a hydrogen atom. A plurality of Rf ₁ may be the same or different. Rf ₂ includes at least carbon and fluorine atoms, may contain at least one of oxygen atom and hydrogen atom, a monovalent organic group or a fluorine atom chain or cyclic. A plurality of Rf ₂ may be the same or different. However, the total number of carbon atoms of Rf ₁ and Rf ₂ in at least one unit among the a units present in the general formula (I) is 3 or more. A represents a single bond or a divalent linking group represented by the general formula (II). A plurality of A may be the same or different. In general formula (I) and general formula (II), Q represents a polymerizable group or a hydrogen atom. Plural Qs may be the same or different. However, at least one of Q in the general formula (I) and the general formula (II) represents a polymerizable group. a represents an integer of 2 to 20, and b and c each independently represents an integer of 0 to 100. ]
2. At least one of Q in the general formula (I) or (II) is —COC (R ₀ ) ═CH ₂ , an allyl group, an epoxyalkylene group, — (CH ₂ ) _x Si (W) ₃ , — (CH _2). ) _Y NCO or — (CH ₂ ) _z CN (where R ₀ represents a hydrogen atom, a halogen atom or an alkyl group which may have a substituent. W represents an alkoxy group or a hydroxyl group. X, y and z) Each represents an integer greater than or equal to 1. Three W may be mutually the same or different.) The polymerizable fluorine-containing compound as described in 1 above,
3. In the general formula (I), the Q is —COC (R) ═CH ₂ (wherein R represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group). 1. The polymerizable fluorine-containing compound according to 1.
4). In the said general formula (I), said a is an integer of 3-6, The polymerizable fluorine-containing compound in any one of said 1-3 characterized by the above-mentioned.
5. 5. The polymerizable fluorine-containing compound as described in any one of 1 to 4 above, wherein in the general formula (I), all A are single bonds.
6). Any one of 1 to 5 above, wherein, in the general formula (I), Rf ₁ is a perfluoroalkyl group having 3 or more carbon atoms which may contain an oxygen atom, and Rf ₂ is a fluorine atom. The polymerizable fluorine-containing compound according to item.
7). In the general formula (I), the Rf is a trivalent to hexavalent organic group substantially composed of only carbon atoms and fluorine atoms, or carbon atoms, fluorine atoms and oxygen atoms. The polymerizable fluorine-containing compound according to any one of 1 to 6.
8). A polymerizable fluorine-containing compound represented by the following general formula (III):

[Wherein, Rf ′ is an a′-valent organic group substantially composed of carbon atoms and fluorine atoms or only carbon atoms, fluorine atoms and oxygen atoms, and Rf ₁ ′ is the number of carbon atoms which may contain oxygen atoms] 3 or more perfluoroalkyl groups, R is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and a ′ represents an integer of 3 to 6. ]
9. An antireflection film comprising a low refractive index layer obtained by curing a curable resin composition containing at least one polymerizable fluorine-containing compound according to any one of 1 to 8 above.
10. 9. An antireflection film comprising a low refractive index layer obtained by curing a curable resin composition containing the polymerizable fluorine-containing compound and inorganic oxide fine particles according to any one of 1 to 8 above.
11. 11. The antireflection film as described in 10 above, wherein the inorganic oxide fine particles are hollow silica fine particles.
12 An antireflection film, wherein the antireflection film according to any one of the above 9 to 11 is provided on a transparent support.
13. 13. An image display device comprising the antireflection film as described in 12 above.
14 A fluorine-containing alcohol represented by the following general formula (IV).

[In General Formula (IV), Rf represents a chain or cyclic a-valent organic group containing at least a carbon atom and a fluorine atom, and may contain at least one of an oxygen atom and a hydrogen atom. Rf ₁ represents a chain or cyclic monovalent organic group which contains at least a carbon atom and a fluorine atom, and may contain at least one of an oxygen atom and a hydrogen atom. A plurality of Rf ₁ may be the same or different. Rf ₂ includes at least carbon and fluorine atoms, may contain at least one of oxygen atom and hydrogen atom, a monovalent organic group or a fluorine atom chain or cyclic. A plurality of Rf ₂ may be the same or different. A represents a single bond or a divalent linking group represented by the general formula (V). A plurality of A may be the same or different. a represents an integer of 2 to 20, and in general formula (V), b and c each independently represents an integer of 0 to 100. ]
15. A fluorine-containing alcohol represented by the following general formula (VI):

[In general formula (VI), Rf ′ is an a′-valent organic group substantially composed of carbon atoms and fluorine atoms or only carbon atoms, fluorine atoms and oxygen atoms, and Rf ₁ ′ includes oxygen atoms. Or a perfluoroalkyl group having 3 or more carbon atoms, and a plurality of Rf ₁ ′ s may be the same or different. a ′ represents an integer of 3 to 6. ]

The polymerizable fluorine-containing compound of the present invention can be polymerized to give a polymer having a low refractive index and excellent hardness, and excellent scratch resistance and antifouling properties. Furthermore, the antireflection film and the antireflection film obtained from the above-described excellent polymerizable fluorine-containing compound have low reflectance and high hardness and excellent scratch resistance, and an image display device using the antireflection film and the antireflection film is an image display unit. In addition, the display surface can be prevented from deteriorating due to contamination of the display surface or reflection of external light.
In addition, the polyvalent fluorine-containing alcohol of the present invention can be used as a synthetic intermediate for the above materials.

The present invention will be described in detail below.
The polymerizable fluorine-containing compound of the present invention is represented by the following general formula (I).

In general formula (I), Rf represents a chain or cyclic a-valent organic group which contains at least a carbon atom and a fluorine atom, and may contain at least one of an oxygen atom and a hydrogen atom. Rf ₁ represents a chain or cyclic monovalent organic group which contains at least a carbon atom and a fluorine atom, and may contain at least one of an oxygen atom and a hydrogen atom. A plurality of Rf ₁ may be the same or different. Rf ₂ includes at least carbon and fluorine atoms, may contain at least one of oxygen atom and hydrogen atom, a monovalent organic group or a fluorine atom chain or cyclic. A plurality of Rf ₂ may be the same or different. However, the total number of carbon atoms of Rf ₁ and Rf ₂ in at least one unit among the a units in parentheses () in the general formula (I) is 3 or more. A represents a single bond or a divalent linking group represented by the general formula (II). A plurality of A may be the same or different. In general formula (I) and general formula (II), Q represents a polymerizable group or a hydrogen atom. Plural Qs may be the same or different. However, at least one of Q in the general formula (I) and the general formula (II) represents a polymerizable group. a represents an integer of 2 to 20, and b and c each independently represents an integer of 0 to 100.

In general formula (I), Rf contains at least a carbon atom and a fluorine atom, and may contain an oxygen atom and / or a hydrogen atom, which is linear or cyclic, for example, having 2 to 1000 carbon atoms (preferably 4 to 100, more Preferably, it represents an a-valent organic group of 5 to 50). a represents an integer of 2 to 20, preferably an integer of 3 to 6. Rf is preferably a trivalent to hexavalent organic group substantially composed of carbon atoms and fluorine atoms or carbon atoms, fluorine atoms and oxygen atoms. The term “substantially composed of carbon atoms and fluorine atoms or carbon atoms, fluorine atoms and oxygen atoms” means that the proportion of subcomponents containing hydrogen atoms is 10 mol% or less, preferably 5 mol% or less, more preferably It means 1 mol% or less.
Specific examples of Rf are shown below, but the present invention is not limited thereto.

In the general formula (I), Rf ₁ represents a chain or cyclic monovalent organic group which contains at least a carbon atom and a fluorine atom, and may contain an oxygen atom and / or a hydrogen atom. Rf ₁ is preferably a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms (for example, trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorooctyl, perfluorododecyl, perfluorooctadecyl, etc.) or 3 to 3 carbon atoms. 12 perfluorocycloalkyl group (for example, perfluorocyclopentyl, perfluorocyclohexyl, etc.), more preferably a linear or branched perfluoroalkyl group having 3 to 10 carbon atoms.

In the general formula (I), Rf ₂ includes at least carbon and fluorine atoms, may contain an oxygen atom and / or a hydrogen atom, a chain or a monovalent organic group of cyclic or fluorine atom. Rf ₂ is preferably a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms (for example, trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorooctyl, perfluorododecyl, perfluorooctadecyl, etc.), C3 12 perfluorocycloalkyl groups (for example, perfluorocyclopentyl, perfluorocyclohexyl and the like) or a fluorine atom, and more preferably a fluorine atom.
Rf ₁ is preferably a perfluoroalkyl group having 3 or more carbon atoms which may contain an oxygen atom, and Rf ₂ is preferably a fluorine atom.
The total number of carbon atoms of Rf ₁ and Rf ₂ in at least one unit among the a units represented by () in general formula (I) is 3 or more. In all the a units, the total number of carbon atoms of Rf ₁ and Rf ₂ is preferably 3 or more.

In General Formula (I), A represents a single bond or a divalent linking group represented by General Formula (II), and b and c each independently represent an integer of 0 to 100. b is preferably 0 and c is preferably 0 or 1. More preferably, b and c are 0. A is preferably a single bond, more preferably all A are single bonds.
In general formula (I) and general formula (II), Q represents a polymerizable group or a hydrogen atom. However, at least one of Q in the general formula (I) and the general formula (II) represents a polymerizable group. Q preferably represents a polymerizable group. The polymerizable group represented by Q is preferably a radical, a cation, or a condensation polymerizable group, and —COC (R ₀ ) ═CH ₂ , an allyl group, an epoxyalkylene group (preferably an epoxymethylene group), More preferably, it is — (CH ₂ ) _X Si (W) ₃ , — (CH ₂ ) _y NCO or — (CH ₂ ) _z CN. Here, R ₀ represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent, W represents an alkoxy group or a hydroxyl group, x, y and z each represents an integer of 1 or more, 3 Of W may be the same or different. Each of x, y, and z is preferably 1 to 5, and more preferably 1 to 3. The substituent for the alkyl group in R ₀ may be any substituent, but is preferably a halogen atom. R ₀ is preferably a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. More preferably, Q is —COC (R) ═CH ₂ (wherein R represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group).

A plurality of Rf ₁ present in one molecule may be the same or different, but is preferably the same.
A plurality of Rf ₂ present in one molecule may be the same or different, but is preferably the same.
A plurality of Q present in one molecule may be the same or different, but is preferably the same.
A plurality of A present in one molecule may be the same or different from each other.

The compound represented by the general formula (I) is preferably a compound represented by the general formula (III). In the general formula (III), Rf ′ represents an a′-valent organic group substantially composed of only a carbon atom and a fluorine atom or a carbon atom, a fluorine atom and an oxygen atom. A hydrogen atom is considered as an atom other than the carbon atom, fluorine atom, and oxygen atom contained in Rf ′. The term “substantially composed of carbon atoms and fluorine atoms or carbon atoms, fluorine atoms and oxygen atoms” means that the proportion of subcomponents containing hydrogen atoms is 10 mol% or less, preferably 5 mol% or less, more preferably It means 1 mol% or less. Rf ₁ ′ is a perfluoroalkyl group having 3 or more carbon atoms which may contain an oxygen atom, and examples thereof include perfluoropropyl, perfluoroisopropyl, perfluorooctyl, perfluorododecyl, and the like. R is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, preferably a hydrogen atom. a ′ represents an integer of 3 to 6.

  Specific examples of the compound represented by formula (I) are shown below, but the present invention is not limited thereto.

  D in said M9 and M24 represents the integer of 1-50, Preferably it is 1-10, More preferably, it is an integer of 1-5.

  The method for synthesizing the polymerizable fluorine-containing compound represented by the general formula (I) is not particularly limited. However, from the viewpoint of the degree of freedom in molecular design and cost, US Pat. It is preferable to use the liquid phase fluorination reaction described in the pamphlet of No. 56694. As a synthesis route for the polymerizable fluorine-containing compound represented by the general formula (I) using the liquid phase fluorination reaction, for example, the following route using a valent hydroxyl group-containing hydrocarbon compound as a starting material is used. However, the present invention is not limited to these.

  X is a halogen atom (for example, chlorine atom, bromine atom, iodine atom), alkyl or arylsulfonyloxy group (for example, methanesulfonyloxy group, trifluoromethanesulfonyloxy group, benzenesulfonyloxy group, p-toluenesulfonyloxy group), etc. Preferably represents a chlorine atom or a bromine atom.

  Introduction of A (step 4 → 5) can be performed by adding one or more selected from ethylene carbonate, ethylene oxide, and glycidyl alcohol to compound 4 in a block form or a random form. When ethylene carbonate or both ethylene oxide and glycidyl alcohol are introduced, ethylene carbonate or ethylene oxide may be introduced first with respect to compound 4, or glycidyl alcohol may be introduced first. These may be reacted at the same time. This step is not necessarily essential, and the polymerizable group Q may be directly introduced into the compound 4.

  The polymerizable fluorine-containing compound represented by the general formula (I) can be obtained from the fluorine-containing alcohol represented by the general formula (IV). As the fluorine-containing alcohol represented by the general formula (IV), the fluorine-containing alcohol represented by the general formula (VI) is more preferable.

[Fluoropolymer]
The polymerizable fluorine-containing compound (fluorine-containing polyfunctional monomer) can be made into a fluorine-containing polymer by various polymerization methods. In the polymerization, homopolymerization or copolymerization may be performed, and furthermore, it may be used as a crosslinking agent.

  As other monomers that can be copolymerized, ordinary monomers can be used. Particularly, typical examples include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. 2-trifluoroethyl (meth) acrylate, 2,3-pentafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (Meth) acrylate, allyla Radical polymerizable monomers such as coal, ethyl allyl ether, α-fluoroacrylic acid methyl ester, vinyl acetate, ethyl vinyl ketone, butyl vinyl ketone, tetrafluoroethylene, hexafluoropropylene, methyl vinyl ether, ethyl vinyl ether, hydroxyethyl vinyl ether ,

  Tetraethoxysilane, ethyltrimethoxysilane, chlorotrimethoxysilane, aminopropyltriethoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxy Silane, or condensation polymerizable monomers represented by the following chemical formula:

  Glycerol diglycidyl ether, glycerol triglycidyl ether, 1,1,1-trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, bisphenol-A-diglycidyl ether, hydroquinone diglycidyl ether, resorcin diglycidyl ether, fluoroglycinol tri And cationically polymerizable monomers such as glycidyl ether, triglycidyl isocyanurate, ethyl vinyl ether, cyclohexyl vinyl ether, and the like. Among these, from the viewpoint of polymerizability, radical or cation polymerizable monomers are preferable, and radical polymerizable monomers are more preferable.

  The polymerization reaction is preferably bulk polymerization or solution polymerization. In order to obtain a thin film, it is preferable to perform polymerization after applying the curable resin composition containing the polymerizable fluorine-containing compound of the present invention on a substrate and volatilizing the solvent. In this case, in the curable resin composition, the content of the polymerizable fluorine-containing compound of the present invention is not particularly limited, but is preferably 5 to 100% by mass, more preferably 10 to 100% by mass, and 30 More preferably, it is -100 mass%. The polymerization initiation method includes a method using a radical initiator, a method of irradiating light or radiation, a method of adding an acid, a method of irradiating light after adding a photoacid generator, a method of dehydrating condensation by heating, and the like. These polymerization methods and polymerization initiation methods are described in, for example, Tsuruta Shinji, “Polymer Synthesis Method” revised edition (published by Nikkan Kogyo Shimbun, 1971), Takatsu Otsu and Masato Kinoshita, “Experimental Methods for Polymer Synthesis” ", Chemistry Dojin, 1972, pp. 124-154.

  Examples of the solvent used include ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, benzene, toluene, acetonitrile, methylene chloride, Examples include chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and the like. These may be used alone or in combination of two or more.

  As the initiator for radical polymerization, any form of those generating radicals by the action of heat or those generating radicals by the action of light is possible.

As the compound that initiates radical polymerization by the action of heat, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Ammonium sulfate, potassium persulfate, etc., 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, etc. as organic azo compounds, diazoaminobenzene as diazo compounds, Examples thereof include p-nitrobenzenediazonium.

When a compound that initiates radical polymerization by the action of light is used, the coating is cured by irradiation with active energy rays.
Examples of such radical photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds , Disulfide compounds, fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Sensitizing dyes can also be used in combination with these photoradical polymerization initiators.

  The amount of the radical polymerization initiator added is not particularly limited as long as the radical reactive group is an amount capable of initiating a polymerization reaction, but is generally 0.1 to the total solid content in the curable resin composition. 15 mass% is preferable, More preferably, it is 0.5-10 mass%, Most preferably, it is 2-5 mass%.

  The polymerization temperature is not particularly limited, but may be appropriately adjusted depending on the type of initiator. In addition, when a radical photopolymerization initiator is used, heating is not particularly required, but heating may be performed.

In addition to the above, the curable resin composition forming the fluoropolymer contains various additives from the viewpoints of film hardness, refractive index, antifouling property, water resistance, chemical resistance, and slipperiness. You can also
For example, inorganic oxide fine particles such as silica and hollow silica, silicone-based or fluorine-based antifouling agents, or slipping agents can be added. When adding these, it is preferable that it is the range of 0-99 mass% with respect to the total solid of a curable resin composition, It is more preferable that it is the range of 0-70 mass%, 0-50 It is particularly preferable that the mass range.

Next, inorganic oxide fine particles (hereinafter referred to as inorganic fine particles) that can be used in the present invention will be described.
By using the curable resin composition containing inorganic fine particles, in the case of forming the low refractive index layer in the antireflection film, coating amount of the inorganic fine ^{particles, 1mg / m 2 ~100mg / m} 2 are preferred, more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . If the amount of the inorganic fine particles is too small, the effect of improving the scratch resistance is reduced.If the amount is too large, for example, the surface of the low refractive index layer of the antireflection film has fine irregularities, and the appearance and integrated reflectance such as black tightening are reduced. Getting worse. Since the inorganic fine particles are contained in the low refractive index layer, it is desirable that the inorganic fine particles have a low refractive index.

Specifically, inorganic oxide particles or hollow inorganic oxide particles that have been subjected to a treatment for improving dispersibility in an organic solvent dispersion and that have a low refractive index are preferably used. For example, fine particles of silica or hollow silica can be mentioned. The average particle diameter of the silica fine particles is preferably 30% to 150% of the thickness of the low refractive index layer, more preferably 35% to 80%, and still more preferably 40% to 60%. That is, when the thickness of the low refractive index layer is 100 nm, the particle diameter of the silica fine particles is preferably 30 nm to 150 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.
If the particle size of the silica fine particles is too small, the effect of improving the scratch resistance is reduced. If it is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated.
The silica fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably spherical, but there is no problem even if it is indefinite. Here, the average particle diameter of the inorganic fine particles is measured by a Coulter counter.

In order to lower the refractive index of the low refractive index layer, it is preferable to use hollow silica fine particles. The hollow silica fine particles have a refractive index of 1.17 to 1.40, more preferably 1.17 to 1.35, and still more preferably 1.17 to 1.30. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica particles. At this time, when the radius of the cavity in the particle is a and the radius of the particle outer shell is b, the porosity x is calculated by the following mathematical formula (I).
Formula (I)
^{x = (4πa 3/3)} / (4πb 3/3) × 100
The porosity x is preferably 10 to 60%, more preferably 20 to 60%, and most preferably 30 to 60%. If hollow silica particles are made to have a lower refractive index and a higher porosity, the thickness of the outer shell becomes thinner and the strength of the particles becomes weaker. From the viewpoint of scratch resistance, particles of 1.17 or more are present. preferable.
The refractive index of these hollow silica particles can be measured with an Abbe refractometer (manufactured by Atago Co., Ltd.).

  Moreover, the refractive index of this layer can be reduced by containing hollow particles in the low refractive index layer. The refractive index of the layer is preferably 1.20 or more and 1.47 or less, more preferably 1.25 or more and 1.41 or less, and most preferably 1.25 or more and 1.39 or less when hollow particles are used. It is. Methods for preparing hollow silica are described in, for example, JP-A Nos. 2001-233611 and 2002-79616.

Further, at least one kind of silica fine particles having an average particle size of less than 25% of the thickness of the low refractive index layer (hereinafter, referred to as “silica fine particles having a small particle size”) is used as silica fine particles having the above particle size (hereinafter, It is preferably used in combination with “large-sized silica particles”. Since the fine silica particles having a small size can be present in the gaps between the fine silica particles having a large size, the fine particles can contribute as a retaining agent for the fine silica particles having a large size.
When the low refractive index layer is 100 nm, the average particle size of the silica fine particles having a small size is preferably from 1 nm to 20 nm, more preferably from 5 nm to 15 nm, and particularly preferably from 10 nm to 15 nm. Use of such silica fine particles is preferable in terms of raw material costs and a retaining agent effect.

In addition, from the viewpoint of storage stability, the curable resin composition may contain a polymerization inhibitor. Examples of polymerization inhibitors that can be suitably used include hydroquinone, hydroquinone monomethyl ether, mono-tert-butylhydroquinone, catechol, p-tert-butylcatechol, p-methoxyphenol, p-tert-butylcatechol, 2,6 -Phenols such as di-tert-butyl-m-cresol, pyrogallol and β-naphthol; quinones such as benzoquinone, 2,5-diphenyl-p-benzoquinone, p-toluquinone and p-xyloquinone; nitrobenzene, m-di Nitro compounds or nitroso compounds such as nitrobenzene, 2-methyl-2-nitrosopropane, α-phenyl-tert-butylnitrone, 5,5-dimethyl-1-pyrroline-1-oxide; chloranil-amine, diphenylamine, diphenyl Examples include radical polymerization inhibitors such as amines such as picrylhydrazine, phenol-α-naphthylamine, pyridine, and phenothiazine; sulfides such as dithiobenzoyl sulfide and dibenzyltetrasulfide. These may be used alone or in combination.
More preferred are compounds belonging to at least one of phenols, quinones, nitro compounds, nitroso compounds, amines and sulfides. Of these, phenols are preferably used from the viewpoints of refractive index and radical scavenging ability.

  These polymerization inhibitors are preferably added in an amount of 0.0001 to 10% by mass with respect to the total solid content in the curable resin composition, more preferably 0.0001 to 5% by mass, especially Preferably it is 0.001-2 mass%.

In addition, additives such as various silane coupling agents, surfactants, thickeners, and leveling agents may be appropriately added to the curable resin composition as necessary.
The fluorine-containing polymer in the present invention is cured after a curable resin composition containing the polymerizable fluorine-containing compound of the present invention is applied to a high refractive index layer, a medium refractive index layer, or other various base materials described later. Can be formed.

[Antireflection film]
The antireflection film of the present invention has a low refractive index layer formed by curing the curable resin composition containing the polymerizable fluorine-containing compound of the present invention.
The antireflection film of the present invention may have a single layer structure or a multilayer structure. That is, when the antireflection film has a single layer structure, it consists of only a low refractive index layer. When the antireflection film has a multilayer structure, for example, it has at least two layers of a low refractive index layer and a high refractive index layer. The antireflection film preferably has a multilayer structure, and has a two-layer structure of the low refractive index layer and the high refractive index layer, or a medium refractive index layer in addition to the low refractive index layer and the high refractive index layer. A layer structure is preferred.

[Low refractive index layer]
The low refractive index layer is preferably disposed on an upper layer of the high refractive index layer as will be described later. In addition, the upper surface of the low refractive index layer is preferably the surface of the antireflection film.
The refractive index of the low refractive index layer is preferably 1.20 or more and 1.47 or less, more preferably 1.25 or more and 1.41 or less, and further preferably 1.25 or more and 1.39 or less. . The refractive index can be obtained by measurement using an Abbe refractometer or estimation from the reflectance of light from the layer surface.
The thickness of the low refractive index layer is preferably 50 to 400 nm, and more preferably 50 to 200 nm. The haze of the low refractive index layer is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less. The specific strength of the low refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test under a 1 kg load.

[High refractive index layer and medium refractive index layer]
In the antireflection film of the present invention, the high refractive index layer and the medium refractive index layer used in combination with the low refractive index layer are layers each having a higher refractive index than the low refractive index layer. The medium refractive index layer is a layer having a refractive index higher than that of the low refractive index layer and lower than that of the high refractive index layer.

The high refractive index layer and the medium refractive index layer are mainly composed of only an organic material or an organic material and an inorganic material, respectively.
Examples of the organic material used here include thermoplastic resin compositions (eg, polystyrene, polystyrene copolymer, polycarbonate, polymers having aromatic rings other than polystyrene, heterocyclic rings, and alicyclic groups, or halogen groups other than fluorine. A thermosetting resin composition (eg, a resin composition using a melamine resin, a phenol resin, or an epoxy resin as a curing agent); a urethane resin-forming composition (eg, an alicyclic or aromatic isocyanate) And a radically polymerizable composition (a composition comprising a modified resin composition or a modified prepolymer that enables radical curing by introducing a double bond into the polymer or monomer). ) And the like. The organic material used for the high refractive index layer or the medium refractive index layer is preferably a material having a high film forming property.

Note that an organic material and an inorganic material can be used in combination in the high refractive index layer or the medium refractive index layer.
When an organic material and an inorganic material are used in combination, a high refractive index can generally be secured by the inorganic material, and therefore, an organic material having a lower refractive index than that used when the organic material is used alone can be used. Examples of such organic materials include copolymers of acrylic monomers such as pentaerythritol hexaacrylate and vinyl monomers, polyesters, alkyd resins, fibrous polymers, urethane resins, and various types of resins that cure these resins. And a composition containing a curing agent or a compound having a curable functional group. These organic materials are transparent and can disperse inorganic materials stably. Specific examples of the compound having a curable functional group include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol. Polyurethane poly (meth) acrylates such as penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, urethane obtained by reaction of polyisocyanate and hydroxyl-containing (meth) acrylate such as hydroxyethyl (meth) acrylate ( And (meth) acrylate.

Furthermore, an organically substituted silicon compound can be used as the organic material. Examples of the silicon-based compound include a compound represented by the following formula (5) or a hydrolysis product thereof.
Formula (5) R ^a _m (R ^b ) _n SiZ _4-mn
Here, R ^a represents an alkyl group, an alkenyl group, or an aryl group, R ^b represents an alkyl group, an alkenyl group, or an aryl group substituted with halogen, epoxy, amino, mercapto, methacryloyl, or cyano, and Z Represents a hydrolyzable group selected from an alkoxy group, an alkoxyalkoxy group, a halogen atom and an acyloxy group, and m and n are 0, 1 or 2 respectively under the condition that m + n is 1 or 2.

Examples of the inorganic material include inorganic fine particles. It is preferable to constitute the inorganic fine particles.
Examples of inorganic compounds include oxides of metal elements such as aluminum, titanium, zirconium, and antimony. The inorganic fine particles are commercially available as a powder or a colloidal dispersion in which the powder is dispersed in a solvent such as water. When using these, it is preferable to mix and disperse in the said organic material or organosilicon compound.

In addition, as the inorganic material, an inorganic material that is film-forming and can be dispersed in a solvent, or is itself liquid can be used. Examples of such inorganic materials include alkoxides of various elements, salts of organic acids, coordination compounds (eg, chelate compounds) bonded to coordination compounds, and inorganic polymers).
More specifically, titanium tetraethoxide, titanium tetra-i-propoxide, titanium tetra-n-propoxide, titanium tetra-n-butoxide, titanium tetra-sec-butoxide, titanium tetra-tert-butoxide, aluminum tri Ethoxide, aluminum tri-i-propoxide, aluminum tributoxide, antimony triethoxide, antimony riboxide, zirconium tetraethoxide, zirconium tetra-i-propoxide, zirconium tetra-n-propoxide, zirconium tetra-n- Metal alcoholate compounds such as butoxide, zirconium tetra-sec-butoxide and zirconium tetra-tert-butoxide; diisopropoxytitanium bis (acetylacetonate), dibut Xititanium bis (acetylacetonate), diethoxytitanium bis (acetylacetonate), bis (acetylacetonezirconium), aluminum acetylacetonate, aluminum di-n-butoxide monoethylacetoacetate, aluminum di-i-propoxide monomethylacetate Examples thereof include chelate compounds such as acetate and tri-n-butoxide zirconium monoethyl acetoacetate; and inorganic polymers mainly composed of carbon zirconyl ammonium or zirconium.

In addition to the compounds listed above, compounds having a relatively low refractive index can be used in combination for the high refractive index layer and the medium refractive index layer. Examples of such a compound include various alkyl silicates or hydrolysates thereof, particulate silica, particularly silica gel dispersed in colloidal form.
A dispersion solvent or a solvent can be used for the high refractive index layer and the medium refractive index layer. Examples of the dispersion solvent or solvent include cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone toluene, toluene, ethyl acetate, DMF, 2-propanol, and n-butanol.
Furthermore, additives that are usually added to conventional antireflection films can be appropriately used in the high refractive index layer and the medium refractive index layer.

As an embodiment of the high refractive index layer and the medium refractive index layer, a dispersion of the above inorganic material, a monomer such as dipentaerythritol hexaacrylate, a polymerization initiator such as a photopolymerization initiator and a thermal polymerization initiator, What was formed using the composition for layer formation formed by melt | dissolving the sensitizer and catalyst used as needed in a solvent (the same thing as the said dispersion | distribution solvent can be illustrated) is mentioned.
For such a configuration, a configuration related to a high refractive index layer and a medium refractive index layer in a conventional antireflection film is appropriately applied.

  The refractive index of the high refractive index layer is preferably in the range of 1.57 to 2.40. The thickness of the high refractive index layer is preferably 5 nm to 10 μm, more preferably 10 nm to 1 μm, and most preferably 30 nm to 0.5 μm. The haze of the high refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The strength of the high refractive index layer is preferably 1H or more, more preferably 2H or more, and most preferably 3H or more, with a pencil hardness of 1 kg.

The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably in the range of 1.50 to 1.85. It is particularly preferable that inorganic fine particles and a polymer are used for the high refractive index layer, and the middle refractive index layer is formed by adjusting the refractive index to be lower than that of the high refractive index layer. The haze of the medium refractive index layer is preferably 3% or less.
The thickness of the medium refractive index layer is preferably 5 nm to 10 μm, more preferably 10 nm to 1 μm, and most preferably 30 nm to 0.5 μm. The strength of the medium refractive index layer is preferably 1H or more, more preferably 2H or more, and most preferably 3H or more, with a pencil hardness of 1 kg.

[Method of forming antireflection film]
The antireflection film of the present invention forms the high refractive index layer by applying the composition for forming the high refractive index layer or the medium refractive index layer to various substrates and curing it by light irradiation or the like. Then, the curable resin composition for the low refractive index layer is coated on the high refractive index layer or the medium refractive index layer, and further cured by light irradiation or heating. .
The antireflection film of the present invention is preferably used for the following antireflection film and display device, and can also be used for a case cover, an optical lens, a spectacle lens, a window shield, a light cover, and a helmet shield.

[Antireflection film]
The antireflection film of the present invention is obtained by providing the antireflection film of the present invention on a transparent support.
A basic configuration of an antireflection film suitable as an embodiment of the antireflection film of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic view showing a cross section of one embodiment of the antireflection film of the present invention.
An antireflection film 1 shown in FIG. 1 has an antireflection film 6 in which a high refractive index layer 8 and a low refractive index layer 5 are formed in this order on a transparent support 2.
In such a configuration, as described in JP-A-59-50401, when the high refractive index layer 8 satisfies the following formula (II) and the low refractive index layer 5 satisfies the following formula (III), It is preferable because an antireflection film having excellent antireflection performance can be obtained.

Formula (II): (mλ / 4) × 0.7 <n ₁ d ₁ <(mλ / 4) × 1.3

Where m is a positive integer (generally 1, 2 or 3), λ is the wavelength (nm), n ₁ is the refractive index of the high refractive index layer, and d ₁ is the high refractive index layer. The layer thickness (nm).

Formula (III): (nλ / 4) × 0.7 <n ₂ d ₂ <(nλ / 4) × 1.3

Where n is a positive odd number (generally 1), n ₂ is the refractive index of the low refractive index layer, and d ₂ is the layer thickness (nm) of the low refractive index layer.
The refractive index n ₁ of the high refractive index layer is generally at least 0.05 higher than the transparent support, and the refractive index n ₂ of the low refractive index layer is generally at least 0.1 lower than the refractive index of the high refractive index layer and At least 0.05 lower than the transparent support. Further, the refractive index n ₁ of the high refractive index layer is generally in the range of 1.57 to 2.40.

  Further, as described above, the antireflection film of the present invention may have a structure having an antireflection film composed of two layers of a low refractive index layer and a high refractive index layer. It is preferable to form a layer in advance and to have three or more antireflection films on which a low refractive index layer and a high refractive index layer are formed according to the method described above. More preferably, it is a form in which three or more layers of middle, high and low refractive index layers are laminated. An embodiment of such an antireflection film is shown in FIG.

That is, the antireflection film 1 shown in FIG. 2 has a hard coat layer 3 on a transparent support 2, and a medium refractive index layer 7, a high refractive index layer 8, and a low refractive index layer 5 are arranged in this order. The antireflection film 6 is formed.
In such a configuration, as described in JP-A-59-50401, the medium refractive index layer 7 is represented by the following formula (IV), the high refractive index layer 8 is represented by the following formula (V), and the low refractive index layer. 5 preferably satisfies the following numerical formula (VI).

Formula (IV): (hλ / 4) × 0.7 <n ₃ d ₃ <(hλ / 4) × 1.3

Where h is a positive integer (generally 1, 2 or 3), n ₃ is the refractive index of the medium refractive index layer, and d ₃ is the layer thickness (nm) of the medium refractive index layer.

Formula (V): (jλ / 4) × 0.7 <n ₄ d ₄ <(jλ / 4) × 1.3

Where j is a positive integer (generally 1, 2 or 3), n ₄ is the refractive index of the high refractive index layer, and d ₄ is the layer thickness (nm) of the high refractive index layer.

Formula (VI): (kλ / 4) × 0.7 <n ₅ d ₅ <(kλ / 4) × 1.3

Where k is a positive odd number (generally 1), n ₅ is the refractive index of the low refractive index layer, and d ₅ is the layer thickness (nm) of the low refractive index layer.

The refractive index n ₃ of the middle refractive index layer is generally in the range of 1.50 to 1.85, and the refractive index n ₄ of the high refractive index layer is generally in the range of 1.57 to 2.40.
Moreover, (lambda) in numerical formula (II)-(VI) is a wavelength of visible light, and is a value of the range of 380-680 nm. The high refractive index, medium refractive index, and low refractive index described here refer to the relative refractive index between layers. For example, the medium refractive index layer is produced by a method such as changing the content of the high refractive index inorganic fine particles added to the high refractive index layer.

The antireflection film can be provided with a hard coat layer as described above, and may further be provided with a moisture proof layer, an antistatic layer, an undercoat layer and a protective layer. The hard coat layer is provided for imparting scratch resistance to the transparent support. The hard coat layer also has a function of strengthening the adhesion between the transparent support and the layer thereon. The hard coat layer can be formed using an acrylic polymer, a urethane polymer, an epoxy polymer, a silicon polymer, or a silica compound. A pigment may be added to the hard coat layer.
The acrylic polymer is preferably synthesized by a polymerization reaction of a polyfunctional acrylate monomer (eg, polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate). Examples of the urethane polymer include melamine polyurethane. As the silicon-based polymer, a cohydrolyzate of a silane compound (eg, tetraalkoxysilane, alkyltrialkoxysilane) and a silane coupling agent having a reactive group (eg, epoxy, methacryl) is preferably used. Two or more kinds of polymers may be used in combination. As the silica compound, colloidal silica is preferably used. The strength of the hard coat layer is a pencil hardness with a 1 kg load, preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher. On the transparent support, in addition to the hard coat layer, an adhesive layer, a shield layer, a sliding layer and an antistatic layer may be provided. The shield layer is provided to shield electromagnetic waves and infrared rays.

[Transparent support]
Examples of the transparent support that can be preferably used in the present invention include a glass plate and a plastic film, but a plastic film is more preferable. Examples of plastic film materials include cellulose acylates (eg, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene naphthalate). Phthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, , Polypropylene, polyethylene, polymethylpentene), polysulfone, polyethersulfone, polyarylate, polyetherimide, polymethyl Methacrylate and polyether ketone are included. Cellulose acylate, polycarbonate, polyethylene terephthalate and polyethylene naphthalate are preferred, and triacetyl cellulose is more preferred.

  The thickness of the transparent support varies depending on the purpose of use, but is usually in the range of 5 to 500 μm, more preferably in the range of 20 to 250 μm, and most preferably in the range of 30 to 180 μm. In addition, as an optical use, the range of 30-110 micrometers is especially preferable. The production of a cellulose acylate film using a non-chlorine solvent is described in detail in JIII Journal of Technical Disclosure No. 2001-1745, and the cellulose acylate film described therein is also preferably used in the present invention. Can do.

The light transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more. The haze of the transparent support is preferably 2.0% or less, and more preferably 1.0% or less. The refractive index of the transparent support is preferably 1.4 to 1.7. An infrared absorber or an ultraviolet absorber may be added to the transparent support. The addition amount of the infrared absorber is preferably 0.01 to 20% by mass of the transparent support, and more preferably 0.05 to 10% by mass. As a slip agent, particles of an inert inorganic compound may be added to the transparent support. Examples of the inorganic _{compound, SiO 2, TiO 2, BaSO} 4, CaCO 3, talc and kaolin. A surface treatment may be performed on the transparent support.
Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferred, and glow discharge treatment and ultraviolet treatment are more preferred.

[Method for forming antireflection film]
Each layer of the antireflection film is formed by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method or an extrusion coating method (described in US Pat. No. 2,681,294). ) Can be formed by coating directly on the transparent support or through another layer. Two or more layers may be applied simultaneously. For the method of simultaneous application, U.S. Pat. Nos. 2,761,791, 2,941,898, 3,508,947, 3,526,528 and Yuji Harasaki Author, “Coating Engineering”, page 253, Asakura Shoten (1973). The antireflection film of the present application is preferably dried after applying the coating composition of each layer and cured by ionizing radiation or heat. It is preferable to use ionizing radiation, and in the case of curing using ultraviolet rays, ultraviolet rays emitted from light rays such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be used.

  The lower the reflectance of the antireflection film, the better. The average reflectance of the antireflection film is preferably 2% or less, more preferably 1% or less, and most preferably 0.7% or less in the wavelength region of 450 to 650 nm. The haze of the antireflection film (when it has no anti-glare function described below) is preferably 3% or less, more preferably 1% or less, and most preferably 0.5% or less. The strength of the antireflection film is preferably H or higher, more preferably 2H or higher, with a pencil hardness of 1 kg.

  The antireflection film may have an antiglare function that scatters external light. The antiglare function is obtained by forming irregularities on the surface of the antireflection film. In a low refractive index layer using fine particles, irregularities can be formed on the surface of the antireflection film by the fine particles. When the antiglare function obtained by the fine particles is insufficient, a small amount (0.1 nm) of relatively large particles (particle size: 50 nm to 2 μm) is added to the low refractive index layer, high refractive index layer, medium refractive index layer or hard coat layer. ˜50 mass%) may be added. The anti-reflection film expands the viewing angle (especially the downward viewing angle) of the liquid crystal display device, and diffuses light for the purpose of suppressing contrast degradation, gradation or black-and-white reversal, or hue change even when the viewing angle in the viewing direction changes. It may have a function. The light diffusing function can be realized by the effect of internal scattering of translucent fine particles contained in the light diffusing film. When the antireflection film has an antiglare function and / or a light diffusion function, the haze of the antireflection film is preferably 3 to 60%, and more preferably 4 to 40%.

[Image display device]
The image display device of the present invention includes the antireflection film of the present invention.
Examples of the image display device include a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), and a cathode ray tube display device (CRT). In the image display device of the present invention, it is preferable that the transparent support side of the antireflection film is bonded to the image display surface of the image display device.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples at all.

<Example 1: Synthesis of fluorine-containing alcohol and polymerizable fluorine-containing compound>
(Synthesis of Compound Example M5)
According to the following scheme, the fluorine-containing alcohol 5 and the polymerizable fluorine-containing compound M5 of the present invention were synthesized.

(Synthesis of Compound 3)
Trimethylolethane (30 g) was added to a solution of t-butoxypotassium (253 g) in t-butanol (1000 ml), and 2-bromopentanoic acid (203 g) was further added dropwise. The reaction solution was stirred at reflux temperature for 6 hours, cooled to room temperature, 36 mass% aqueous hydrochloric acid (200 ml) and methanol (500 ml) were added, and insoluble materials were filtered off. The filtrate was concentrated under reduced pressure, methanol (1 L) and concentrated sulfuric acid (20 ml) were added, and the mixture was stirred at reflux temperature for 5 hours. After distilling off methanol (about 800 ml) under reduced pressure, the reaction solution was slowly poured into ethyl acetate (1.5 L) / sodium hydrogen carbonate (100 g) / water (1.5 L). The organic layer was washed with brine and dried over magnesium sulfate. After concentration under reduced pressure, purification by column chromatography (developing solvent: ethyl acetate / hexane = 1/5) gave Compound 3 (44 g, yield 38%).

(Synthesis of Compound 4)
To a 1000 ml Teflon (registered trademark) container equipped with a raw material supply port, a fluorine supply port, a helium gas supply port and an exhaust port connected to a fluorine trap via a reflux device cooled with dry ice, a chlorofluorocarbon solvent ( 750 ml) and helium gas was blown at an internal temperature of 30 ° C. for 30 minutes at a flow rate of 100 ml / min. Subsequently, 20% F ₂ / N ₂ gas was blown at 100 ml / min for 30 minutes, the fluorine flow rate was changed to 200 ml / min, and a mixed solution of compound 3 (15 g) and hexafluorobenzene (4.35 ml) was added at 1.1 ml / min. Added in h. The fluorine flow rate was lowered to 100 ml / min, hexafluorobenzene (1.3 ml) was added at 0.6 ml / h, and 20% F ₂ / N ₂ gas was further allowed to flow at 100 ml / min for 15 minutes. After replacing the reactor with helium gas, methanol (100 ml) was added and stirred for 1 hour, and then the solvent was distilled off under reduced pressure. The concentrated residue was washed with an ether / aqueous sodium bicarbonate solution, and the ether layer was dried over magnesium sulfate. After the ether was distilled off, the residue was purified by distillation at 2 mmHg to obtain Compound 4 (10.4 g, 30%).

(Synthesis of Compound 5)
Lithium aluminum hydride (1.75 g) was dispersed in diethyl ether (100 ml), and compound 4 (4.8 g) was dissolved in diethyl ether (30 ml) at a temperature of 10 ° C. or lower and added dropwise. The reaction solution was stirred at room temperature for 6 hours, and ethyl acetate (100 ml) was slowly added dropwise. This solution was slowly poured into dilute hydrochloric acid / ice / ethyl acetate, and insolubles were filtered off. The organic layer was washed with water and brine, dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by column chromatography (developing solvent: ethyl acetate / hexane = 1/2) to give Compound 5 (4.2 g, 95%) as a viscous oil.

(Synthesis of Compound M5)
Acrylic acid chloride (1.1 ml) was added dropwise to a solution of compound 5 (4.0 g) and potassium carbonate (3.4 g) in acetonitrile (50 ml) at a temperature of 10 ° C. or lower. The reaction mixture was stirred at room temperature for 5 hours, potassium carbonate (3.4 g) and acrylic acid chloride (1.1 ml) were added, and the mixture was further stirred for 20 hours. The reaction mixture was poured into ethyl acetate (200 ml) / dilute aqueous hydrochloric acid (200 ml) and separated. The organic layer was washed with aqueous sodium hydrogen carbonate solution and brine, and purified by column chromatography (developing solvent: ethyl acetate / hexane = 1/4) to give compound M5 (2.8 g, 61%) as a viscous oil. ) The results of NMR measurement of Compound M5 were as follows.
[ ¹ H NMR (CDCl ₃ ) δ 4.62 to 4.81 (m, 6H), 5.98 (dd, J = 10.5, 1.2 Hz, 3H), 6.15 (dd, J = 17 .1, 10.5 Hz, 3H), (dd, J = 17.1, 1.2 Hz, 3H)]
[ ¹⁹ F NMR (CDCl ₃ ) δ −63.23 (brs, 3F), −63.54 (d, J = 147 Hz, 3F), −65.90 (d, J = 147 Hz, 3F), −80. 70 (t, J = 8.50 Hz, 9F), −122.9 (m, 6F), −122.90 (m, 6F), −126.54 (m, 6F), −133.39 to −133 .48 (m, 3F)] The compounds M1 to M4 and M6 to M24 can also be synthesized by the same method as described above.

<Example 2 Production and Evaluation of Antireflection Film>
(Preparation of curable resin composition)
Each component shown in Table 1 is mixed (in parentheses indicate solid content concentration (% by mass)), dissolved in methyl ethyl ketone to prepare a 30% by mass solution, and then a polytetrafluoroethylene filter having a pore size of 0.25 μm And curable resin composition was prepared.
Irg907 in the table represents a photopolymerization initiator Irgacure 907 (trade name) manufactured by Ciba Specialty Chemicals.

(Preparation and evaluation of antireflection film)
The curable resin composition prepared as described above was applied onto a glass substrate using a bar coater. After drying at 90 ° C., irradiation with ultraviolet rays was performed, followed by heating at 115 ° C. for 12 minutes, and then cooling to room temperature. The UV curing conditions were as follows: irradiation with an illuminance of 600 mW / cm ² using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen so that the atmosphere had an oxygen concentration of 0.1% by volume or less. The irradiation amount was 600 mJ / cm ² .
Thus, the universal hardness of the produced antireflection film (samples P-1 to P-9), refractive index, and antifouling property were evaluated. The results are shown in Table 1. As a comparative compound, the compound used in the examples of JP 2008-106036 A was used.

(Evaluation method)
Evaluation of universal hardness The hardness was measured using a micro hardness meter (Fischer Scope H100VP-HUC) manufactured by Fisher Instruments Co., Ltd. At this time, a square pyramid indenter (tip-to-face angle; 136 ^o ) made of diamond was used, and the indentation depth under an appropriate test load was measured in a range where the indentation depth did not exceed 1 μm. Universal hardness value (HU) is expressed as the test load divided by the surface area calculated from the geometry of the indentation produced by the test load.

Refractive index evaluation It measured using the Abbe refractometer (made by Atago Co., Ltd.).

Evaluation of antifouling property The antifouling property against the magic when the surface of the prepared coating film is drawn with red, blue and black oily magic, left at room temperature for 24 hours, and then wiped off with a dry cloth or paper. Confirmed the level. The determination was in accordance with the following criteria.
Not at all ： ○
A slight color remains: △
Coloring is remarkable: ×

<Example 3 Production and Evaluation of Antireflection Film>

(Preparation of coating liquid for hard coat layer (HCL-1))
With respect to 90 parts by mass of MEK, 10 parts by mass of cyclohexanone, 95 parts by mass of partially caprolactone-modified polyfunctional acrylate (DPCA-20, Nippon Kayaku Co., Ltd.), photopolymerization initiator (Irgacure 184, Ciba Specialty Chemicals ( 5 parts by mass) were added and stirred. It filtered with the polypropylene filter with the hole diameter of 0.4 micrometer, and prepared the coating liquid (HCL-1) for hard-coat layers.

(Preparation of antireflection film sample)
An 80 μm-thick triacetyl cellulose film “TAC-TD80U” (manufactured by FUJIFILM Corporation) is unwound in the form of a roll, and the hard coat layer coating solution (HCL-1) is directly applied to the 180-wire film. Using a micro gravure roll with a diameter of 50 mm and a doctor blade having a gravure pattern with a depth of 40 μm and a doctor blade, it was applied at a gravure roll rotational speed of 30 rpm and a conveying speed of 30 m / min, and dried at 60 ° C. for 150 seconds. Furthermore, using an “air-cooled metal halide lamp” {manufactured by Eye Graphics Co., Ltd.) with an oxygen concentration of 0.1% by volume under a nitrogen purge, ultraviolet rays having an irradiance of 400 mW / cm ² and an irradiation amount of 70 mJ / cm ² are emitted. The coating layer was cured by irradiation to form a 10.0 μm thick layer and wound up. In this way, a hard coat layer (HC-1) was obtained.

(Preparation of hollow silica particle dispersion)
Hollow silica particle fine particle sol (isopropyl alcohol silica sol, CS60-IPA manufactured by Catalytic Chemical Industry Co., Ltd., average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20 mass%, silica particle refractive index 1.31) in 500 parts by mass, After 20 parts by mass of acryloyloxypropyltrimethoxysilane and 1.5 parts by mass of diisopropoxyaluminum ethyl acetate were added and mixed, 9 parts by mass of ion-exchanged water was added. After reacting at 60 ° C. for 8 hours, the mixture was cooled to room temperature, and 1.8 parts by mass of acetylacetone was added to obtain dispersion A. Then, while adding cyclohexanone so that the silica content was almost constant, solvent substitution was performed by distillation under reduced pressure at a pressure of 30 Torr, and finally a dispersion having a solid content concentration of 18.2% by mass was obtained by adjusting the concentration. The amount of IPA remaining in the obtained dispersion was analyzed by gas chromatography and found to be 0.5% by mass or less.

(Preparation of coating solution for low refractive index layer)
Each component was mixed as shown in Table 2 and dissolved in MEK to prepare a coating solution for a low refractive index layer having a solid content concentration of 6% by mass.

  In Table 2, the numerical value of content represents solid content concentration (mass%).

In addition, the symbol in the said Table 2 is as follows.
“P-1”: fluorine-containing copolymer P-3 described in JP-A No. 2004-45462 (weight average molecular weight of about 50,000)
DPHA: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd., Irg. 127: Irgacure 127, polymerization initiator (manufactured by Ciba Geigy Japan)
RMS-033: Methacryloxy-modified silicone (manufactured by Gelest Co., Ltd.)

(Preparation of coating liquid A for medium refractive index layer)
Hard coating agent containing ZrO ₂ fine particles (Desolite Z7404 [refractive index 1.72, solid content concentration: 60% by mass, zirconium oxide fine particle content: 70% by mass (solid content), average particle size of zirconium oxide fine particles: about 20 nm, Solvent composition: MIBK / MEK = 9/1, manufactured by JSR Corporation]) 10.0 parts by mass, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA) 3.0 parts by mass, photopolymerization started 0.1 parts by weight of an agent (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.), methyl isobutyl ketone 86.9. A part by mass was added and stirred. After sufficiently stirring, the solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution A for medium refractive index layer.

(Preparation of coating liquid A for high refractive index layer)
Hard coating agent containing ZrO ₂ fine particles (Desolite Z7404 [refractive index 1.72, solid content concentration: 60% by mass, zirconium oxide fine particle content: 70% by mass (solid content), average particle size of zirconium oxide fine particles: about 20 nm, Solvent composition: MIBK / MEK = 9/1, manufactured by JSR Corporation]) 15.0 parts by mass was added with 85.0 parts by mass of methyl isobutyl ketone and stirred. Filtration through a polypropylene filter having a pore diameter of 0.4 μm prepared a coating solution A for a high refractive index layer.

(Production of Samples No. 1 to No. 8)
On the hard coat layer (HC-1), using the above-mentioned coating solutions Ln-1 to Ln-8 for the low refractive index layer, adjusting the film thickness of the low refractive index layer to 95 nm, Antireflection film samples No. 1 to No. 8 were prepared by the method.

The low refractive index layer was dried at 60 ° C. for 60 seconds, and the ultraviolet curing condition was 240 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere had an oxygen concentration of 0.1% by volume or less. ), And the irradiation amount was 600 mW / cm ² and the irradiation amount was 600 mJ / cm ² .

(Preparation of sample No. 9)
On the hard coat layer (HC-1), the medium refractive index layer is formed by a microgravure coating method by adjusting the film thickness of the medium refractive index layer to 60 nm by using the coating liquid A for medium refractive index layer. After coating, the high refractive index layer is coated on the high refractive index layer by using the coating liquid A for high refractive index layer so that the film thickness becomes 112 nm, and finally the high refractive index layer is applied by the microgravure coating method. An antireflective film sample No. 9 was prepared by providing the low refractive index layer so that the low refractive index layer thickness was 90 nm using the low refractive index layer coating liquid Ln-2. The coating conditions of the low refractive index layer were the same as those of the antireflection film samples 1 to 8.

The medium refractive index layer was dried at 90 ° C. for 30 seconds, and the ultraviolet curing condition was 180 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere had an oxygen concentration of 1.0% by volume or less. ), And an irradiation dose of 400 mW / cm ² and an irradiation dose of 240 mJ / cm ² was used.

The drying condition of the high refractive index layer is 90 ° C. for 30 seconds, and the ultraviolet curing condition is a 240 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0 volume% or less. ), And an irradiation dose of 400 mW / cm ² and an irradiation dose of 240 mJ / cm ² was used.

(Evaluation of antireflection film sample)
The following evaluation was performed using said antireflection film sample.

(Evaluation 1) Steel Wool Scratch Resistance Evaluation Using a rubbing tester, a rubbing test was performed under the following conditions to obtain an index of scratch resistance.
Evaluation environmental conditions: 25 ° C., 60% RH
Rubbing material: Steel wool (Nippon Steel Wool Co., Ltd., gelled No. 0000)
Wrap around the tip (1cm x 1cm) of the scraper of the tester that comes into contact with the sample, and fix the band.
Travel distance (one way): 13cm
Rubbing speed: 13 cm / second,
Load: 500 g / cm ²
Tip contact area: 1 cm × 1 cm, rubbing frequency: 20 reciprocations.
Oily black ink was applied to the back side of the rubbed sample, and the scratches on the rubbing portion were visually observed with reflected light, and evaluated according to the following criteria. The evaluation results are shown in Table 3.
A: Even if you look very carefully, no scratches are visible.
B: Slightly weak scratches can be seen when viewed very carefully.
C: A weak wound is visible.
D: A moderate crack is visible.
E: There is a scratch that can be seen at first glance.

(Evaluation 2) Antifouling property A film is fixed on a glass surface with an adhesive, and the diameter is 5 mm with a pen tip (thin) of black magic “Mackey extra fine (product name: made by ZEBRA)” under conditions of 25 ° C. and 60 RH%. The circle is written 3 times, and after 5 seconds, it is wiped back and forth 20 times with a load that dents the bundle of Bencot (Brand name, Asahi Kasei Co., Ltd.). The above writing and wiping were repeated under the above conditions until the magic traces did not disappear by wiping, and the antifouling property was evaluated by the number of times that the wiping was completed. The evaluation results are shown in Table 3. The number of times until it no longer disappears is preferably 5 times or more, and more preferably 10 times or more.

(Evaluation 3) Evaluation of specular reflectivity The specular reflectivity is measured by attaching an adapter “ARV-474” to a spectrophotometer “V-550” [manufactured by JASCO Corporation], and a wavelength region of 380 to 780 nm. , The specular reflectance at an exit angle of −5 ° at an incident angle of 5 ° was measured, the average reflectance at 450 to 650 nm was calculated, and the antireflection property was evaluated. The evaluation results are shown in Table 3.

  The evaluation results are shown in Table 3.

As is clear from the above results, the coating film and the antireflection film using the fluorine-containing compound of R4 have a high refractive index, a high reflectance, and insufficient hardness, scratch resistance, and antifouling properties. Met.
On the other hand, the coating film and the antireflection film using the polymerizable fluorine-containing compound (M1, M5, M15, M17, M20) of the present invention have a high fluorine content and a high content of polymerizable groups. While having a refractive index and a low reflectance, it had excellent hardness, scratch resistance and antifouling properties. Among the compounds of the present invention, the higher the fluorine content, the more advantageous in terms of reflectance, and the greater the number of polymerizable groups contained in one molecule, the more in terms of hardness and scratch resistance. It was advantageous.

Based on the above results, the sample of the present invention having the same structure except that the substituent Rf ₁ is different in the polymerizable monomer was compared with the comparative sample. Specifically, (1) a sample using the compound M5 of the present invention and a sample using the comparative compound R1, (2) a sample using the compound M15 of the present invention and a sample using the comparative compound R2, (3) A sample using the compound M20 of the present invention was compared with a sample using the comparative compound R3. As a result, it can be seen that the sample using the compound of the present invention compared to the comparative example has the same hardness and scratch resistance, and the refractive index and the reflectance are greatly reduced. It was an unexpected result that the hardness and scratch resistance did not decrease. From this, it can be seen that the polymerizable fluorine-containing compound of the present invention can provide an antireflection film and an antireflection film having high hardness and excellent scratch resistance in desired optical characteristics.

<Example 4>
(Preparation of coating solution)
A solution of ethyl orthotitanate (0.05 g) and acetylacetone (0.044 g) in ethanol (30 ml) was stirred at room temperature for 10 minutes, water (0.01 ml) was added, and the mixture was further stirred at room temperature for 1 hour. A catalyst solution was prepared.
To this solution was added a solution of the polymerizable fluorine-containing compound M18 (0.5 g) in methyl ethyl ketone (25 ml) and water (0.75 ml), and the mixture was stirred at room temperature for 4 hours and allowed to stand overnight to prepare Solution A. did.

(Preparation and evaluation of antireflection film)
150 μl of the solution A was spin-coated on a 5 cm × 5 cm glass plate (rotation speed: 2000 rpm, rotation time: 20 s) and heated at 150 ° C. for 30 minutes to prepare a treated substrate A.
(Evaluation of refractive index)
It was 1.41 when the refractive index was measured using the Abbe refractometer (made by Atago Co., Ltd.).
(Evaluation of antifouling properties)
When the antifouling property was evaluated by the same method as in Example 3, the result was 12.
(Evaluation of scratch resistance)
When the surface appearance after rubbing 10 reciprocations with a load of 200 g / cm ² using a steel wool # 0000 manufactured by Nippon Steel Wool Co., Ltd. was visually observed, no scratch was observed.

<Example 5>
An image display device was produced using each of the antireflection films of the present invention (samples Nos. 1, 2, 4, and 6). All of these image display devices were excellent in surface strength while preventing a decrease in contrast and reflection of an image due to reflection of external light.

It is sectional drawing which shows typically the antireflection film one embodiment of this invention. It is sectional drawing which shows typically another embodiment of the antireflection film of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Antireflection film 2 Transparent support 3 Hard coat layer 5 Low refractive index layer 6 Antireflection film 7 Middle refractive index layer 8 High refractive index layer

Claims (12)

A polymerizable fluorine-containing compound represented by the following general formula (I):

[In General Formula (I), Rf represents any organic group of the following structural formulas Rf-1 to Rf-11 . Rf ₁ represents a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms or a perfluorocycloalkyl group having 3 to 12 carbon atoms. A plurality of Rf ₁ may be the same or different. Rf ₂ represents a linear or branched perfluoroalkyl group, perfluorocycloalkyl group or a fluorine atom having 3 to 12 carbon atoms having 1 to 20 carbon atoms. A plurality of Rf ₂ may be the same or different. However, the total number of carbon atoms of Rf ₁ and Rf ₂ in at least one unit among the a units present in the general formula (I) is 3 or more. A represents a single bond or a divalent linking group represented by the general formula (II). A plurality of A may be the same or different. In the general formula (I) and general formula (II), Q is a hydrogen _{atom, -COC (R 0) = CH} 2, allyl, epoxy alkylene _{group, - (CH 2) X Si} (W) 3, - (CH ₂ ) _y NCO or — (CH ₂ ) _z CN (where R ₀ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, W represents an alkoxy group or a hydroxyl group, x, y and z are Each represents an integer greater than or equal to 1. Three W may mutually be same or different. Plural Qs may be the same or different. However, at least one of Q in the general formula (I) and the general formula (II) is —COC (R ₀ ) ═CH ₂ , an allyl group, an epoxyalkylene group, — (CH ₂ ) _X Si (W) ₃ , - _{(CH 2)} y NCO or - represents a _{(CH 2)} z CN. a represents an integer of 3 to 6, and b and c each independently represents an integer of 0 to 100. ]

In the general formula (I), the Q is —COC (R) ═CH ₂ (wherein R represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group). Item 6. The polymerizable fluorine-containing compound according to item 1.   The polymerizable fluorine-containing compound according to claim 1 or 2, wherein in the general formula (I), all A are single bonds. The polymerization according to any one of claims 1 to 3, wherein, in the general formula (I), the Rf ₁ is a perfluoroalkyl group having 3 or more carbon atoms, and the Rf ₂ is a fluorine atom. Fluorinated compounds. A polymerizable fluorine-containing compound represented by the following general formula (III):

[In the general formula (III), Rf ′ is a chain or cyclic a ′ having 5 to 50 carbon atoms composed of only carbon atoms and fluorine atoms, or composed of only carbon atoms, fluorine atoms and oxygen atoms. Rf ₁ ′ is a perfluoroalkyl group having 3 or more carbon atoms, R is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and a ′ represents an integer of 3 to 6 . ] An antireflection film comprising a low refractive index layer obtained by curing a curable resin composition containing at least one polymerizable fluorine-containing compound according to any one of claims 1 to 5 . An antireflection film comprising a low refractive index layer obtained by curing the curable resin composition containing the polymerizable fluorine-containing compound according to any one of claims 1 to 5 and inorganic oxide fine particles. The antireflection film according to claim 7 , wherein the inorganic oxide fine particles are hollow silica fine particles. An antireflection film, wherein the antireflection film according to any one of claims 6 to 8 is provided on a transparent support. An image display device comprising the antireflection film according to claim 9 . A fluorine-containing alcohol represented by the following general formula (IV).

[In General Formula (IV), Rf represents any organic group of the following structural formulas Rf-1 to Rf-11 . Rf ₁ represents a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms or a perfluorocycloalkyl group having 3 to 12 carbon atoms. A plurality of Rf ₁ may be the same or different. Rf ₂ represents a linear or branched perfluoroalkyl group, perfluorocycloalkyl group or a fluorine atom having 3 to 12 carbon atoms having 1 to 20 carbon atoms. A plurality of Rf ₂ may be the same or different. However, the total number of carbon atoms of Rf ₁ and Rf ₂ in at least one unit among the a units present in the general formula (IV) is 3 or more. A represents a single bond or a divalent linking group represented by the general formula (V). A plurality of A may be the same or different. a represents an integer of 3 to 6, and in the general formula (V), b and c each independently represents an integer of 0 to 100. ]

A fluorine-containing alcohol represented by the following general formula (VI):

[In the general formula (VI), Rf ′ is a chain or cyclic a ′ having 5 to 50 carbon atoms composed of only carbon atoms and fluorine atoms, or composed of only carbon atoms, fluorine atoms and oxygen atoms. Rf ₁ ′ is a perfluoroalkyl group having 3 or more carbon atoms, and a plurality of Rf ₁ ′ may be the same or different from each other. a ′ represents an integer of 3 to 6. ]

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