JP2005097371A - Fluorine-containing resin composition and optical article and image display device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorine-containing resin composition efficiently forming a periodic uneven microstructure having excellent optical characteristics and stain resistance and an optical article suitably used in various optical applications such as an antireflection coating, an antireflection film, an optical waveguide, a relief hologram, a lens, an optical card, an optical disk and a polarizing separation element and to provide an image display device using the optical article. <P>SOLUTION: The fluorine-containing resin composition comprises at least a fluorine-containing compound and is used for forming the uneven microstructure of the optical article. The fluorine-containing compound is preferably a mode which is at least any selected from a fluorine-containing monomer, a fluorine-containing silane coupling agent, a fluorine-containing surfactant and a fluorine-containing polymer. The optical article has the uneven microstructure formed by using the fluorine-containing resin composition and comprises fluorine atoms on the surface. The image display device comprises the optical article arranged therein. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention provides a fluorine-containing resin composition capable of efficiently forming a periodic fine concavo-convex structure excellent in optical characteristics and stain resistance, and an antireflection film, an antireflection film, an optical waveguide, a relief hologram, a lens, light The present invention relates to an optical article suitably used for various optical applications such as a card, an optical disk, and a polarization separation element, and an image display device using the optical article.

In recent years, optical articles having a periodic fine concavo-convex structure of a visible light wavelength or less have attracted attention in terms of the possibility of developing them in various optical applications such as antireflection films, antireflection films, optical waveguides, and polarization separation elements. (Refer nonpatent literature 1).
For example, the antireflection film and the antireflection film are used in display devices such as a cathode ray tube display (CRT), a plasma display (PDP), an electroluminescence display (ELD), and a liquid crystal display (LCD), and in a show window. It is used to prevent contrast reduction and image reflection due to light reflection. Moreover, it is used in solar cells and the like to prevent reflection and increase the light utilization efficiency.

  Conventionally, as an antireflection film and an antireflection film, a multilayer film in which a plurality of layers having different refractive indexes are laminated on a support by vapor deposition, sputtering, or coating is generally used. The multilayer film prevents reflection by canceling reflected light from the interface of each layer based on the principle of optical interference. By increasing the number of layers, low reflectance characteristics and low reflectance wavelength dependency are achieved. In terms of cost, one having about 1 to 4 layers has been put into practical use. However, the multilayer film has a limit of an average reflectance of about 0.2 to 0.3%, and the wavelength dependency of the reflectance is large. Therefore, coloring such as reddish and bluedish becomes a problem. In addition, there is a drawback that the reflectance characteristic changes greatly depending on the incident angle of light.

  On the other hand, as another means for preventing reflection, there is a method of scattering reflected light by mixing a large particle in a binder and forming a rough uneven structure on the surface of the film, which is used in combination with the optical interference method by the multilayer film. It has also been done. These methods are relatively inexpensive but have a problem that a rough uneven structure causes an increase in haze and a decrease in contrast, and a sufficient antireflection effect cannot be obtained.

  When a periodic fine concavo-convex structure having a visible light wavelength or less is formed on the surface of the film, a surface having a low refractive index can be formed without scattering visible light. By providing a fine uneven shape such as a cone or a triangular pyramid, the refractive index can be continuously changed in the thickness direction from the refractive index of air to the refractive index of the base material, without forming a clear interface, and with a wide wavelength It is known that a very excellent antireflection effect is obtained with a low reflectance over a region and a small incidence angle dependency (see Non-Patent Document 2). Note that when the cross section of the fine concavo-convex structure is rectangular or the like, the refractive index does not change continuously, but it is effective as a method of forming a layer having a low refractive index by mixing air and a matrix.

  As a method for forming the fine concavo-convex structure, a method of filling fine particles by reducing the amount of binder, an etching method (for example, a film obtained by sol-gel reaction of borosilicate is immersed in an acid, and the inside of the film from the film surface according to the diffusion of the acid The method of changing the elution amount of the borate component toward the surface) has been conventionally known. However, these methods have difficulty in precisely controlling the fine uneven shape and have a problem in accuracy.

In recent years, a method for forming a fine relief shape by direct drawing using an electron beam resist or laser two-beam interference exposure method has been developed as a more reliable method for forming a fine concavo-convex structure (see Non-Patent Document 1). However, this method has a problem that it takes time for exposure and is not suitable for large area and mass production. Therefore, shape transfer methods such as an injection molding method and a press processing method have been proposed as methods suitable for large area processing and mass production (see Non-Patent Document 3 and Patent Document 1). These proposals utilize a master in which a fine uneven shape is formed on a resist material by the direct drawing method, and further, by producing a stamper (die) having a fine uneven structure complementary to the master by electroforming. Is used to transfer the shape to a resin or the like.
As another means, a method using phase separation of a resin has also been reported, and large area processing is possible and it is possible to manufacture at low cost (see Patent Document 2).

  Therefore, the periodic fine concavo-convex structure exhibits excellent optical characteristics, is inexpensive, and is capable of processing a large area, but the fine concavo-convex structure is likely to soak oil droplets and is exposed to the external environment. In order to use it under conditions, the improvement of the stain resistance is a big problem, and at present the early solution is strongly desired.

Hisao Kikuta Papers of IEICE J83-C (3), 173-181 (2000) Bernhard, C.G., Endeavor, 26, 79 (1967) A. Gombert et.al., Thin Solid Films, 351, 73 (1999) JP 2002-267816 A European Patent Publication No. 1094103

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention relates to a fluorine-containing resin composition capable of forming a periodic fine concavo-convex structure having a visible light wavelength or less excellent in optical characteristics and stain resistance, and an antireflection film, an antireflection film, an optical waveguide, a relief, and the like. An object of the present invention is to provide an optical article suitable for various optical applications such as a hologram, a lens, an optical card, an optical disk, and a polarization separation element, and an image display device using the optical article.

Means for solving the problems are as follows. That is,
<1> A fluorine-containing resin composition comprising at least a fluorine-containing compound and used for forming a fine relief structure of an optical article.
<2> The fluorine-containing resin composition according to <1>, wherein the fluorine-containing compound has a fluoroalkyl group represented by the following general formula (1).
- _{(CF 2)} n X Formula (1)
However, in said general formula (1), X represents a fluorine atom or a hydrogen atom. n represents an integer.
<3> The <1> or <2>, wherein the fluorine-containing compound is at least one selected from a fluorine-containing monomer, a fluorine-containing silane coupling agent, a fluorine-containing surfactant, and a fluorine-containing polymer. The fluorine-containing resin composition.
<4> A fluorine-containing polymer is a polymer of a fluoroalkyl group-containing monomer, a copolymer of a fluoroalkyl group-containing monomer and a poly (oxyalkylene) group-containing monomer, and a fluoroalkyl group-containing monomer and a crosslinking reactive group-containing monomer The fluorine-containing resin composition according to <3>, including any one of the copolymers.
<5> The fluorine-containing resin composition according to any one of <1> to <4>, wherein the fluorine-containing compound is blended as any one of an additive and a binder.
<6> An optical article characterized in that a fine concavo-convex structure is formed using the fluorine-containing resin composition according to any one of <1> to <5>, and the surface contains fluorine atoms.
<7> The optical article according to <6>, wherein the fluorine atom concentration at a depth of 10 nm or less from the surface is 20 atomic percent or more.
<8> The optical article according to any one of <6> to <7>, wherein the surface tension is 25 mN / m or less.
<9> The optical article according to any one of <6> to <8>, wherein the concavo-convex height in the fine concavo-convex structure is 50 to 1000 nm and the concavo-convex cycle is 10 to 400 nm.
<10> The optical article according to any one of <6> to <9>, wherein the refractive index of the fine concavo-convex structure is n, and satisfies the following formula: concavo-convex cycle <400 / n (nm).
<11> The optical article according to any one of <6> to <10>, wherein a mirror surface average reflectance in a wavelength region of 450 to 650 nm is 2% or less.
<12> A stamper having a fine concavo-convex structure complementary to the fine concavo-convex structure formed on the optical article is manufactured, and the stamper is pressed against a layer formed from the fluorine-containing resin composition to transfer the fine concavo-convex structure of the stamper. The optical article according to any one of <6> to <11>.
<13> Any one of <6> to <12>, wherein the optical article is any one selected from an antireflection film, an antireflection film, an optical waveguide, a relief hologram, a lens, an optical card, an optical disk, and a polarization separation element It is an optical article as described in above.
<14> An image display device comprising the optical article according to any one of <6> to <13>.

  The fluorine-containing resin composition of the present invention contains at least a fluorine-containing compound and is used to form a fine uneven structure of an optical article. Even if the fluorine-containing compound has a low surface tension and a structure in which liquid droplets are likely to penetrate, such as a fine concavo-convex structure, entry of liquid droplets can be reliably prevented. Therefore, a fine concavo-convex structure excellent in optical characteristics and stain resistance can be formed, and can be suitably used for various optical applications.

  The optical article of the present invention has a fine relief structure formed using the fluorine-containing resin composition of the present invention, and contains fluorine atoms on the surface. Since the optical article of the present invention has a fine concavo-convex structure excellent in optical characteristics and stain resistance, an antireflection film, an antireflection film, an optical waveguide, a relief hologram, a lens, an optical card, an optical disk, and polarization separation It is suitable for various optical uses such as elements.

  The image display device of the present invention is one in which the optical article of the present invention is arranged. In the image display device of the present invention, there is almost no reflection of the surrounding scenery, it shows a comfortable visibility and has a sufficient antifouling property, and is particularly suitable as a liquid crystal display device.

  According to the present invention, conventional problems can be solved, antireflection performance is high, antifouling property is high, antireflection film, antireflection film, optical waveguide, relief hologram, lens, optical card, optical disk, and polarization An optical article suitably used for various optical applications such as a separation element can be provided. In addition, since the image display device of the present invention is equipped with the optical article, the image display device has good visibility, can be hardly stained, and can display a high-quality image, and is particularly suitable as a liquid crystal display device. .

(Fluorine-containing resin composition)
The fluorine-containing resin composition of the present invention is used to form a fine concavo-convex structure of an optical article and contains at least a fluorine-containing compound and further contains other components as necessary.
In this specification, the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”.

There is no restriction | limiting in particular as said fluorine-containing compound, According to the objective, it can select suitably, For example, what has the fluoroalkyl group represented by following General formula (1) is suitable.
- _{(CF 2)} n X Formula (1)
However, in said general formula (1), X represents a fluorine atom or a hydrogen atom.
n represents an integer, preferably 1 to 20, more preferably 3 to 10, and still more preferably 4 to 8.

  The fluorine-containing compound is not particularly limited as long as it contains fluorine, and can be appropriately selected according to the purpose. Examples thereof include a fluorine-containing monomer, a fluorine-containing silane coupling agent, a fluorine-containing surfactant, and fluorine. At least one selected from the containing polymer is preferable. At least one of the fluorine-containing monomer and the fluorine-containing polymer, which is the fluorine-containing compound, may be added in a small amount as an additive to the non-fluorine-containing binder (binder resin). (Mass% or more), or two kinds of fluorine-containing compounds may be used in combination.

The fluorine-containing monomer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a fluoroalkyl group-substituted vinyl monomer and a fluoroalkyl group-substituted ring-opening polymerizable monomer.
As the fluoroalkyl group-substituted vinyl monomer. Examples include fluoroalkyl group-substituted (meth) acrylate derivatives, fluoroalkyl group-substituted (meth) acrylamide derivatives, fluoroalkyl group-substituted vinyl ether derivatives, fluoroalkyl group-substituted styrene derivatives.
Examples of the fluoroalkyl group-substituted ring-opening polymerizable monomer include fluoroalkyl group-substituted epoxy derivatives, fluoroalkyl group-substituted oxetane derivatives, and fluoroalkyl group-substituted oxazoline derivatives.
Among these, fluoroalkyl group-substituted vinyl monomers are preferable, and fluoroalkyl group-substituted (meth) acrylate derivatives are particularly preferable.

  Preferred examples of the fluoroalkyl group-substituted (meth) acrylate derivative include compounds represented by the following general formula (2).

前記一般式（２）中、Ｒは、水素原子又はメチル基を表す。Ｘは、水素原子又はフッ素原子を表す。
ｍは、１〜６の整数を表し、１〜３が好ましく、１又は２がより好ましい。
ｎは、１〜２０の整数を表し、３〜１０が好ましく、４〜８がより好ましい。

In the general formula (2), R represents a hydrogen atom or a methyl group. X represents a hydrogen atom or a fluorine atom.
m represents an integer of 1 to 6, preferably 1 to 3, and more preferably 1 or 2.
n represents an integer of 1 to 20, preferably 3 to 10, and more preferably 4 to 8.

  Specific examples of the fluoroalkyl group-substituted (meth) acrylate derivative include those shown below.

As the fluorine-containing silane coupling agent, for example, a fluoroalkyl group-substituted silane coupling agent is suitable, and those represented by the following general formula (3) are particularly preferred.
(Rf) ₃ R ¹ _b SiX _c General formula (3)
In the general formula (3), Rf represents a C1-C20 fluorine-substituted alkyl group which may contain one or more ether bonds or ester bonds, for example, a 3,3,3-trifluoropropyl group. , Tridecafluoro-1,1,2,2-tetrahydrooctyl group, 3-trifluoromethoxypropyl group, 3-trifluoroacetoxypropyl group, and the like.
R ¹ represents an alkyl group having 1 to 10 carbon atoms, and represents, for example, a methyl group, an ethyl group, a cyclohexyl group, or the like.
X represents a hydroxyl group or a hydrolyzable group, and the hydrolyzable group is not particularly limited as long as it is a hydrolyzable group and can be appropriately selected according to the purpose. For example, an alkoxy group , Halogen atoms, RCOO (where R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), and the like.
The alkoxy group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. For example, methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i -Butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, And a lauryloxy group.
Examples of the halogen atom include Cl, Br, I, and the like.
Examples of the RCOO, for _example, CH 3 _COO, include _{C 2} H 5 COO and the like.
a, b, and c are integers satisfying a + b + c = 4 and satisfying a ≧ 1, c ≧ 1, and preferably a = 1, b = 0, and c = 3.

  Examples of the fluorine-containing silane coupling agent represented by the general formula (3) include 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriacetoxysilane, dimethyl-3, Examples include 3,3-trifluoropropylmethoxysilane, tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane, and the like.

  The addition amount of the fluorine-containing silane coupling agent is preferably 0.01 to 10 parts by mass and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin.

  The fluorine-containing surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an anionic surfactant having a fluoroalkyl group and a cationic surfactant having a fluoroalkyl group. Preferably mentioned.

Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (C _6- C ₁₁₎ oxy] -1-alkyl _(C 3 _{~C 4)} sulfonate, sodium 3- [omega - fluoroalkanoyl _{(C 6 ~C} 8) -N- ethylamino] -1-sodium sulfonic acid, fluoroalkyl _(C 11 ~C ₂₀₎ carboxylic acids or metal salts thereof, perfluoroalkyl carboxylic acids _(C 7 _{~C 13)} or metal salts thereof, perfluoroalkyl _(C 4 _{~C 12)} sulfonic acid or metal salts thereof, perfluoroalkyl Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydride Kishiechiru) perfluorooctane sulfonamide, perfluoroalkyl _(C 6 _{-C 10)} sulfonamide propyl trimethyl ammonium salts, perfluoroalkyl _{(C 6} -C 10)-N-ethylsulfonyl glycine salts, monoperfluoroalkyl _{(C 6} -C ₁₆₎ ethyl phosphoric acid ester, and the like.
As the anionic surfactant having a fluoroalkyl group, a commercially available product may be used. Examples of the commercially available product include Surflon S-111, S-112, and S-113 (trade names, manufactured by Asahi Glass Co., Ltd.). , FLORARD FC-93, FC-95, FC-98, FC-29 (above trade name, manufactured by Sumitomo 3M), Unidyne DS-101, DS-102 (above trade name, manufactured by Daikin Industries), MegaFuck F -L0, F-120, F-113, F-191, F-812, F-833 (above trade name, manufactured by Dainippon Ink and Company), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (above trade names, manufactured by Tochem Products), Fantent F-100, F150 (above trade names, manufactured by Neos), and the like. It is.

Examples of the cationic surfactant having a fluoroalkyl group include aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, and perfluoroalkyl (C ₆ -C ₁₀ ) sulfonamidopropyltrimethylammonium salts. Examples include aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like.
As the cationic surfactant having a fluoroalkyl group, a commercially available product may be used. Examples of the commercially available product include Surflon S-121 (manufactured by Asahi Glass Co., Ltd.), Florard FC-135 (manufactured by Sumitomo 3M Company), Unidyne. DS-202 (manufactured by Daikin Industries, Ltd.), MegaFac F-150, F-824 (above trade names, manufactured by Dainippon Ink, Inc.), Xtop EF-132 (manufactured by Tochem Products), and Footgent F-300 ( Neos)).

  Among the fluorine-containing quaternary ammonium salt compounds, a compound represented by the following general formula (4) is particularly preferable.

ただし、前記一般式（４）中、Ｒｆは、パーフルオロアルキル基を表す。Ｒ^２は、水素原子、フッ素原子又は炭化水素基を表す。Ｒ^３〜Ｒ^５は、互いに同一であってもよいし、異なっていてもよく、水素原子、フッ素原子又は炭化水素基を表す。Ｘは、二価有機基を表す。Ｙは、対イオンを表す。ｍは、１以上の整数を表す。

However, in said general formula (4), Rf represents a perfluoroalkyl group. R ² represents a hydrogen atom, a fluorine atom or a hydrocarbon group. R ^{3 to} R ⁵ may be the same as or different from each other, and each represents a hydrogen atom, a fluorine atom, or a hydrocarbon group. X represents a divalent organic group. Y represents a counter ion. m represents an integer of 1 or more.

In the general formula (4), Rf represents a perfluoroalkyl group. The perfluoroalkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 15 carbon atoms, for example, C _n F _2n-1 (where n is 1 to 30, preferably 3 to 3). Specifically, for example, CF ₃ (CF ₂ ) ₅ —, CF ₃ (CF ₂ ) ₆ —, CF ₃ (CF ₂ ) ₇ —, CF ₃ (CF _{2) 8 -, CF 3 (} CF 2) 9 -, CF 3 (CF 2) 10 -, CF 3 (CF 2) 11 -, CF 3 (CF 2) 12 -, CF 3 (CF 2) 13 -, CF ₃ (CF ₂ ) _14- , CF ₃ (CF ₂ ) _15- , CF ₃ (CF ₂ ) _16- , CF ₃ (CF ₂ ) _17- , (CF ₃ ) ₂ CF (CF ₂ ) _6- , etc. Are preferable.

  In the general formula (4), Y represents a counter ion. Examples of the counter ion include halogen ions, sulfate ions, nitrate ions, phosphate ions, thiocyanate ions, organic acid ions, and the like. Among these, halogen ions such as fluorine, chlorine, bromine and iodine are particularly preferable.

In the general formula (4), X represents a divalent organic group. Examples of the divalent organic group, for _{example, -SO 2 -, - CO -} , - (CH 2) x -, - SO 2 N (R 6) - (CH 2) x -, - (CH 2) x- _{CH (OH) - (CH 2} ) x-, and the like. Here, x represents an integer of 1 to 6. R ⁶ represents an alkyl group having 1 to 10 carbon atoms. Among these, —SO ₂ —, —CO—, — (CH ₂ ) ₂ —, —SO ₂ N (C ₂ H ₅ ) — (CH ₂ ) ₂ —, or —CH ₂ CH (OH) CH ₂ — Are preferred, and —SO ₂ — or —CO— is particularly preferred.
In the said General formula (4), m represents an integer greater than or equal to 1, 1-20 are preferable and 1-10 are more preferable.

In the general formula (4), R ² represents a hydrogen atom, a fluorine atom, or a hydrocarbon group. R ^{3 to} R ⁵ may be the same as or different from each other, and each represents a hydrogen atom, a fluorine atom, or a hydrocarbon group. There is no restriction | limiting in particular as this hydrocarbon group, Although it can select suitably according to the objective, For example, an alkyl group, an alkenyl group, an aryl group, etc. are mentioned. These may be further substituted with a substituent.
As the alkyl group, those having 1 to 10 carbon atoms are preferable, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, n-hexyl group, Examples include isohexyl group, n-heptyl group, n-octyl group, isooctyl group, n-decyl group, isodecyl group, and the like, which may be further substituted with a substituent. As the alkenyl group, those having 2 to 10 carbon atoms are more preferable, and examples thereof include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group, and an octenyl group. And may be further substituted. As said aryl group, a C6-C24 thing is more preferable, For example, a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a styryl group, a mesityl group, a cinnamyl group, a phenethyl group, a benzhydryl group etc. are mentioned. These may be further substituted with a substituent.

  The addition amount of the fluorine-containing surfactant is preferably 0.01 to 10 parts by mass and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin.

  Next, examples of the fluorine-containing polymer include polymers of fluoroalkyl group-containing monomers, copolymers of fluoroalkyl group-containing monomers and poly (oxyalkylene) group-containing monomers, and crosslinking reactions with fluoroalkyl group-containing monomers. Any copolymer with a functional group-containing monomer is preferred.

The fluorine-containing polymer may be composed of, for example, polymerized units of only the fluorine-containing monomer, but may be a copolymer with another copolymerizable monomer.
Examples of the other copolymerizable monomer include Polymer Handbook 2nd ed. , J .; Brandrup, Wiley lnterscience (1975) Chapter 2 pages 1-483 can be used.
Examples of the other copolymerizable monomer include (meth) acrylic acid, (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, dialkyl itaconates, and fumaric acid. And dialkyl esters or monoalkyl esters, crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleronitrile, styrene, and the like.
Etc.

  Examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, Methylolpropane mono (meth) acrylate, benzyl (meth) acrylate, methoxybenzyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate, methacryloyloxypropyl Trimethoxysilane, terminal (meth) acryloylated silicone macromer, and the like. As the terminal (meth) acryloylated silicone macromer, commercially available products can be used. For example, Silaplane 0721, 0725 (above, trade name, manufactured by Chisso Corporation), AK-5, AK-30, AK-32 (The trade name, manufactured by Toa Gosei Co., Ltd.)

  Examples of the (meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide, and N-2. -Acetamidoethyl-N-acetyl (meth) acrylamide, etc. are mentioned. As said N-alkyl (meth) acrylamide, that whose carbon number of an alkyl group is 1-3 is preferable, for example, a methyl group, an ethyl group, a propyl group, etc. are mentioned. The N, N-dialkyl (meth) acrylamide is preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group and an ethyl group.

  Examples of the allyl compound include allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.) Examples include allyloxyethanol.

  Examples of the vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, Examples thereof include hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, and the like.

  Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate. Vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate, and the like.

Examples of the dialkyl itaconates include dimethyl itaconate, diethyl itaconate, dibutyl itaconate, and the like.
Examples of the dialkyl ester or monoalkyl ester of fumaric acid include dibutyl fumarate.

The fluorine-containing polymer used by adding a small amount to another binder in the present invention is preferably a fluorine-containing copolymer copolymerized with the poly (oxyalkylene) group-containing monomer.
As said poly (oxyalkylene) group, what is represented by general formula:-(OR) x is preferable.
In the general formula, R represents an alkylene group having 2 to 4 carbon atoms, for example, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH (CH ₃ ) CH ₂ —, _{-CH (CH 3) CH (CH} 3) -, and the like.

  The oxyalkylene unit in the poly (oxyalkylene) group may be the same as in poly (oxypropylene), or two or more different oxyalkylenes are randomly distributed. Alternatively, either a linear or branched oxypropylene unit or an oxyethylene unit, or a linear or branched oxypropylene unit block or an oxyethylene unit block may be used.

The poly (oxyalkylene) chain includes those linked by one or more linking groups (for example, -CONH-Ph-NHCO-, -S-, etc., where Ph represents a phenylene group). be able to. When the linking group has a valence of 3 or more, a branched oxyalkylene unit is obtained.
Moreover, when using the copolymer containing the polymer unit which has the said poly (oxyalkylene) group, the mass average molecular weight (Mw) of a poly (oxyalkylene) group has preferable 250-3000.

Examples of the poly (oxyalkylene) (meth) acrylate include commercially available hydroxypoly (oxyalkylene) materials such as “Pluronic” (Pluronic (manufactured by Asahi Denka Kogyo Co., Ltd.)), Adeka polyether (Asahi Denka Kogyo ( "Carbowax" [Carbowax (Glico Products)], "Triton" (Toriton (Rohm and Haas)) and P.I. E. What is sold as G (Daiichi Kogyo Seiyaku Co., Ltd.) can be manufactured by reacting with acrylic acid, methacrylic acid, acrylic chloride, methacrylic chloride or acrylic acid anhydride by a known method. Separately, poly (oxyalkylene) diacrylate produced by a known method can also be used.
Moreover, you may use commercially available oxyalkylene chain containing macromers, such as PE-300 and the same PE-600 (above a brand name, Dai-ichi Kogyo Seiyaku Co., Ltd. product).

  Specific examples of the fluoroalkyl group-containing monomer containing the poly (oxyalkylene) group are shown below, but the present invention is not limited thereto. The poly (oxyalkylene) group is often a mixture of those having different degrees of polymerization X, and the degree of polymerization is expressed by an integer close to the average of the degrees of polymerization in the compounds shown as specific examples.

The polymer having a fluoroalkyl group is synthesized by appropriately copolymerizing another monomer with a fluoroalkyl group-containing monomer as an essential component.
50-100 mass% is preferable, as for content of the said fluoroalkyl group containing monomer, 70-100 mass% is more preferable, and 80-100 mass% is still more preferable. When the content of the fluoroalkyl group-containing monomer is less than 50% by mass, a sufficient surface energy reduction effect cannot be obtained, and the antifouling property of the optical article may be insufficient.

  When the fluoroalkyl group-containing monomer and the (poly) oxyalkylene group-containing monomer are copolymerized, the content of the (poly) oxyalkylene group-containing monomer is preferably 0.1 to 50% by mass, 1-30 mass% is more preferable, and 0.5-10 mass% is still more preferable.

  In order to enhance the durability of the optical article, the fluoroalkyl group-containing polymer preferably has a crosslinking reactive group. The crosslinkable group is preferably a group that reacts with at least one of the polymer and monomer constituting the main component of the binder.

  The method for introducing a crosslinking reactive group into the fluoroalkyl group-containing copolymer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, (1) glycidyl (meth) acrylate, allyl Monomers containing two different groups of reactivity, such as (meth) acrylate, glycidyloxypropyltrimethoxysilane, (meth) acryloyloxypropyltrimethoxysilane, allyltrimethoxysilane, etc. by radical polymerization or ionic polymerization Examples include a method in which only one polymerizable group is polymerized, and (2) a method in which a reactive group-containing copolymer such as a hydroxyl group is synthesized in advance and then a crosslinking reactive group is introduced by a polymer reaction.

For example, methods for introducing the (meth) acryloyl group into the fluorine-containing copolymer include the following methods (i) to (vi).
(I) After synthesizing a polymer having a nucleophilic group such as a hydroxyl group and an amino group, (meth) acrylic acid chloride, (meth) acrylic anhydride, mixed acid anhydride of (meth) acrylic acid and methanesulfonic acid, etc. (Ii) a method in which (meth) acrylic acid is allowed to act on the polymer having the nucleophilic group in the presence of a catalyst such as sulfuric acid, (iii) methacryloyloxypropyl isocyanate, etc. on the polymer having the nucleophilic group (Iv) A method in which (meth) acrylic acid is allowed to act after synthesizing a polymer having an epoxy group, (v) Glycidyl methacrylate on a polymer having a carboxyl group A method of allowing a compound having both an epoxy group and a (meth) acryloyl group to act, etc. (vi) - method for performing dehydrochlorination after obtained by polymerizing a vinyl monomer having a chloropropionic acid ester moiety.
In addition, other functional groups can be introduced by selecting any one of the above methods according to the stability of the functional group.

  The introduction rate of the crosslinking reactive group is preferably from 1 to 80 mol%, more preferably from 5 to 60 mol%, still more preferably from 10 to 50 mol%, based on the fluorine-containing monomer of the fluorine-containing copolymer.

1000-5 million are preferable, as for the mass mean molecular weight (Mw) of the copolymer which is the said fluorine-containing polymer obtained as mentioned above, 2000-500,000 are more preferable, 5000-100000 are still more preferable.
When the mass average molecular weight (Mw) is less than 1000, sufficient film hardness cannot be obtained, and the scratch resistance of the optical article is insufficient, or a continuous antifouling effect cannot be obtained due to dropping off of the fluorine-containing polymer component. If it exceeds 5,000,000, the solvent solubility may be reduced, making it difficult to handle, or the storage stability of the fluorine-containing resin composition may be reduced.

  Although the preferable example of the said fluorine-containing copolymer is shown below, this invention is not limited to these. In addition, the number represented by x, y, z in a formula represents the molar ratio of each monomer component. Mw represents a mass average molecular weight.

  The fluorine-containing copolymer can be synthesized by various polymerization methods such as solution polymerization, suspension polymerization, intelligent precipitation polymerization, bulk polymerization, and emulsion polymerization. Moreover, after synthesizing a precursor such as a hydroxyl group-containing polymer by these methods, it can be synthesized by introducing a (meth) acryloyl group or the like by the polymer reaction. The said polymerization reaction can be performed by well-known operation, such as a batch type, a semi-continuous type, and a continuous type.

  Examples of the polymerization initiation method include a method using a radical initiator and a method of irradiating light or radiation. These polymerization methods and polymerization initiation methods are described in, for example, Tsuruta Junji “Polymer Synthesis Method” revised edition (published by Nikkan Kogyo Shimbun, 1971), Takayuki Otsu, Masato Kinoshita, “Experimental Method for Polymer Synthesis” , Published in 1972, pages 124-154.

Among the polymerization methods, a solution polymerization method using a radical initiator is particularly preferable. There is no restriction | limiting in particular as a solvent used by this solution polymerization method, According to the objective, it can select suitably, For example, 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, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and the like. These may be used alone or as a mixture of two or more, or as a mixed solvent with water.
The polymerization temperature needs to be set in relation to the molecular weight of the polymer to be produced, the type of initiator, etc., and can be from 0 ° C. or lower to 100 ° C. or higher, but it is preferable to perform polymerization in the range of 50 to 100 ° C. . The reaction time is usually about 5 to 30 hours.

  The obtained polymer can be used as it is without purification, but it is preferable to carry out purification by reprecipitation. As the reprecipitation solvent, isopropanol, hexane, methanol and the like are preferable.

In the present invention, the fluorine-containing compound (fluorine-containing monomer, fluorine-containing polymer, etc.) can be added to a binder and used.
As the binder, known monomers, oligomers, prepolymers, or thermoplastic resins that are cured by the action of heat or active energy rays can be used, but shape transferability during production and strength of the formed shape can be used. -From the viewpoint of achieving both heat resistance and weather resistance, preferably a curable resin, more preferably a prepolymer from the viewpoint of low curing shrinkage, and curing by the action of active energy rays from the viewpoint of rapid curability. Resins are particularly preferred.

  Examples of the curable resin include two or more ethylenically unsaturated groups (for example, ((meth) acryloyl group, vinyl group, vinyloxy group, allyl group, etc.), ring-opening polymerizable group (for example, epoxy group, Oxetanyl group, oxazolyl group, etc.), reactive silyl group (eg, alkoxysilyl group, acetoxysilyl group, hydroxysilyl group, etc.), polyaddition reactive group (eg, isocyanate group + hydroxyl group, vinyl group + hydrosilyl group, etc.), Monomers, oligomers, or prepolymers having a polycondensation reactive group (for example, polybasic acid or anhydride thereof, N-methylol group, aldehyde group / carbonyl group + active methylene / hydrazine group, etc.), etc. Like a blocked isocyanate, it may have a functional group that exhibits crosslinkability as a result of a decomposition reaction, As those which cure quickly by the action of sexual energy ray, a compound having an ethylenically unsaturated group or a ring-opening polymerizable group is preferable, in particular compounds having an ethylenically unsaturated group in the present invention is preferred.

  Examples of the compound having two or more ethylenically unsaturated groups in one molecule include (meth) acrylic acid esters of polyhydric alcohols (for example, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane). Diacrylate, pentaerythritol tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol Penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetra (meth) acrylate, polyurethane (meth) acrylate, polyester (meth) acrylate Polyether (meth) acrylate, polyol (meth) acrylate, etc.), vinylbenzene or derivatives thereof (for example, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone, etc.) Vinyl sulfone (for example, divinyl sulfone), acrylamide (for example, methylenebisacrylamide), methacrylamide, and the like.

  As the compound having a plurality of ring-opening polymerizable groups in one molecule, for example, the ethylenically unsaturated group of the above compound was replaced with a ring-opening polymerizable group (for example, epoxy group, oxetanyl group, oxazolyl group, etc.). Compounds, glycidyl (meth) acrylate, and the like. Examples of commercially available products include Denacol EX 314, 411, 421, 521, 611, 612, etc. (manufactured by Nagase Kasei Kogyo Co., Ltd.), Celoxide, GT301, 401, etc. Company-made).

In the present invention, the fluorine-containing compound (any of fluorine-containing monomer and fluorine-containing polymer) is used as the main component (50% by mass or more) of the binder that forms the fine uneven structure (fluorine-containing resin layer). be able to. In this case, it is not necessary to add the fluorine-containing surfactant or the like separately, but it can be used in combination in order to enhance the antifouling effect.
The addition amount of the fluorine-containing polymer is preferably 0.5 to 70% by mass, more preferably 1 to 60% by mass in terms of solid content with respect to the fluorine-containing resin composition.
When using the said fluorine-containing compound as a binder, it needs to be able to express sufficient mechanical characteristics, and the fluorine-containing prepolymer which has favorable hardening reactivity is suitable.
The amount of the binder added is preferably 10 to 80% by mass and more preferably 20 to 70% by mass in terms of solid content with respect to the fluorine-containing resin composition.

  When the fluorine-containing compound is used as a binder, the content of the crosslinking reactive group-containing monomer in the fluorine-containing copolymer is preferably 30 mol% to 95 mol%, more preferably 40 mol% to 90 mol%, and 45 to 80 mol%. Is more preferable.

  Examples of the fluorine-containing prepolymer include a compound used as a copolymer obtained by copolymerizing a monomer having a fluorine-containing alkyl group and a crosslinking reactive group-containing monomer. Among them, as the crosslinking reactive group-containing monomer, Those having a high cross-linking group content (for example, P-29 and the like) can be suitably used.

  Similarly, in copolymers of perfluoroolefin (fluoroethylene, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, etc., preferably hexafluoropropylene) and vinyl ethers, vinyl esters, etc. A structure having a reactive group-containing monomer is also suitable.

  Hereinafter, although the specific example of the fluorine-containing prepolymer which can be utilized suitably as a binder of a fluorine-containing resin layer is shown, this invention is not limited to these.

  There is no restriction | limiting in particular as said fluorine-containing polymer, Although it can synthesize | combine according to the above-mentioned general synthesis method, when using perfluoroolefin which is a gas monomer, it synthesize | combines using an autoclave. In this case, the reaction pressure can be appropriately selected, but usually 0.1 to 10 MPa is preferable, and 0.1 to 3 MPa is more preferable.

In the fluorine-containing polymer layer, the fluorine-containing compound, the non-fluorine binder material and the like may be appropriately selected and used in combination of two or more.
Since the fluorine-containing polymer having a crosslinkable group has a crosslinkable group in the polymer, high hardness can be obtained without increasing the amount of a curing agent to be described later. Therefore, the addition amount of the fluorine-containing polymer having a crosslinkable group is preferably 20 to 95% by mass and more preferably 30 to 80% by mass with respect to the fluorine-containing resin composition.

  In addition to the fluorine-containing compound, the fluorine-containing resin composition of the present invention is further required from the viewpoints of hardness, brittleness, adhesion to a substrate, dustproof property (antistatic property), releasability and the like. In addition, various additives such as a curing agent, fine particles, a surfactant, and a release agent can be blended.

There is no restriction | limiting in particular as said hardening | curing agent, According to the objective, it can select suitably, For example, ethylenically unsaturated group (For example, (meth) acryloyl group, a vinyl group, a vinyloxy group, an allyl group etc. in a molecule | numerator etc. ), Ring-opening polymerizable group (for example, epoxy group, oxetanyl group, oxazolyl group, etc.), reactive silyl group (for example, alkoxysilyl group, acetoxysilyl group, hydroxysilyl group, etc.), polyaddition reactive group (for example, Isocyanate group + hydroxyl group, vinyl group + hydrosilyl group, etc.), polycondensation reactive group (for example, polybasic acid or its anhydride, N-methylol group, aldehyde group or carbonyl group and active methylene group or hydrazine group), Suitable examples include monomers, oligomers, and prepolymers having the following.
Moreover, although there can be suitably mentioned those having a functional group that exhibits crosslinkability as a result of the decomposition reaction, such as blocked isocyanate, it is preferably cured rapidly by the action of active energy rays, and particularly ethylenic. A compound having an unsaturated group or a ring-opening polymerizable group is preferred.

Examples of the curing agent having an ethylenically unsaturated group include (meth) acrylic acid esters of polyhydric alcohols, vinyl benzene or derivatives thereof, vinyl sulfone, (meth) acrylamide, and the like.
Examples of the (meth) acrylic acid esters of the polyhydric alcohol include, for example, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol tetra (meth) acrylate), and pentaerythritol tri (meth) acrylate. , Trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3 -Cyclohexanetetra (meth) acrylate, polyurethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate , And the like. Examples of the vinylbenzene or derivatives thereof include 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone, and the like. Examples of the vinyl sulfone include divinyl sulfone. Examples of the (meth) acrylamide include methylene bisacrylamide and methacrylamide.

The curing agent having a ring-opening polymerizable group is not particularly limited and may be appropriately selected depending on the purpose. For example, the curing agent having an ethylenically unsaturated group may be a ring-opening polymerizable group (for example, A compound substituted with an epoxy group, an oxetanyl group or an oxazolyl group), glycidyl (meth) acrylate, or the like.
As the curing agent having a ring-opening polymerizable group, a commercially available product can be used. For example, Denacol EX314, 411, 421, 521, 611, 612, etc. (above, manufactured by Nagase Chemical Industries, Ltd.) ), Celoxide, GT301, GT401 and the like (manufactured by Daicel Industries, Ltd.).

  The compounding amount of the curing agent is preferably 1 to 97% by mass, more preferably 1 to 70% by mass, still more preferably 5 to 50% by mass, and more preferably 10 to 30% by mass with respect to the fluorine-containing resin composition. Is particularly preferred.

As the fine particles, for example, inorganic fine particles such as SiO ₂ , MgF ₂ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ and ITO are suitable. Among these, SiO ₂ is particularly preferable.
As the fine particles, commercially available products can be used, and examples thereof include Snowtex IPA-ST and MIBK-ST manufactured by Nissan Chemical Industries, Ltd., AEROSIL300, AEROSIL130 and AEROSIL50 manufactured by Nippon Aerosil Co., Ltd.
The particle diameter of the fine particles is preferably 1 to 100 nm, more preferably 1 to 50 nm, and still more preferably 5 to 30 nm.
In order to bond the resin more strongly with the resin forming the binder, it is preferable to use the fine particles whose surface is modified with a reactive group such as a (meth) acryloyl group or an epoxy group. The surface modification of the fine particles can be performed using a silane coupling agent having a functional group such as a (meth) acryloyl group or an epoxy group.
1-50 mass% is preferable with respect to the total solid of the said fluorine-containing resin composition, and, as for the addition amount of the said fine particle, 5-40 mass% is more preferable, and 10-30 mass% is still more preferable.

There is no restriction | limiting in particular as said surfactant, According to the objective, it can select suitably, For example, both the said fluorosurfactant and silicone type surfactant can be used.
As the fluorine-based surfactant, the same ones as described above can be used.
Examples of the silicone surfactant include polydimethylsiloxane in which side chains and main chain ends are modified with various substituents such as oligomers such as ethylene glycol and propylene glycol.
0.001-10 mass% is preferable with respect to the total solid of a fluorine-containing resin composition, and, as for the addition amount of the said surfactant, 0.01-5 mass% is more preferable, and 0.5-5 mass% is still more. preferable.

  When the fine concavo-convex structure is formed by a shape transfer method, the resin layer preferably contains a release agent component. As the release agent component, a silicone material is preferable. As the release agent component, commercially available products can be used. For example, AK-5, AK-30, AK-32 (all manufactured by Toa Gosei Co., Ltd.), Silaplane FM0275, Silaplane FM0721 (both Manufactured by Chisso Corporation), KF-100T, X-22-169AS, KF-102, X-22-3701IE, X-22-164B, X-22-164C, X-22-5002, X-22-173B, X-22-174D, X-22-167B, X-22161AS (all manufactured by Shin-Etsu Chemical Co., Ltd.), RMS033 (manufactured by Asmax Co., Ltd.), and the like.

  1-20 mass% is preferable with respect to the total solid of the said fluorine-containing resin composition, 2-15 mass% is more preferable, and, as for the addition amount of the said mold release agent component, 3-10 mass% is still more preferable.

  If necessary, the fluorine-containing resin composition of the present invention may further contain a curing catalyst or an initiator. For example, a radical polymerization initiator is added to initiate the polymerization of ethylenically unsaturated groups. As the radical polymerization initiator, either a polymerization initiator that generates radicals by the action of heat or a polymerization initiator that generates radicals by the action of active energy rays can be used.

  The compound that initiates radical polymerization by the action of heat is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include organic peroxides, inorganic peroxides, organic azo compounds, and diazo compounds. Is preferred. Examples of the organic peroxide include benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide, and the like. Examples of the inorganic peroxide include hydrogen peroxide, ammonium persulfate, and potassium persulfate. Examples of the organic azo compound include 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, and the like. Examples of the diazo compound include diazoaminobenzene, p-nitrobenzenediazonium, and the like.

The compound that initiates radical polymerization by the action of the active energy ray is not particularly limited and may be appropriately selected depending on the intended purpose. For example, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, Anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums and the like can be mentioned. Examples of the acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, Examples include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone. Examples of the 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, p-chlorobenzophenone, and the like. Examples of the phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
In addition, a sensitizing dye can also be preferably used in combination with these photo radical polymerization initiators.

  The amount of the compound that initiates radical polymerization by the action of heat or active energy rays is not particularly limited as long as the polymerization of carbon-carbon double bonds is initiated, and may be appropriately selected according to the purpose. However, 0.1-15 mass% is preferable with respect to the total solid of the said fluorine-containing resin composition, and 0.5-5 mass% is more preferable.

On the other hand, in order to start the reaction of the ion polymerizable compound or the sol-gel material, a known catalyst can be appropriately blended. Examples of the catalyst include an acid catalyst and a base catalyst. Examples of the acid catalyst include inorganic Bronsted acids such as hydrochloric acid, sulfuric acid and nitric acid, organic Bronsted acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and paratoluenesulfonic acid, dibutyltin dilaurate, dibutyltin diacetate And Lewis acids such as dibutyltin dioctate, triisopropoxyaluminum, and tetrabutoxyzirconium. Examples of the base catalyst include inorganic bases such as sodium hydroxide, potassium hydroxide, and ammonia, and organic bases such as triethylamine, pyridine, and tetramethylethylenediamine.
The addition amount of the curing catalyst varies depending on the type of the catalyst, the difference in the curing reactive site, etc., and cannot be unconditionally specified, but is 0.1 to 15 mass relative to the total solid content of the fluorine-containing resin composition. % Is preferable, and 0.5 to 5% by mass is more preferable.

  Moreover, you may use the compound which generate | occur | produces hardening accelerators, such as an acid or a base, by the effect | action of an active energy ray from a viewpoint of the storage stability of the said fluorine-containing resin composition. When these compounds are used, there is an advantage that the film can be cured by irradiation with active energy rays.

Examples of the compound that generates an acid by the action of the active energy ray include those described in “Organic Materials for Imaging” p187 to 198 edited by Organic Electronics Materials Research Group (Bunshin Publishing) and Japanese Patent Laid-Open No. 10-282644. Compounds can be used. Specifically, as the compound, RSO ₃ ⁻ (wherein R represents an alkyl group or an aryl group), AsF ₆ ⁻ , SbF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ^{− and the} like are used as counter ions. Various onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts, organic halides such as oxadiazole derivatives substituted with a trihalomethyl group, S-triazine derivatives, organic acids o-Nitrobenzyl ester, benzoin ester, imino ester, disulfone compound and the like. Among these, onium salts, sulfonium salts, and iodonium salts are preferable.
The compound that generates a base by the action of the active energy ray is not particularly limited and can be appropriately selected from known compounds according to the purpose. For example, nitrobenzyl carbamates, dinitrobenzyl carbamates, etc. Is mentioned.
A sensitizing dye can also be suitably used in combination with a compound that generates an acid or a base by the action of these active energy rays. The amount of the compound that accelerates the curing reaction by the action of the active energy rays or the addition amount of the sensitizing dye is preferably 0.1 to 15% by mass with respect to the total solid content in the fluorine-containing resin composition, 0.5 to 5 mass% is more preferable.

Further, when a dehydrating condensable compound such as a sol-gel material or aminoplast is used, a dehydrating agent may be appropriately used for the purpose of accelerating curing. There is no restriction | limiting in particular as this dehydrating agent, According to the objective, it can select suitably, For example, carboxylic acid orthoester (For example, a methyl orthoformate, an orthoformate ethyl, ortho orthomethyl etc.), an acid anhydride (for example, , Acetic anhydride, etc.).
The addition amount of the dehydrating agent is preferably 0.5 to 500 parts by mass, more preferably 5 to 200 parts by mass, and further more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the total solid content of the fluorine-containing resin composition. preferable.

  The fluorine-containing resin composition of the present invention can be produced by using the above-mentioned fluorine-containing compound as an essential component and further blending other components as necessary. In this case, when any of the above components is a liquid compound, it is not necessary to add a solvent separately if other components can be dissolved using the component as a solvent, but if this is not the case, the solvent is not added. A fluorine-containing resin composition can be produced by dissolving each constituent component.

  The solvent used in the fluorine-containing resin composition is not particularly limited as long as the composition is uniformly dissolved or dispersed without causing precipitation, and can be appropriately selected according to the purpose. For example, ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (for example, ethyl acetate, butyl acetate, etc.), ethers (for example, tetrahydrofuran, 1,4-dioxane, etc.), alcohols (for example, Methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, etc.), aromatic hydrocarbons (eg, toluene, xylene, etc.), water, and the like. These may be used individually by 1 type and may use 2 or more types together.

  The fluorine-containing resin composition of the present invention has a fine concavo-convex structure excellent in optical properties and antifouling properties, and can be suitably used in various fields, but is particularly preferably used as the following optical article. Can do.

(Optical article)
The optical article of the present invention has a fine concavo-convex structure formed using the fluorine-containing resin composition of the present invention, and further includes other members as necessary.

  The optical article is not particularly limited as long as it is an optical element using a periodic fine concavo-convex structure of a visible light wavelength or less, and can be appropriately selected according to the size and shape of the fine concavo-convex, for example, an antireflection film And various uses such as an antireflection film, a polarization separation element, an optical waveguide, a relief hologram, a lens, an optical card, and an optical disk. Among these, it is particularly suitably used for antireflection material applications such as an antireflection film and an antireflection film. For details on the use of the optical article, see Hisao Kikuta J83-C (3), p. 173-181 (2000), and the like.

The concavo-convex period (Λ) of the fine concavo-convex structure on the outermost surface of the optical article is preferably 10 to 400 nm, and Λ <400 / n (nm) is more preferable when the refractive index of the fine concavo-convex structure layer is n. Under such conditions, no visible light scattering occurs.
The height (depth) of the fine irregularities is preferably 50 to 1000 nm, more preferably 200 to 1000 nm, and still more preferably 300 to 1000 nm.

The shape of the fine concavo-convex structure is not particularly limited and may be appropriately selected depending on the intended purpose. For example, when used for an antireflection film, a conical shape, a triangular pyramid shape, a bell shape, an air interface A structure in which the average refractive index from the air interface (refractive index of about 1) to the support continuously changes depending on the shape of the undulated uniaxially shaped side is preferable. Among these, a cone type, Those with a fine concavo-convex structure with no directionality such as a triangular pyramid type and a bell shape are more preferable, and those with a continuous change in refractive index in the thickness direction are linear (linear function) such as a cone type and a triangular pyramid type. Particularly preferred.
Note that a shape having a fine concavo-convex structure with a rectangular cross section and the like in which there is no continuous change in the refractive index in the thickness direction can be used as a low refractive index layer of a multilayer film although it is not a preferable form in an antireflection film.

The reflectance of the optical article of the present invention (fine concavo-convex structure film such as an antireflection film or antireflection film) is preferably as low as possible. Specifically, the mirror surface average reflectance in the wavelength region of 450 to 650 nm is 2% or less. Preferably, it is 1% or less, more preferably 0.5% or less.
Here, the specular average reflectance in the wavelength region of 450 to 650 nm is measured by measuring the spectral reflectance at an incident angle of 5 ° in the wavelength region of 380 to 780 nm using a spectrophotometer, for example, and 450 to 650 nm. It is possible to calculate and obtain the mirror surface average reflectance.

  The fine concavo-convex structure is known to act in the direction of enhancing the wettability of droplets (for example, described in detail in Surface 35 (12), page 629 (1997)). That is, when the surface tension of the solid is not sufficiently low relative to the surface tension of the droplet (specifically, when the contact angle of the droplet on a flat surface is less than 90 °), It will act in the direction of more wetting. On the other hand, when the surface tension of the solid is sufficiently low, the droplet is more repelled. Although it is relatively easy to create a surface that repels water with high surface tension, it is more difficult to repel oil droplets with low surface tension.

In the present invention, in order to improve the antifouling property (particularly the penetration of oil droplets) which is a problem in the fine concavo-convex structure, the fine concavo-convex structure is a fluorine-containing resin layer having a low surface tension. The surface tension of the fine concavo-convex structure is preferably 25 mN / m or less, more preferably 20 mN / m or less, and even more preferably 15 mN / m or less.
When the surface tension exceeds 25 mN / m, the antifouling property of the optical article may be insufficient.

  The refractive index of the fluorine-containing resin composition (refractive index when fine irregularities are not imparted) is not particularly limited and can be appropriately selected according to the purpose, preferably 1.25 to 1.70. 30 to 1.60 is more preferable, and 1.40 to 1.55 is still more preferable. The higher the refractive index, the shorter the optimum fine irregularity period for preventing the scattering of visible light, which may increase the difficulty of manufacturing. On the other hand, if the refractive index is lowered, scratch resistance, etc. It may be difficult to achieve both film properties.

The optical article of the present invention contains fluorine atoms on the surface, and the fluorine atom content is preferably 20 atomic percent or more, more preferably 30 to 75 atomic percent.
When the fluorine atom content is less than 20 atomic percent, the antifouling property of the optical article may be insufficient.
The fluorine atom content can be suitably measured by, for example, X-ray photoelectron spectroscopy. The X-ray photoelectron spectroscopy (XPS) can be performed using, for example, a known X-ray photoelectron spectroscopy (XPS) apparatus (for example, a 1600S type X-ray photoelectron spectrometer manufactured by PHI), and the fluorine The atomic content can be measured by separating peaks caused by fluorine atoms.

  The existence region of the fluorine concavo-convex structure of the fluorine atom is not particularly limited and may be appropriately selected depending on the purpose, but is preferably a surface layer of about several nm from the surface of the micro concavo-convex structure, The surface layer is more preferably 0 to 10 nm from the particle surface.

  The method for forming the fine concavo-convex shape is not particularly limited and can be appropriately selected from known methods according to the purpose, but is inexpensive and complementary from the viewpoint of stable production of large-area processing. Forming a fine relief structure by pressing a stamper with a fine relief structure and transferring the shape to the resin, or using a phase separation of two types of resins and eluting only one component using an appropriate solvent Among them, a shape transfer method using a stamper is particularly preferable.

  A stamper used for the shape transfer method is known in which a prototype having a fine irregular shape is produced by a laser interference exposure method or an electron beam exposure method for a photosensitive resin, and further electroformed with Ni or the like on the prototype. It can produce by the method of. Shape transfer can be performed by pressing the stamper to an uncured or semi-cured resin or a thermoplastic resin. There are no particular limitations on the temperature conditions and pressure conditions when performing the shape transfer, and they can be appropriately selected according to the purpose. The temperature conditions are preferably 50 to 250 ° C, more preferably 50 to 200 ° C. Preferably, 50 to 150 ° C is more preferable. As this pressure condition, 0.1-15 MPa is preferable, 0.5-10 MPa is more preferable, 1-5 MPa is still more preferable.

  As the stamper, if an embossing roll mounted around a metal roll is used, large-area processing can be performed in a roll-to-roll process.

  When shape transfer is performed on the ultraviolet curable resin, (1) an uncured or semi-cured resin is coated on the support, pressed with the stamper, and further irradiated with ultraviolet light from the back side of the support. After the resin layer is cured while transferring the shape, the stamper is peeled off. (2) After the stamper is pressed against the uncured or semi-cured resin layer and the stamper is peeled off, the ultraviolet ray is removed. There is a method of curing the resin layer by irradiation, and any form is preferably used in the present invention.

Each layer is cured by the action of ionizing radiation and / or heat. The irradiation with ionizing radiation is preferably performed using a high-pressure mercury lamp. At this time, the ultraviolet irradiation is preferably performed under a predetermined oxygen concentration. The oxygen concentration is preferably 0.5% or less, more preferably 0.3% or less, and still more preferably 0.2% or less. The irradiation energy is not particularly limited as long as it is an amount necessary for the curing reaction to proceed sufficiently, and can be appropriately selected according to the purpose. For example, 300 mJ / cm ^{2 to} 1500 mJ / cm ² is preferable, and 400 mJ / Cm ^{2 to} 1000 mJ / cm ² is more preferable, and 500 mJ / cm ^{2 to} 800 mJ / cm ² is still more preferable.

  In the case of performing the heating, the heating temperature is preferably 30 to 200 ° C, more preferably 80 to 180 ° C, and further preferably 100 to 150 ° C. The heating time is preferably 30 seconds to 100 hours, more preferably 1 minute to 1 hour, and even more preferably 2 minutes to 15 minutes.

  The resin may be partially cured by the ultraviolet irradiation or heating means before pressing the stamper to transfer the shape. Moreover, at the time of shape transfer, the curing reaction may be performed by simultaneously applying two energies of light and heat, or the curing may be performed with only one energy. The method of applying at least one of the above light and heat can also be used when completely curing after forming the shape.

  When the optical article of the present invention has a multi-layer structure, it is preferable to coat the upper layer after each layer is sufficiently cured in sequence.

-Antireflection film-
The antireflection film as the optical article of the present invention is composed of a resin film having a fine concavo-convex structure formed using the fluorine-containing resin composition of the present invention.
In this case, it is preferable that a resin layer having a fine concavo-convex shape is formed on the support and then used by being placed in a device (for example, an image display device such as a display). You may arrange directly.

The antireflection film is applied to a polarizing plate, a display device, for example, an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), or a cathode ray tube display device (CRT). To do. The antireflection film is arranged so that the fine uneven structure is on the air interface side. When the antireflection film is provided on a support and used as an antireflection film, the support side is adhered to an image display surface of an image display device.
In addition to the image display device, the antireflection film can be used for a case cover, an optical lens, a spectacle lens, a window shield, a light cover, and a helmet shield.

  The antireflection film may have an antiglare function for scattering external light. The antireflection film of the present invention is provided with a periodic fine concavo-convex structure having a visible light wavelength or less on the surface, and in addition to this, by providing a gentle concavo-convex structure having a visible light wavelength or more, an antiglare function is provided. (That is, this is a structure in which a fine uneven structure is provided on a large gentle uneven shape). The gentle concavo-convex shape includes a method using a stamper having a complementary shape, a method in which a surface having a large concavo-convex structure is formed by fine particles, and a method of pressing a stamper, and forming a large concavo-convex structure using fine particles. It can be produced by a method of forming a small uneven structure using phase separation.

The haze (when there is no antiglare function) of the antireflection film is preferably 3% or less, more preferably 1% or less, and still more preferably 0.5% or less. The strength of the antireflection film is 1H or higher, preferably 1H or higher, more preferably 2H or higher, and still more preferably 3H or higher, with a pencil hardness of 1 kg.
When the antireflection film has an antiglare function, the haze of the antireflection film is preferably 3 to 30%, more preferably 5 to 20%, and still more preferably 7 to 20%.

  The antireflection layer (fine concavo-convex structure layer) may be provided directly on the CRT image display surface or the lens surface. Usually, a fine concavo-convex structure layer is provided on the support, for example, as an antireflection film or the like. It is preferable to be mounted on the device.

-Antireflection film-
The antireflection film as the optical article of the present invention is provided with a support and a fine uneven structure layer (antireflection layer) formed from the fluorine-containing resin composition on the support, and further required. Accordingly, layers such as a hard coat layer, a moisture-proof layer, an antistatic layer, and an undercoat layer may be provided.

There is no restriction | limiting in particular as said support body, Although it can select suitably according to the objective, A plastic film is more preferable than points, such as a moldability and mass-productivity, than a glass plate.
Examples of the plastic film material include cellulose ester, polyamide, polycarbonate, polyester, polystyrene, polyolefin, polysulfone, polyethersulfone, polyarylate, polyetherimide, polymethylmethacrylate, polyetherketone, and the like.
Examples of the cellulose ester include triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose, and the like. Examples of the polyester include polyethylene terephthalate, polyethylene naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, and polybutylene terephthalate. It is done. Examples of the polystyrene include syndiotactic polystyrene. Examples of the polyolefin include polypropylene, polyethylene, and polymethylpentene.
Among these, triacetyl cellulose, polycarbonate, polyethylene terephthalate and polyethylene naphthalate are particularly preferable.

An infrared absorber or an ultraviolet absorber may be added to the support, and the amount of the infrared absorber or the ultraviolet absorber added to the support is preferably 0.01 to 20% by mass, and 0.05 to 10%. The mass% is more preferable.
There is no restriction | limiting in particular in the thickness of the said support body, According to the objective, it can select suitably, For example, 50-200 micrometers is preferable.

  When forming a fine concavo-convex shape on the resin layer using a stamper, when selecting a method of irradiating active energy rays from the support side to cure the resin layer, the support has active energy rays such as an ultraviolet absorber. It is desirable not to add a substance that absorbs light, and it is preferable to select a support that does not absorb in the exposure wavelength region.

From the viewpoints of increasing the strength and reducing the thermal expansion, inorganic compound particles may be added to the support. Examples of inorganic compounds include SiO ₂ , TiO ₂ , BaSO ₄ , CaCO ₃ , talc, kaolin, and the like.

  The support may be subjected to a surface treatment. 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, ozone oxidation treatment, and the like. It is done. Among these, glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment, and flame treatment are preferable, and glow discharge treatment and ultraviolet treatment are particularly preferable.

  The light transmittance of the support is preferably 80% or more, and more preferably 86% or more. The haze of the support is preferably 2.0% or less, and more preferably 1.0% or less. The support preferably has a refractive index of 1.4 to 1.7, and when used as an antireflection film, a support having a small refractive index difference from the resin layer is preferable.

  The fine concavo-convex structure layer formed on the support 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 (US Pat. No. 2,681,294). It can be formed by coating according to the description. Two or more layers may be applied simultaneously. The methods of simultaneous application are described in US Pat. Nos. 2,761,789, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973).

The hard coat layer is provided for imparting scratch resistance to the support, and also has a function of strengthening the adhesion between the support and the layer thereon.
The hard coat layer can be formed using an acrylic polymer, a urethane polymer, an epoxy polymer, a silicone 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 (for example, polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate). Examples of the urethane polymer include melamine polyurethane. Examples of the silicone polymer include co-hydrolysis of a silane compound (eg, tetraalkoxysilane, alkyltrialkoxysilane) and a silane coupling agent having a reactive group (eg, epoxy group, (meth) acryloyl group). A thing is mentioned suitably. Two or more kinds of polymers may be used in combination. As said silica type compound, colloidal silica is mentioned suitably.
The strength of the hard coat layer is a pencil hardness of 1 kg load, preferably H or higher, more preferably 2H or higher, and further preferably 3H or higher. In addition to the hard coat layer, an adhesive layer, a shield layer, and an antistatic layer may be provided on the support. The shield layer is provided to shield electromagnetic waves and infrared rays.

(Image display device)
The image display device includes any one of the antireflection film of the present invention and the antireflection film of the present invention as the optical article, and further includes other members as necessary.
There is no restriction | limiting in particular as said image display apparatus, According to the objective, it can select suitably, For example, a cathode-ray tube display apparatus (CRT), a plasma display (PDP), an electroluminescent display (ELD), a liquid crystal display apparatus ( LCD). Among these, a liquid crystal display device is particularly preferable.

  As the liquid crystal display device, liquid crystal is sealed between a pair of substrates arranged opposite to each other. As the liquid crystal in the liquid crystal display device, for example, STN type, TN type, GH type, ECB type, strong Preferred examples include dielectric liquid crystals, antiferroelectric liquid crystals, VA type, ASM type, and other various types.

  As a basic configuration mode of the liquid crystal display device of the present invention, for example, (1) a driving element such as a thin film transistor (hereinafter sometimes referred to as “TFT”) and a pixel electrode (conductive layer) are arranged and formed. The drive side substrate and the color filter side substrate including the color filter and the counter electrode (conductive layer) are arranged to face each other with a spacer interposed therebetween, and a liquid crystal material is sealed in the gap portion, (2) A color filter integrated drive substrate in which a color filter is directly formed on the drive side substrate and a counter substrate having a counter electrode (conductive layer) are arranged to face each other with a spacer interposed therebetween, and a liquid crystal material is sealed in the gap portion. And the like.

  Hereinafter, although the Example of this invention is described, this invention is not limited to this Example at all.

(Synthesis Example 1)
-Synthesis of fluorine-containing copolymer (P-2)-
In a reactor equipped with a stirrer and a reflux condenser, 39.93 g of 1H, 1H, 7H-dodecafluoroheptyl acrylate, 1.1 g of dimethyl 2,2′-azobisisobutyrate, and 30 g of 2-butanone are added, The reaction was completed by heating at 78 ° C. for 6 hours under a nitrogen atmosphere. As described above, a fluorine-containing copolymer (P-2) represented by the following structural formula was synthesized.
The obtained fluorine-containing copolymer (P-2) had a mass average molecular weight (Mw) of 2.9 × 10 ⁴ .

(Synthesis Example 2)
-Synthesis of fluorine-containing copolymer (P-13)-
In a reactor equipped with a stirrer and a reflux condenser, 1H, 1H, 7H-dodecafluoroheptyl acrylate 31.98 g, Blemmer AP-400 (trade name, manufactured by NOF Corporation), 7.95 g of dimethyl 2,2 ′ -1.1 g of azobisisobutyrate and 30 g of 2-butanone were added, and the reaction was completed by heating at 78 ° C for 6 hours under a nitrogen atmosphere. As described above, a fluorine-containing copolymer (P-13) represented by the following structural formula was synthesized.
The obtained fluorine-containing copolymer (P-13) had a mass average molecular weight (Mw) of 3.4 × 10 ⁴ .

(Synthesis Example 3)
-Synthesis of fluorine-containing copolymer (P-37)-
To 71 g of the fluorine-containing polymer solution obtained in Synthesis Example 2, 2.81 g of 2-isocyanatoethyl methacrylate and 0.1 g of dibutyltin dilaurate were added and reacted at room temperature for 12 hours. As described above, a fluorine-containing copolymer (P-37) represented by the following structural formula was synthesized.
From the IR spectrum of the obtained fluorine-containing copolymer-containing solution, the isocyanate groups were completely consumed, a new peak due to urethane bonds was observed, and the mass average molecular weight of the polymer was 3.7 × 10 ⁴ .

(Synthesis Example 4)
-Synthesis of fluorine-containing copolymer (PP-1)-
In an autoclave with a stirrer made of stainless steel having an internal volume of 100 ml, 40 ml of ethyl acetate, 14.7 g of hydroxyethyl vinyl ether and 0.55 g of dilauroyl peroxide were charged, and the inside of the system was deaerated and replaced with nitrogen gas. Furthermore, 25 g of hexafluoropropylene (HFP) was introduced into the autoclave and the temperature was raised to 65 ° C. The pressure when the temperature in the autoclave reached 65 ° C. was 0.54 MPa. The reaction was continued for 8 hours while maintaining the temperature, and when the pressure reached 0.32 MPa, the heating was stopped and the mixture was allowed to cool. When the internal temperature dropped to room temperature, unreacted monomers were driven out, the autoclave was opened, and the reaction solution was taken out.
The obtained reaction solution was poured into a large excess of hexane, and the polymer was precipitated by removing the solvent by decantation. The polymer was then dissolved in a small amount of ethyl acetate and the remaining monomer was completely removed by reprecipitation from hexane twice. After drying, 28 g of a fluorine-containing copolymer having a molar ratio of hexafluoropropylene and hydroxyethyl vinyl ether of 1: 1 was obtained. The refractive index of the obtained fluorine-containing copolymer was 1.406.
Next, 20 g of the fluorine-containing copolymer was dissolved in 100 ml of N, N-dimethylacetamide, and 11.4 g of acrylic acid chloride was added dropwise under ice cooling, followed by stirring at room temperature for 10 hours. Ethyl acetate was added to the reaction solution, washed with water, and the organic layer was extracted and concentrated. The resulting polymer was reprecipitated with hexane. As a result, 19 g of a fluorine-containing copolymer (PP-1) represented by the following structural formula was obtained.
The number average molecular weight (Mn) of the obtained polymer was 31,000, and the refractive index was 1.421.

  The fluorine-containing polymers “P-38” and “P-30” used in the examples described later can also be synthesized by the same method.

(Synthesis Example 5)
-Synthesis of binder resin A-
A binder resin A represented by the following structural formula was synthesized according to the method described in Example 1 of JP-A-2003-82043.
That is, a 2-liter flask equipped with a condenser, a dropping funnel and a thermometer was charged with 40 g of toluene and 40 g of methyl ethyl ketone together with an azo polymerization initiator, 20.8 g of 2-hydroxymethyl methacrylate, 39.0 g of methyl methacrylate, A mixture of 45.0 g of nyl methacrylate, 20 g of toluene, and 20 g of methyl ethyl ketone was reacted at a temperature of 100 ° C. for 8 hours while being dropped with a dropping funnel, and then cooled to room temperature. A mixed liquid of 23.4 g of 2-isocyanatoethyl methacrylate (manufactured by Showa Denko, Karenz MOI (trade name)), 20 g of toluene, and 20 g of methyl ethyl ketone was added thereto, and an addition reaction was performed using dibutyltin laurate as a catalyst.
By IR analysis of the obtained reaction product, the disappearance of the absorption peak of isocyanate was confirmed, and the reaction was completed. The solid content of the obtained binder resin A solution was 38.2% by mass, the mass average molecular weight (Mw) was 30,000 in terms of polystyrene, and the introduction amount of carbon-carbon double bonds (C = C) was 12.5. %Met.

(Example 1)
-Preparation of fluorine-containing resin composition-
1 part by mass of the fluorine-containing copolymer “P-37” of Synthesis Example 1, 94 parts by mass of DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., polyfunctional curing agent KAYARAD) as a curing agent, RMS033 (as a release agent) Trade name, 5 parts by mass of Azmax methacryloyl-modified silicone oil) and 5 parts by mass of Irgacure (IRG) 907 (trade name, manufactured by Ciba Specialty Chemicals) as photo-radical polymerization initiator were added to 30% by mass of methyl ethyl ketone ( The fluorine-containing resin composition of Example 1 was prepared.

(Example 2)
-Preparation of fluorine-containing resin composition-
1 part by mass of the fluorine-containing copolymer “P-37” of Synthesis Example 1, 64 parts by mass of Binder Resin A of Synthesis Example 5, DPHA as a curing agent (trade name, manufactured by Nippon Kayaku Co., Ltd., polyfunctional curing agent KAYARAD) 30 parts by mass, 5 parts by mass of RMS033 (trade name, methacryloyl-modified silicone oil manufactured by Asmax Co., Ltd.) as a release agent, and Irgacure (IRG) 907 (trade name, manufactured by Ciba Specialty Chemicals) as a photo radical polymerization initiator 5 mass parts was melt | dissolved in methyl ethyl ketone so that it might become 30 mass% (solid content), and the fluorine-containing resin composition of Example 2 was prepared.

(Example 3)
-Preparation of fluorine-containing resin composition-
1 part by mass of the fluorine-containing copolymer “P-38”, 64 parts by mass of the binder resin A of Synthesis Example 5, 30 parts by mass of DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., polyfunctional curing agent KAYARAD), 5 parts by mass of RMS033 (trade name, methacryloyl-modified silicone oil manufactured by Asmax Co., Ltd.) as a release agent and 5 parts by mass of Irgacure (IRG) 907 (trade name, manufactured by Ciba Specialty Chemicals) as a photo radical polymerization initiator The fluorine-containing resin composition of Example 3 was prepared by dissolving in methyl ethyl ketone at 30% by mass (solid content).

Example 4
-Preparation of fluorine-containing resin composition-
Fluorine-containing copolymer “P-30” 50 parts by mass, DPHA as a curing agent (trade name, manufactured by Nippon Kayaku Co., Ltd., polyfunctional curing agent KAYARAD) 45 parts by mass, RMS033 as a release agent (trade name, Azmax) 5 parts by mass of methacryloyl-modified silicone oil (trade name) and 5 parts by mass of Irgacure (IRG) 907 (trade name, manufactured by Ciba Specialty Chemicals) as a photo radical polymerization initiator, and 30% by mass (solid content) in methyl ethyl ketone Thus, the fluorine-containing resin composition of Example 4 was prepared.

(Example 5)
-Preparation of fluorine-containing resin composition-
70 parts by mass of the fluorine-containing copolymer “PP-1” of Synthesis Example 4, 1 part by mass of the fluorine-containing copolymer “P-38”, DPHA as a curing agent (trade name, manufactured by Nippon Kayaku Co., Ltd., multifunctional curing 45 parts by weight of the agent KAYARAD, 5 parts by weight of RMS033 (trade name, methacryloyl-modified silicone oil manufactured by Asmax Co., Ltd.) as a release agent, and Irgacure (IRG) 907 (trade name, Ciba Specialty Chemicals) as a radical photopolymerization initiator 5 parts by mass) were dissolved in methyl ethyl ketone so as to be 30% by mass (solid content) to prepare a fluorine-containing resin composition of Example 4.

(Comparative Example 1)
-Preparation of fluorine-containing resin composition-
67 parts by mass of binder resin A in Synthesis Example 5, 28 parts by mass of DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., polyfunctional curing agent KAYARAD) as a curing agent, KF-860 (trade name, Shin-Etsu Silicone) as a release agent 30 parts by mass (solid content) of methyl ethyl ketone with 5 parts by mass of amino-modified silicone oil (trade name) and 5 parts by mass of Irgacure (IRG) 184 (trade name, manufactured by Ciba Specialty Chemicals) as a photo-radical polymerization initiator The fluorine-containing resin composition of Comparative Example 1 was prepared.

(Comparative Example 2)
-Preparation of fluorine-containing resin composition-
39 parts by mass of binder resin A in Synthesis Example 5, 17 parts by mass of DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., polyfunctional curing agent KAYARAD) as a curing agent, MEK-ST (trade name, Nissan as silica fine particle dispersion) Silica fine particle dispersion manufactured by Chemical Industry Co., Ltd.) 39 parts by mass, 5 parts by mass of KF-860 (trade name, amino-modified silicone oil manufactured by Shin-Etsu Silicone Co., Ltd.) as a release agent, and Irgacure (IRG) as a photo radical polymerization initiator 5 parts by mass of 184 (trade name, manufactured by Ciba Specialty Chemicals) was dissolved in methyl ethyl ketone so as to be 30% by mass (solid content) to prepare a fluorine-containing resin composition of Comparative Example 2.

＊表１中、（ ）内の数字は各成分の質量部を表す。

* In Table 1, the numbers in () represent parts by mass of each component.

-Production of antireflection film-
After applying each fluorine-containing resin composition of Examples 1-5 and Comparative Examples 1-2 on a polyethylene terephthalate (PET) film having a thickness of 100 μm to a thickness of 3 μm using a bar coater, at 90 ° C. Dry for 5 minutes.
Next, a stamper made of Ni material having a periodic fine concavo-convex structure of a cone shape having a period of about 250 nm × a height of about 250 nm is pressed on the resin layer application surface of the film, and a stamper is applied for 1 minute under a pressure of 1 MPa. After pressure-contacting the film, the resin layer was cured by irradiating ultraviolet rays with energy of 750 mJ / cm ² from the back surface of the PET film. Thereafter, the film and the stamper were peeled off, and further, an ultraviolet ray was irradiated from the surface of the resin layer with an energy of 750 mJ / cm ^{2 in} a nitrogen atmosphere (oxygen concentration 0.1%) to form a fine uneven structure on the surface. Each antireflection film of Examples 1-5 and Comparative Examples 1-2 was produced.

<Performance evaluation of antireflection film>
About the antireflection films of Examples 1 to 5 and Comparative Examples 1 and 2 thus obtained, the mirror surface average reflectance, scratch resistance, fingerprint adhesion, magic adhesion, surface tension, and fluorine content were as follows. evaluated. The results are shown in Table 2.

(1) Specular Average Reflectance Using a spectrophotometer (manufactured by JASCO Corporation, V-550), the spectral reflectance at an incident angle of 5 ° is measured in a wavelength region of 380 to 780 nm, and a specular surface of 450 to 650 nm. Results were expressed as average reflectance.

(2) Scratch resistance test The film surface was rubbed 10 times under a load of 200 g using steel wool # 0000, and then the level of scratching was evaluated according to the following criteria.
〔Evaluation criteria〕
◎ ・ ・ ・ No scratches.
○ ・ ・ ・ Slightly scratched.
Δ: Fine scratches are noticeable.
X: Scratches are remarkable.

(3) Fingerprint adhesion evaluation Each antireflection film was conditioned at a temperature of 25 ° C. and a humidity of 60% RH for 2 hours, and then a fingerprint was attached to the surface of the antireflection film. The state when the product was wiped off was observed, and the fingerprint adhesion was evaluated as follows.
〔Evaluation criteria〕
◎ ・ ・ ・ Fingerprints can be easily wiped off.
〇 ... Wipe it normally to wipe off fingerprints.
Δ: Fingerprints can be wiped off by rubbing firmly.
X: Fingerprints remain without being wiped off.

(4) Magic adhesion evaluation Each antireflection film was conditioned at a temperature of 25 ° C. and a humidity of 60% RH for 2 hours, and then a magic (Macchi-extra fine (trade name; manufactured by ZEBRA)) was attached to the sample surface. Then, the state when the cloth was wiped with Ben Cotton (manufactured by Asahi Kasei Co., Ltd.) was observed, and the magic adhesion was evaluated as follows.
〔Evaluation criteria〕
◎ ・ ・ ・ Magic can be easily wiped off.
〇 ・ ・ ・ Magic can be wiped off by wiping normally.
Δ: Magic can be wiped off by rubbing firmly.
X ... Magic remains without being wiped off.

(5) Measurement of surface tension Each fluorine-containing resin composition was applied onto a PET film having a thickness of 100 nm using a bar coater so as to have a film thickness of 2 μm, and then in a nitrogen atmosphere (oxygen concentration 0.1%). A sample was prepared by irradiating ultraviolet rays with an energy of 750 mJ / cm ² to cure the coating film. About this sample, the contact angle of water and methylene iodide having a known surface tension was measured using a contact angle meter CA-DT • A manufactured by Kyowa Interface Chemical Co., Ltd. to determine the surface tension.

(6) Measurement of fluorine content The fluorine content in the fine concavo-convex structure of each antireflection film was measured by X-ray photoelectron spectroscopy (XPS) according to the following measuring apparatus and measurement conditions. In addition, the fluorine atom existed in the region of the extreme surface about several nm from the surface of the antireflection film.
[Measurement equipment and measurement conditions]
Measuring apparatus: 1600S type X-ray photoelectron spectrometer (PHI)
X-ray source: MgKα (400W)
Analysis area: 0.8 × 2.0mm
Pretreatment: The sample was placed on an aluminum dish and the surface was smoothed for measurement.
For calculation of the surface fluorine atom concentration, a relative sensitivity factor manufactured by PHI was used. The result of the fluorine content is atomic% (number of atoms%).

表２の結果から、比較例１及び２の反射防止フィルムは防汚性（指紋拭き取り性及びマジック拭き取り性）が劣るのに対して、実施例１〜５の反射防止フィルムは広い波長領域で、非常に低い表面反射率とともに優れた防汚性（指紋拭き取り性及びマジック拭き取り性）を有していることが認められる。

From the results in Table 2, the antireflection films of Comparative Examples 1 and 2 have poor antifouling properties (fingerprint wiping properties and magic wiping properties), whereas the antireflection films of Examples 1 to 5 are in a wide wavelength region. It is recognized that it has excellent antifouling properties (fingerprint wiping and magic wiping properties) with very low surface reflectance.

(Example 6)
-Production of image display device-
The obtained antireflection films of Examples 1 to 5 and Comparative Examples 1 to 2 were attached to the surface of a liquid crystal display of a personal computer PC9821NS / 340W (manufactured by NEC Corporation) to prepare an image display device sample.

  The degree of landscape reflection of each image display device sample produced was visually evaluated. As a result, the image display devices provided with the antireflection films of Examples 1 to 5 were hardly visible in the surrounding scenery, showed comfortable visibility, and had sufficient antifouling properties. On the other hand, the image display devices provided with the antireflection films of Comparative Examples 1 and 2 were inferior in antifouling property although the surrounding reflections could be similarly reduced.

The fluorine-containing resin composition of the present invention is suitably used for producing an optical article having a periodic fine concavo-convex structure having a visible light wavelength or less that is excellent in optical properties and stain resistance. Since the optical article of the present invention has high antireflection performance and excellent anti-contamination properties, various optical articles such as an antireflection film, an antireflection film, an optical waveguide, a relief hologram, a lens, an optical card, an optical disk, and a polarization separation element are used. It is suitably used for optical applications. In addition, since the optical article is disposed in the image display device of the present invention, the visibility is good, and the image display device can display a high-quality image that is not easily soiled, and is particularly suitable as a liquid crystal display device. .

Claims (14)

  A fluorine-containing resin composition comprising at least a fluorine-containing compound and used for forming a fine uneven structure of an optical article. The fluorine-containing resin composition according to claim 1, wherein the fluorine-containing compound has a fluoroalkyl group represented by the following general formula (1).
- _{(CF 2)} n X Formula (1)
However, in said general formula (1), X represents a fluorine atom or a hydrogen atom. n represents an integer.   The fluorine-containing resin composition according to claim 1, wherein the fluorine-containing compound is at least one selected from a fluorine-containing monomer, a fluorine-containing silane coupling agent, a fluorine-containing surfactant, and a fluorine-containing polymer. .   The fluorine-containing polymer is a polymer of a fluoroalkyl group-containing monomer, a copolymer of a fluoroalkyl group-containing monomer and a poly (oxyalkylene) group-containing monomer, and a copolymer of a fluoroalkyl group-containing monomer and a crosslinking reactive group-containing monomer. The fluorine-containing resin composition according to claim 3, comprising any one of polymers.   The fluorine-containing resin composition according to any one of claims 1 to 4, wherein the fluorine-containing compound is blended as any one of an additive and a binder.   An optical article, wherein a fine concavo-convex structure is formed using the fluorine-containing resin composition according to any one of claims 1 to 5, and the surface contains fluorine atoms.   The optical article according to claim 6, wherein the fluorine atom concentration at a depth within 10 nm from the surface is 20 atomic percent or more.   The optical article according to any one of claims 6 to 7, wherein the surface tension is 25 mN / m or less.   The optical article according to any one of claims 6 to 8, wherein the fine uneven structure has an uneven height of 50 to 1000 nm and an uneven period of 10 to 400 nm.   The optical article according to any one of claims 6 to 9, wherein when the refractive index of the fine concavo-convex structure is n, the following formula, concavo-convex cycle <400 / n (nm) is satisfied.   The optical article according to any one of claims 6 to 10, wherein a mirror surface average reflectance in a wavelength region of 450 to 650 nm is 2% or less.   A stamper having a fine concavo-convex structure complementary to a fine concavo-convex structure formed on an optical article is produced, and the stamper is pressed against a layer formed from a fluorine-containing resin composition to transfer the fine concavo-convex structure of the stamper. The optical article according to claim 6.   The optical article according to any one of claims 6 to 12, wherein the optical article is any one selected from an antireflection film, an antireflection film, an optical waveguide, a relief hologram, a lens, an optical card, an optical disk, and a polarization separation element.   An image display device comprising the optical article according to claim 6.