JP2005092099A - Curable resin composition and optical article, and image display device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition which permits formation of periodic fine ruggedness structures and an optical article suitable for various optical applications and an image display device using the same. <P>SOLUTION: The curable resin composition contains polysiloxane which is a hydrolysis condensate prepared by hydrolyzing and condensing a trifunctional silane compound expressed by general formula (1): RSiX<SB>3</SB>and is formed by silane bonding of ≥90% of one silicon atom to other three silicon atoms . The above curable resin composition is used for forming the fine ruggedness structure of the optical article. The optical article has the fine ruggedness structure formed by using the curable resin composition. The image display device is arranged with the optical article. In the general formula (1), R represents a group including a reactive unsaturated group or ring-opening polymerizing group and X represents a hydroxyl group or hydrolyzable group. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a curable resin composition capable of efficiently forming a periodic fine concavo-convex structure excellent in optical characteristics and scratch resistance, and an antireflection film, an antireflection film, an optical waveguide, a relief hologram, a lens, and an optical card. The present invention relates to an optical article suitably used for various optical applications such as 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 injection molding and press working have been proposed as methods suitable for large areas 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).

  However, the fine concavo-convex structure can exhibit excellent optical properties, is inexpensive, and is capable of processing a large area. However, when a known material such as a thermoplastic resin or an ultraviolet curable resin is used (patent document) 1-2) has a problem in mechanical properties such as the formed fine concavo-convex structure being easily crushed and damaged by an external force. In order to solve this problem, it is expected to improve the mechanical properties of the film by introducing an inorganic skeleton such as silicate. However, the usual sol-gel reaction is slow in curing time and large in shrinkage, thus achieving the object. It is difficult. In addition, introduction of inorganic fine particles has also been studied (see Patent Document 3), but the mechanical properties have not necessarily been improved in terms of compatibility with the film.

  Therefore, it is desired to provide a curable resin composition having a fine concavo-convex structure excellent in optical characteristics and scratch resistance and suitably used for various optical applications, and an image display device using the optical article. The current situation is.

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 JP 2003-82043 A

  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 curable resin composition capable of forming a periodic fine concavo-convex structure having a visible light wavelength or less excellent in optical characteristics and scratch resistance, and an antireflection film, an antireflection film, an optical waveguide, and a relief hologram. An object of the present invention is to provide an optical article suitable for various optical applications such as a lens, an optical card, an optical disk, and a polarization separation element, and an image display device using the same.

ただし、前記一般式（２）中、Ｒ^１は、反応性不飽和基又は開環重合性基を表す。Ｒ^２は、置換基を表す。Ｒ^１及びＲ^２は、互いに同一であってもよいし異なっていてもよい。ｎは、重合度を表す。
＜３＞ ポリシロキサンが、下記一般式（３）で表されるかご構造のポリシロキサンを含む前記＜１＞に記載の硬化性樹脂組成物である。

ただし、前記一般式（３）中、Ｒ^３は、反応性不飽和基又は開環重合性基を表す。Ｒ^４〜Ｒ^１０は、置換基を表す。Ｒ^３〜Ｒ^１０は、互いに同一であってもよいし異なっていてもよい。
＜４＞ 前記＜１＞から＜３＞のいずれかに記載の硬化性樹脂組成物を用いて形成される微細凹凸構造層を有することを特徴とする光学物品である。
＜５＞ 微細凹凸構造層が、一のケイ素原子の９５％以上が他の３つのケイ素原子とシロキサン結合してなるポリシロキサンを含む前記＜４＞に記載の光学物品である。
＜６＞ 微細凹凸構造層における凹凸高さが５０〜１０００ｎｍ、凹凸周期が１０〜４００ｎｍである前記＜４＞から＜５＞のいずれかに記載の光学物品である。
＜７＞ 微細凹凸構造層の屈折率をｎとした時、次式、凹凸周期＜４００／ｎ（ｎｍ）を満たす前記＜４＞から＜６＞のいずれかに記載の光学物品である。
＜８＞ ４５０〜６５０ｎｍの波長領域での鏡面平均反射率が２％以下である前記＜４＞から＜７＞のいずれかに記載の光学物品である。
＜９＞ 光学物品の表面に形成する微細凹凸構造と相補的な微細凹凸構造を有するスタンパーを作製し、該スタンパーを硬化性樹脂組成物から形成される層に圧接させて該スタンパーの微細凹凸構造を転写してなる前記＜４＞から＜８＞のいずれかに記載の光学物品である。
＜１０＞ 光学物品が、反射防止膜、反射防止フィルム、光導波路、レリーフホログラム、レンズ、光カード、光ディスク及び偏光分離素子から選択されるいずれかである前記＜４＞から＜９＞のいずれかに記載の光学物品である。
＜１１＞ 前記＜４＞から＜１０＞のいずれかに記載の光学物品を配置したことを特徴とする画像表示装置である。 Means for solving the problems are as follows. That is,
<1> A hydrolysis-condensation product obtained by hydrolyzing and condensing a trifunctional silane compound represented by the following general formula (1), and 90% or more of one silicon atom is bonded to other three silicon atoms and siloxane bonds A curable resin composition comprising a polysiloxane formed as described above and used for forming a fine relief structure of an optical article.
RSix ₃ ... General formula (1)
However, in the general formula (1), R represents a group containing a reactive unsaturated group or a ring-opening polymerizable group. X represents a hydroxyl group or a hydrolyzable group.
<2> The curable resin composition according to <1>, wherein the polysiloxane includes either a ladder polymer or a ladder oligomer having a repeating unit represented by the following general formula (2) in the molecule.

However, in the general formula (2), R ¹ represents a reactive unsaturated group or a ring-opening polymerizable group. R ² represents a substituent. R ¹ and R ² may be the same as or different from each other. n represents the degree of polymerization.
<3> The curable resin composition according to <1>, wherein the polysiloxane includes a caged polysiloxane represented by the following general formula (3).

However, In the general formula (3), R ³ represents a reactive unsaturated group or a ring-opening polymerizable group. R ^{4 to} R ¹⁰ represent a substituent. R ^{3 to} R ¹⁰ may be the same as or different from each other.
<4> An optical article comprising a fine concavo-convex structure layer formed using the curable resin composition according to any one of <1> to <3>.
<5> The optical article according to <4>, wherein the fine concavo-convex structure layer includes polysiloxane in which 95% or more of one silicon atom is bonded to another three silicon atoms by siloxane bonding.
<6> The optical article according to any one of <4> to <5>, wherein the fine uneven structure layer has an uneven height of 50 to 1000 nm and an uneven period of 10 to 400 nm.
<7> The optical article according to any one of <4> to <6>, wherein the refractive index of the fine concavo-convex structure layer is n, and satisfies the following formula: concavo-convex cycle <400 / n (nm).
<8> The optical article according to any one of <4> to <7>, wherein a mirror surface average reflectance in a wavelength region of 450 to 650 nm is 2% or less.
<9> A stamper having a fine concavo-convex structure complementary to the fine concavo-convex structure formed on the surface of the optical article is manufactured, and the stamper is pressed against a layer formed from the curable resin composition to thereby form the fine concavo-convex structure of the stamper. Is an optical article according to any one of <4> to <8>.
<10> Any one of <4> to <9>, 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.
<11> An image display device comprising the optical article according to any one of <4> to <10>.

The curable resin composition of the present invention is a hydrolytic condensate obtained by hydrolyzing and condensing a trifunctional silane compound represented by RSiX ₃ and 90% or more of one silicon atom is another three silicon atoms. And polysiloxane formed by siloxane bonding. The curable resin composition is used to form a fine uneven structure of an optical article. In the polysiloxane, an inorganic hard skeleton is not formed at the time of curing as in the sol-gel reaction, but is formed outside the system in advance, and the curing reaction for film formation is performed by a rapid radical reaction or cation reaction. Since the curing shrinkage is small, it is suitable for forming fine irregularities. In addition, a film having a fine uneven shape is excellent in mechanical properties because an inorganic component is homogeneously incorporated into the film, unlike a form in which fine particles are dispersed. Therefore, a fine concavo-convex structure excellent in optical properties and scratch resistance can be formed for various optical articles, and can be suitably used for various optical applications.

  The optical article of the present invention comprises a fine concavo-convex structure layer containing polysiloxane formed using the curable resin composition of the present invention and having 95% or more of silicon atoms bonded to other three different silicon atoms by siloxane bonding. Have. Since the optical article of the present invention has a fine concavo-convex structure excellent in optical characteristics and scratch resistance, 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 suitable for various optical uses.

  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 comfortable visibility and has sufficient scratch resistance, and is particularly suitable as a liquid crystal display device.

  ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition suitable for producing the optical article of the fine concavo-convex structure possession type which can solve the conventional problems and was excellent in an optical characteristic and scratch resistance can be provided. In addition, according to the present invention, it has high antireflection performance, excellent scratch resistance, and various optical components 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. An optical article that is suitably used for a typical application can be provided. Moreover, since the image display device of the present invention is equipped with the optical article, the image display device has good visibility, can be easily scratched, and can display a high-quality image, and is particularly suitable as a liquid crystal display device. .

(Curable resin composition)
The curable resin composition of the present invention is a hydrolyzed condensate that is used to form a fine relief structure of an optical article and is obtained by hydrolyzing and condensing a trifunctional silane compound represented by the following general formula (1). Contains certain polysiloxanes and other ingredients as required.
RSix ₃ ... General formula (1)
However, in the general formula (1), R represents a group containing a reactive unsaturated group or a ring-opening polymerizable group. X represents a hydroxyl group or a hydrolyzable group.

In the general formula (1), R represents a group containing a reactive unsaturated group or a ring-opening polymerizable group. There is no restriction | limiting in particular as said reactive unsaturated group, According to the objective, it can select suitably, For example, the group which has a non-aromatic unsaturated carbon-carbon bond (a double bond or a triple bond), etc. Among these, an ethylenically unsaturated group is preferable.
As said ethylenically unsaturated group, a C2-C20 thing is preferable, A C2-C15 thing is more preferable, A C2-C10 thing is still more preferable, for example, (meth) acryloyl group, (meth) acryloyloxy A propyl group, a vinyl group, a vinyloxy group, an allyl group, a cinnamoyl group, etc. are mentioned, Among these, a (meth) acryloyl group is particularly preferable.
As the ring-opening polymerizable group, those having 2 to 20 carbon atoms are preferable, those having 2 to 15 are more preferable, those having 2 to 10 are more preferable, and examples thereof include an epoxy group, an oxetanyl group, and an oxazolyl group. Among these, an epoxy group is particularly preferable.

X represents a hydroxyl group or a hydrolyzable group. 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, a halogen atom, or RCOO (where R is a hydrogen atom) Or an alkyl group having 1 to 10 carbon atoms).
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.

  Specific examples of suitable trifunctional silane compounds represented by the general formula (1) are shown below, but are not limited thereto.

In the hydrolysis condensation reaction of the polysiloxane (siloxane resin) of the present invention, in addition to the trifunctional silane compound represented by the general formula (1), a silane compound having a non-reactive group is further added as necessary. Can be blended. As the silane compound having the non-reactive group (Y), known silane compounds having 1 to 4 hydrolyzable groups are suitable, and silane compounds having 3 hydrolyzable groups, for example, the general formula: YSiX ₃ (wherein Y represents a non-reactive group) is particularly preferable.

Examples of the non-reactive group include an alkyl group, a cycloalkyl group, a fluorine-substituted alkyl group, and an aryl group. For the purpose of releasability and antifouling property, silicone having a hydrolyzable silyl group at the terminal may be appropriately blended.
As said alkyl group, a C1-C10 thing is preferable, For example, a methyl group, an ethyl group, n-butyl group etc. are mentioned. As said cycloalkyl group, a C3-C10 thing is preferable, For example, a cyclopentyl group, a cyclohexyl group, etc. are mentioned. The fluorine-substituted alkyl group preferably has 1 to 20 carbon atoms and may contain one or more ether bonds or ester bonds, such as 3,3,3-trifluoropropyl group, tridecafluoro- Examples include 1,1,2,2-tetrahydrooctyl group, 3,3,3-trifluoromethoxypropyl group, 3,3,3-trifluoroacetoxypropyl group, and the like. As said aryl group, a C6-C20 thing is preferable, for example, a phenyl group, a naphthyl group, etc. are mentioned.

Preferred examples of the trifunctional silane compound having a non-reactive group (general formula: YSiX ₃ ) that can be blended with the trifunctional silane compound of the general formula (1) are shown below, but are not limited thereto. .

  The addition amount of the non-reactive silane compound is preferably 0.1 to 200 parts by mass, more preferably 1 to 100 parts by mass with respect to 100 parts by mass of the silane compound represented by the general formula (1). -50 mass parts is still more preferable.

  The hydrolytic condensation reaction of the trifunctional silane compound represented by the general formula (1) can be performed without a solvent or in a solvent. There is no restriction | limiting in particular as this solvent, Although it can select suitably according to the objective, An organic solvent is suitable. Examples of the organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, toluene, xylene, tetrahydrofuran, 1,4-dioxane, and the like. . These may be used individually by 1 type and may use 2 or more types together.

The hydrolytic condensation reaction of the trifunctional silane compound represented by the general formula (1) is preferably performed in the presence of a catalyst.
Examples of the catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, trifluoroacetic acid, methanesulfonic acid, and toluenesulfonic acid; sodium hydroxide, potassium hydroxide, ammonia, and the like Inorganic bases; organic bases such as triethylamine and pyridine; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium. These may be used individually by 1 type and may use 2 or more types together.

  The hydrolysis condensation reaction is performed by adding water to the trifunctional silane compound represented by the general formula (1). The amount of water added is preferably 0.3 to 2.0 mol per mol of the hydrolyzable group (for example, alkoxy group) of the trifunctional silane compound represented by the general formula (1). 5-1.0 mol is more preferable. The hydrolysis condensation reaction is performed by stirring at 25 to 100 ° C. in the presence of a solvent and a catalyst. 0.01-10 mol% is preferable with respect to the hydrolyzable group (alkoxy group) of a silane compound, and, as for the addition amount of the said catalyst, 0.1-5 mol% is more preferable. The reaction conditions are appropriately adjusted according to the reactivity of the silane compound represented by the general formula (1).

  When an organic acid such as carboxylic acid is used as the catalyst, water is generated in the system by a condensation reaction (esterification reaction) with an alcohol generated by reaction with alkoxysilane or an alcohol added as a solvent. Therefore, the hydrolysis reaction can be carried out without adding water separately.

The polysiloxane, which is a hydrolysis-condensation product of the trifunctional silane compound represented by the general formula (1), has a low curing shrinkage and a high hardness film because the hydrolysis-condensation reaction is almost completely advanced. A ratio of one silicon atom (T3) bonded to other three silicon atoms via a siloxane bond (Si-O bond) (hereinafter referred to as "polysiloxane condensation rate") May be 90%, preferably 95% or more, more preferably 98% or more, and most preferably 100%. The condensation rate of the polysiloxane was determined by using ²⁹ Si-NMR to reduce the ratio of the peak area derived from T3 observed around −65 ppm to about 10 ppm as the peak area of all silicon atoms (the number of siloxane bonds decreases by 1). (Shifted to the magnetic field side).

  In the polysiloxane, an inorganic hard skeleton is not formed at the time of curing like a sol-gel reaction, but is formed outside the system in advance, and the curing reaction for film formation is performed by a rapid radical reaction or a cation reaction. In addition, since the curing shrinkage is small, it is suitable for forming a fine uneven shape. Further, unlike the form in which the fine particles are dispersed in the film, the inorganic component is homogeneously incorporated into the film, so that the mechanical characteristics are also excellent.

  The polysiloxane preferably includes a ladder polymer or a ladder oligomer having a repeating unit represented by the following structural formula (1) in the molecule.

ただし、前記一般式（２）中、Ｒ^１は、反応性不飽和基又は開環重合性基を表す。Ｒ^２は、置換基を表す。Ｒ^１及びＲ^２は、互いに同一であってもよいし、異なっていても良い。
ｎは、重合度を表し、４〜１０００が好ましく、１０〜５００がより好ましく、１５〜１００が特に好ましい。

However, in the general formula (2), R ¹ represents a reactive unsaturated group or a ring-opening polymerizable group. R ² represents a substituent. R ¹ and R ² may be the same as or different from each other.
n represents a degree of polymerization, preferably 4 to 1000, more preferably 10 to 500, and particularly preferably 15 to 100.

In the general formula (2), R ¹ represents the same meaning as R in the general formula (1). R ² represents a substituent and may be the same group as R ¹ or may contain a non-reactive group.
The non-reactive group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an alkyl group, a cycloalkyl group, a fluorine-substituted alkyl group, an aryl group, and a group having a polydimethylsiloxane structure. Is mentioned.
As said alkyl group, a C1-C10 thing is preferable, For example, a methyl group, an ethyl group, n-butyl group etc. are mentioned. As said cycloalkyl group, a C3-C10 thing is preferable, For example, a cyclopentyl group, a cyclohexyl group, etc. are mentioned. The fluorine-substituted alkyl group preferably has 1 to 20 carbon atoms and may contain one or more ether bonds or ester bonds, such as 3,3,3-trifluoropropyl group, tridecafluoro- Examples include 1,1,2,2-tetrahydrooctyl group, 3,3,3-trifluoromethoxypropyl group, 3,3,3-trifluoroacetoxypropyl group, and the like. As said aryl group, a C6-C20 thing is preferable, for example, a phenyl group, a naphthyl group, etc. are mentioned.

  Ladder polymers or ladder oligomers having a repeating unit represented by the general formula (2) in the molecule are described in Journal of Japan Adhesion Association Vol. 39 (2), page 56 (2003), JP-A No. 2002-167552, etc. It can be synthesized according to the method described.

  Hereinafter, although the specific example of the ladder polymer or ladder oligomer used suitably for this invention is illustrated, it is not limited to these.

  The polysiloxane of the present invention preferably includes a polysiloxane having a cage (cubic type) structure represented by the following general formula (3).

ただし、前記一般式（３）中、Ｒ^３は、反応性不飽和基又は開環重合性基を表す。Ｒ^４〜Ｒ^１０は、置換基を表す。なお、Ｒ^３〜Ｒ^１０は、互いに同一であってもよいし、異なっていても良い。

However, In the general formula (3), R ³ represents a reactive unsaturated group or a ring-opening polymerizable group. R ^{4 to} R ¹⁰ represent a substituent. Note that R ^{3 to} R ¹⁰ may be the same as or different from each other.

In the general formula (3), R ³ represents the same meaning as R in the general formula (1). R ^{4 to} R ¹⁰ represent a substituent, and may be the same group as R ^3, and R ^{3 to} R ¹⁰ may be the same as or different from each other. Moreover, you may contain a non-reactive group.
Preferably three or more of R ⁴ to R ¹⁰ is the same group as ^{R 3,} more preferably more than six of the R 4 ^{to R 10} is the same group as ^{R 3, R} 4 ~ Most preferably, all of R ¹⁰ are the same groups as R ³ .

The non-reactive group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an alkyl group, a cycloalkyl group, a fluorine-substituted alkyl group, an aryl group, and a group having a polydimethylsiloxane structure. Is mentioned.
As said alkyl group, a C1-C10 thing is preferable, For example, a methyl group, an ethyl group, n-butyl group etc. are mentioned. As said cycloalkyl group, a C3-C10 thing is preferable, For example, a cyclopentyl group, a cyclohexyl group, etc. are mentioned. The fluorine-substituted alkyl group preferably has 1 to 20 carbon atoms and may contain one or more ether bonds or ester bonds, such as 3,3,3-trifluoropropyl group, tridecafluoro- Examples include 1,1,2,2-tetrahydrooctyl group, 3,3,3-trifluoromethoxypropyl group, 3,3,3-trifluoroacetoxypropyl group, and the like. As said aryl group, a C6-C20 thing is preferable, for example, a phenyl group, a naphthyl group, etc. are mentioned.

  Examples of the polysiloxane having a cubic structure represented by the general formula (3) include, for example, the methods described in JP-A-10-316757, JP-A-11-199673, and JP-A-11-29640. It can be synthesized according to

  Specific examples of the silane compound represented by the general formula (3) are shown below, but are not limited thereto.

  The number average molecular weight (Mn) of the polysiloxane is not particularly limited and may be appropriately selected depending on the purpose. It is preferably 1000 to 1 million, more preferably 2000 to 100,000, and still more preferably 3000 to 30,000. . If the number average molecular weight (Mn) is less than 1000, the coating film may have insufficient hardness or curing shrinkage may increase. If the number average molecular weight (Mn) exceeds 1,000,000, the solvent solubility will decrease and it will be difficult to handle. Or the storage stability of the curable resin composition may be reduced.

30-100 mass% is preferable with respect to the total solid of the said curable resin composition, The addition amount of the said polysiloxane has more preferable 50-100 mass%, and 70-100 mass% is still more preferable. When the addition amount is less than 30% by mass, the characteristics of the polysiloxane such as low curing shrinkage and rapid formation of a high hardness film may not be sufficiently exhibited.
The polysiloxane is preferably soluble in an aprotic organic solvent such as ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene and the like from the viewpoint of handleability.

  In addition to the polysiloxane, the curable resin composition of the present invention further includes hardness, brittleness, adhesion to a substrate, dustproof property (antistatic property), antifouling property, releasability, and the like. If necessary, various additives such as a curing agent, fine particles, a silane coupling agent, 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, carbonyl group, active methylene group, hydrazine group, etc.), And other monomers, oligomers, and prepolymers.
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.).

  1-70 mass% of the total solid content of the curable resin composition is preferable, 5-50 mass% is more preferable, and 10-30 mass% is still more preferable.

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 more strongly with the resin (polysiloxane) forming the binder, it is preferable to use the surface of the fine particles 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 curable resin composition, 5-40 mass% is more preferable, and 10-30 mass% is still more preferable.

The silane coupling agent can be used from the viewpoint of antifouling property, adhesion, and the like, and examples thereof include the silane compound of the general formula (1) or the non-hydrolyzable silane compound. In particular, when fine particles such as silica are used in combination, it may be effective in terms of increasing the bonding force between the matrix and the particles.
The addition amount of the silane coupling agent is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and still more preferably 1 to 10% by mass based on the total solid content of the curable resin composition.

There is no restriction | limiting in particular as said surfactant, According to the objective, it can select suitably, For example, both a fluorine-type surfactant and a silicone type surfactant can be used.
Examples of the fluorine-based surfactant include perfluoroalkylsulfonic acid amide group-containing nonions such as Fluorard FC-431 manufactured by 3M, Megafac F-171, F-172, and F-173 manufactured by Dainippon Ink. And perfluoroalkyl group-containing oligomers such as F-176PF.
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.
The addition amount of the surfactant is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, and further preferably 0.5 to 5% by mass with respect to the total solid content of the curable resin composition. 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. Commercially available products can be used as the release agent component. For example, AK-5, AK-30, AK-32 (all manufactured by Toa Gosei Co., Ltd.), Silaplane FM0275, Silaplane FM0721 (all Chisso) 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 a curable 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.

  The curable resin composition of the present invention may further contain a curing catalyst or an initiator as necessary. 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. Although it can do, 0.1-15 mass% is preferable with respect to the total solid of the said curable 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 kind of the catalyst, the difference in the curing reactive site, etc., and cannot be specified unconditionally, but is 0.1 to 15% by mass with respect to the total solid content of the curable resin composition. Is preferable, and 0.5-5 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 curable 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 curable resin composition, and is preferably 0.5 to 5%. The 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 preferably 10 to 100 parts by mass with respect to 100 parts by mass of the total solid content of the curable resin composition. preferable.

  The curable resin composition of the present invention can be produced by using the polysiloxane 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 curable resin composition can be produced by dissolving each constituent component.

  The solvent used in the curable 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. , Ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (eg, ethyl acetate, butyl acetate, etc.), ethers (eg, tetrahydrofuran, 1,4-dioxane, etc.), alcohols (eg, 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 curable resin composition of the present invention has a fine concavo-convex structure excellent in optical properties and scratch resistance, and can be suitably used in various fields. However, it can be particularly suitably used as the following optical article. it can.

(Optical article)
The optical article of the present invention has a fine concavo-convex structure layer formed using the curable resin composition of the present invention, and further includes other members as necessary.
The polysiloxane condensation rate in the fine concavo-convex structure layer (ratio of one silicon atom (T3) bonded to the other three silicon atoms via a siloxane bond) is preferably 95% or more, more preferably 98% or more. Preferably, 100% is most preferable. If the condensation rate of the polysiloxane is less than 95%, the film hardness may be insufficient, or deformation of the fine irregularities may be a problem due to curing shrinkage.

  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 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 light and / or heat as described above can also be used when completely curing after shape formation.

  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 an optical article of the present invention comprises a fine concavo-convex structure layer formed using the curable 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 an optical article of the present invention is provided with a support and a fine uneven structure layer (antireflection layer) formed from the curable 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 addition amount of the infrared absorber or the ultraviolet absorber is preferably 0.01 to 20% by mass of the support, 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 polysiloxane "S-5"-
According to the method described in Journal of Japan Adhesion Association Vol. 39 (2), page 56 (2003), 24.84 g of methacryloyloxypropyltrimethoxysilane, 20 ml of water, and 1.01 g of triethylamine were mixed and heated to 50 ° C. After heating for 12 hours, separation and purification were performed by adding ethyl acetate and brine. The obtained organic layer was dried over sodium sulfate, and then the solvent was concentrated and reprecipitated in hexane. Thus, 13 g of polysiloxane “S-5” represented by the following structural formula was obtained.
The number average molecular weight (Mn) of the obtained polysiloxane “S-5” was 4000. Further, from ²⁹ Si-NMR, since almost all silicon atoms have three siloxane bonds, it was confirmed to have a ladder structure. The polysiloxane condensation rate was determined as follows.

The polysiloxane “S-17” can be synthesized by the same method as the polysiloxane “S-5”. The “S-17” has a number average molecular weight (Mn) of 4000 and a ladder structure.
Further, “C-35” and “S-48” having a cage structure can be obtained from Aldrich and Toagosei Co., Ltd. (trade name, OX-SQ), respectively. Can also be synthesized according to the methods described in JP-A-11-199673 and JP-A-11-29640.

<Measurement method of polysiloxane condensation rate>
The polysiloxane condensation rate in the polysiloxanes “S-5”, “S-17”, “S-35”, and “S-48” (bonded to other three different silicon atoms via siloxane bonds). The ratio of one silicon atom (T3) is ²⁹ Si-NMR, the ratio of the peak area derived from T3 observed at around -65 ppm is reduced to the peak area of all silicon atoms (the siloxane bond is reduced by one). According to the above, it shifts to the low magnetic field side by about 10 ppm). The results are shown in Table 10.

(Synthesis Example 2)
-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 resulting binder resin A solution had a solid content of 38.2% by mass, a weight average molecular weight (Mw) of 30,000 in terms of polystyrene, and an introduction amount of carbon-carbon double bonds (C = C) of 12.5. %Met.

- Synthesis of surface-modified silica fine particles acryloyl group (ASiO ₂₎ -
50 g of methanol silica sol (manufactured by Nissan Chemical Industries, Ltd., silica particle methanol dispersion having a particle size of 10 to 15 nm, solid content of 30% by mass), acryloyloxypropyltrimethoxysilane (KBM5103 (trade name), manufactured by Shin-Etsu Chemical Co., Ltd.) 12.3 g and 57 g of dimethoxyethane were mixed and heated to reflux for 10 hours. Thereafter, unreacted acryloyloxypropyltrimethoxysilane was adsorbed on silica gel and filtered. Thus, an acryloyl group-modified silica dispersion (ASiO ₂ ) (solid content: 20% by mass) was obtained.
The obtained acryloyl group-modified silica dispersion (ASiO ₂ ) has a particle surface directly modified with an acryloyl group-containing silane coupling agent based on ²⁹ Si-NMR and elemental analysis, and the acryloyl group introduction rate into the particles is 0. 0.5 mmol / g.
The resulting acryloyl group-modified particles are tetrafunctional silane compounds, and polysiloxanes “S-5”, “S-17”, “S-35”, and “S-35”, which are hydrolysis condensates of trifunctional silane compounds. Since the chemical shift of ²⁹ Si-NMR is observed on the high magnetic field side with respect to S-48 ", the two can be clearly distinguished.

(Example 1)
-Preparation of curable resin composition-
95 parts by mass of polysiloxane “S-5” of Synthesis Example 1, 5 parts by mass of RMS033 (trade name, methacryloyl-modified silicone oil manufactured by Azmax Co., Ltd.) as a release agent, and Irgacure (IRG) 907 as a photoradical polymerization initiator 5 parts by mass (trade name, manufactured by Ciba Specialty Chemical Co., Ltd.) was dissolved in methyl ethyl ketone so as to be 30% by mass (solid content) to prepare a curable resin composition of Example 1.

(Example 2)
-Preparation of curable resin composition-
80 parts by mass of polysiloxane “S-5” of Synthesis Example 1, 15 parts by mass of DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., polyfunctional curing agent KAYARAD) as a curing agent, RMS033 (trade name, as a release agent) 5 parts by mass of Asmax 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 in 30% by mass (solid content) of methyl ethyl ketone The curable resin composition of Example 2 was prepared.

(Example 3)
-Preparation of curable resin composition-
65 parts by mass of polysiloxane “S-5” of Synthesis Example 1, 20 parts by mass of acryloyl group-modified silica dispersion (ASiO ₂ , solid content 20% by mass), DPHA as a curing agent (trade name, manufactured by Nippon Kayaku Co., Ltd., 10 parts by mass of 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 Irgacure (IRG) 907 (trade name, Ciba as a photo radical polymerization initiator) 5 parts by mass of Specialty Chemical Co., Ltd. was dissolved in methyl ethyl ketone so as to be 30% by mass (solid content) to prepare a curable resin composition of Example 3.

Example 4
-Preparation of curable resin composition-
50 parts by mass of polysiloxane “S-5” of Synthesis Example 1, 45 parts by mass of DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., polyfunctional curing agent KAYARAD) as a curing agent, RMS033 (trade name, as a release agent) 5 parts by mass of Asmax 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 in 30% by mass (solid content) of methyl ethyl ketone The curable resin composition of Example 4 was prepared.

(Example 5)
-Preparation of curable resin composition-
80 parts by mass of polysiloxane “S-17”, Celoxide 2021P (trade name, manufactured by Daicel Chemical Industries, Ltd., bifunctional alicyclic epoxy curing agent) as a curing agent, X-22-163B (product) as a release agent Name, 5 parts by mass of Shin-Etsu Silicone Co., Ltd., epoxy group-modified silicone oil) and 5 parts by mass of UVI 6990 (trade name, manufactured by Union Carbide Japan Co., Ltd.) as a photopolymerization initiator, 30% by mass (solid content) The curable resin composition of Example 5 was prepared.

(Example 6)
-Preparation of curable resin composition-
90 parts by mass of polysiloxane “S-35”, DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., polyfunctional curing agent KAYARAD) as a curing agent, X-22-163B (trade name, as release agent) 5 parts by mass of Shin-Etsu Silicone Co., Ltd., epoxy group-modified silicone oil) and 5 parts by mass of UVI 6990 (trade name, manufactured by Union Carbide Japan Co., Ltd.) as a photopolymerization initiator are 30% by mass (solid content) in methyl ethyl ketone. The curable resin composition of Example 6 was prepared.

(Example 7)
-Preparation of curable resin composition-
5 parts by mass of polysiloxane “S-48”, Celoxide 2021P as a curing agent (trade name, manufactured by Daicel Chemical Industries, Ltd., bifunctional alicyclic epoxy curing agent), RMS033 as a release agent (trade name, manufactured by Asmax Corporation) 5 parts by mass of methacryloyl-modified silicone oil) and 5 parts by mass of Irgacure (IRG) 907 (trade name, manufactured by Ciba Specialty Chemicals) as a photoradical polymerization initiator are 30% by mass (solid content) in methyl ethyl ketone. The curable resin composition of Example 7 was prepared.

(Comparative Example 1)
-Preparation of curable resin composition-
67 parts by mass of binder resin A in Synthesis Example 2, 5 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 curable resin composition of Comparative Example 1 was prepared.

(Comparative Example 2)
-Preparation of curable resin composition-
39 parts by mass of binder resin A in Synthesis Example 2, 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 Industries 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 A curable resin composition of Comparative Example 2 was prepared by dissolving 5 parts by mass of 184 (trade name, manufactured by Ciba Specialty Chemical Co., Ltd.) in methyl ethyl ketone so as to be 30% by mass (solid content).

＊表１０中、（ ）内の数字は各成分の質量部を表す。

* In Table 10, the numbers in () represent parts by mass of each component.

-Production of antireflection film-
After applying each curable resin composition of Examples 1-7 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 1-7 and Comparative Examples 1-2 was produced.

<Performance evaluation of antireflection film>
About the obtained antireflection film of Examples 1-7 and Comparative Examples 1-2, the specular average reflectance, the scratch resistance test, and the polysiloxane condensation rate were evaluated as follows. The results are shown in Table 11.

(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) Condensation rate of polysiloxane For each antireflection film, the ratio of one silicon atom (T3) bonded to the other three silicon atoms via a siloxane bond (Si-O bond) is determined as ²⁹ Si- Using NMR, calculate the ratio of the peak area derived from T3 observed in the vicinity of −65 ppm with respect to the peak area of all silicon atoms (shifting to the low magnetic field side by about 10 ppm as one siloxane bond decreases). Sought by.

表１１の結果から、実施例１〜７の反射防止フィルムは、比較例１〜２の反射防止フィルムに比べて、広い波長領域で低い表面反射率を有すると共に、優れた耐傷性を有していることが認められる。

From the results of Table 11, the antireflection films of Examples 1 to 7 have low surface reflectance in a wide wavelength region and excellent scratch resistance as compared with the antireflection films of Comparative Examples 1 and 2. It is recognized that

(Example 8)
-Production of image display device-
The obtained antireflection films of Examples 1 to 7 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 7 were hardly visible in the surrounding scenery, showed comfortable visibility, and had sufficient scratch resistance. On the other hand, the image display devices provided with the antireflection films of Comparative Examples 1 and 2 were inferior in scratch resistance, although the surrounding reflections could be similarly reduced.

The curable resin composition of the present invention is suitably used for producing an optical article having a periodic fine concavo-convex structure with a visible light wavelength or less excellent in optical properties and scratch resistance. Since the optical article of the present invention has high antireflection performance and excellent scratch resistance, various optical components 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 general purposes. 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 scratched, and is particularly suitable as a liquid crystal display device. .

Claims (11)

A hydrolysis-condensation product obtained by hydrolyzing and condensing a trifunctional silane compound represented by the following general formula (1), and 90% or more of one silicon atom is bonded to the other three silicon atoms by siloxane bonds A curable resin composition comprising polysiloxane and used to form a fine relief structure of an optical article.
RSix ₃ ... General formula (1)
However, in the general formula (1), R represents a group containing a reactive unsaturated group or a ring-opening polymerizable group. X represents a hydroxyl group or a hydrolyzable group. The curable resin composition according to claim 1, wherein the polysiloxane contains either a ladder polymer or a ladder oligomer having a repeating unit represented by the following general formula (2) in the molecule.

However, in the general formula (2), R ¹ represents a reactive unsaturated group or a ring-opening polymerizable group. R ² represents a substituent. R ¹ and R ² may be the same as or different from each other. n represents the degree of polymerization. The curable resin composition according to claim 1, wherein the polysiloxane contains a caged polysiloxane represented by the following general formula (3).

However, In the general formula (3), R ³ represents a reactive unsaturated group or a ring-opening polymerizable group. R ^{4 to} R ¹⁰ represent a substituent. R ^{3 to} R ¹⁰ may be the same as or different from each other.   An optical article comprising a fine concavo-convex structure layer formed using the curable resin composition according to claim 1.   The optical article according to claim 4, wherein the fine concavo-convex structure layer includes polysiloxane in which 95% or more of one silicon atom is bonded to other three silicon atoms by siloxane bonding.   The optical article according to any one of claims 4 to 5, wherein the concavo-convex height in the fine concavo-convex structure layer is 50 to 1000 nm and the concavo-convex cycle is 10 to 400 nm.   The optical article according to any one of claims 4 to 6, wherein when the refractive index of the fine concavo-convex structure layer is n, the following formula, concavo-convex cycle <400 / n (nm) is satisfied.   The optical article according to any one of claims 4 to 7, 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 the fine concavo-convex structure formed on the surface of the optical article is prepared, and the stamper is pressed against a layer formed from the curable resin composition to transfer the fine concavo-convex structure of the stamper. The optical article according to any one of claims 4 to 8.   The optical article according to any one of claims 4 to 9, 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 apparatus comprising the optical article according to claim 4.