JP2008201922A - Coating agent, cured coating layer, and structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating agent for forming a coating layer to be interposed in between an organic substrate and a metallic or inorganic compound vacuum-deposition film for the purpose of improving the adhesion therebetween. <P>SOLUTION: The coating agent comprises (A) a polyorganosiloxane sol prepared by the hydrolysis or condensation of (a-1) a silane compound of the following general formula (I) or its partial hydrolyzate and (a-2) a silane compound of the following general formula (II) or its partial hydrolyzate and (B) an acrylic organic macromolecular compound. The general formula (I) is as follows: CH<SB>2</SB>=C(R)-COO-A-SiR<SP>1</SP><SB>n</SB>(OR<SP>2</SP>)<SB>3-n</SB>(wherein, R is H or CH<SB>3</SB>; A is an alkylene group; R<SP>1</SP>and R<SP>2</SP>are each a 1-10C alkyl; and n is an integer of 0-2). The general formula (II) is as follows: R<SP>3</SP><SB>m</SB>Si(OR<SP>4</SP>)<SB>4-m</SB>(wherein, R<SP>3</SP>is H, a 1-10C alkyl, aryl, aralkyl or vinyl; R<SP>4</SP>is a 1-10C alkyl; and m is an integer of 0-3). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a coating agent, a cured coating layer, and a structure. More specifically, the present invention relates to a coating agent for forming a coating layer interposed between them in order to improve the adhesion between the organic base material and the deposited metal or inorganic compound film, and an organic layer is formed using this coating agent. The present invention relates to a cured coating layer provided on a system substrate, and a structure having the cured coating layer, particularly a structure in which a metal or inorganic compound vapor deposition film is provided on the cured coating layer.

Conventionally, a glass substrate is often used in optical components such as a reflection mirror and an optical lens. In the reflective mirror, a reflective film is formed by depositing a metal such as aluminum on a glass substrate by vacuum deposition or the like. In addition, in the optical lens, in order to prevent reflection on the component surface, an antireflection film comprising a multilayer film in which a thin film of a high refractive index material such as TiO ₂ and a thin film of a low refractive index material such as SiO ₂ are alternately deposited is provided. Has been made.

  However, in recent years, it is lightweight, low cost, and has excellent productivity, so transparent resins such as acrylic resins represented by polymethyl methacrylate, polycarbonate resins, polyester resins such as polyethylene terephthalate, polynorbornene, etc. These polycycloolefin resins are used as substrates for optical materials. Examples of providing a metal-based vapor deposition film on such a plastic substrate include the following.

  In displays such as a plasma display (PDP), a cathode ray tube (CRT), and a liquid crystal display (LCD), light is incident on the screen from the outside, and this light is reflected to make it difficult to view the displayed image. As the size of flat panel displays increases, solving the above problems has become an increasingly important issue. In order to solve such a problem, various antireflection treatments and antiglare treatments have been taken for various displays so far. As one of them, an antireflection film is used for various displays.

As a method for producing the antireflection film, a dry process method (evaporation method) and a wet process method (coating method) are known. According to the dry process method, a low refractive index substance ( With a method of thinning MgF ₂ ), a method of alternately stacking a material having a high refractive index [ITO (tin-doped indium oxide), TiO _2, etc.) and a material having a low refractive index (MgF ₂ , SiO _2, etc.) Produced.

  In addition, to reduce heat and save energy in building windows, vehicle windows, refrigerated and frozen showcase windows, etc., these windows are given the ability to reflect or absorb heat rays (infrared rays). A method has been proposed. For example, a method is known in which a heat ray reflective film formed by sputtering or vapor deposition of a metal thin film such as aluminum, silver, or gold on the surface of a transparent substrate film is attached to a window.

  On the other hand, an organic base material having a conductive material layer on its surface, particularly a plastic film, is used for an electroluminescence element (EL element), a liquid crystal display element (LCD element), a solar cell, etc., and further an electromagnetic wave shielding film or antistatic property. It is used as a film. Examples of conductive materials used in such applications include metal oxides such as indium oxide, tin oxide, zinc oxide, cadmium oxide, and ITO, and metals such as gold, platinum, silver, nickel, aluminum, and copper. Inorganic or metallic conductive materials are used. These inorganic or metallic conductive materials are usually about 5 to 200 nm thick on an organic substrate such as a plastic film by known means such as vacuum deposition, sputtering, or ion plating. It is formed as a thin film.

  Furthermore, in recent years, magnetic reversal of magnetic films has been utilized using thermal energy such as semiconductor laser light as an optical recording medium that has features such as rewritable, high-density, large-capacity storage capacity, and non-contact with the recording / reproducing head. As a result, magneto-optical disks and crystals that record information and read out using the magneto-optic effect have been developed and put into practical use.

  In general, such an optical recording medium is formed by sequentially laminating an optical recording material layer, a dielectric layer, a metal reflective layer, an organic protective layer, etc. on a transparent organic substrate, for example, a substrate such as polycarbonate or polymethyl methacrylate. In some cases, a dielectric underlayer is provided between the substrate and the optical recording material layer.

For the optical recording material layer provided on the substrate, for example, an inorganic magneto-optical recording material such as Tb—Fe, Tb—Fe—Co, Dy—Fe—Co, Tb—Dy—Fe—Co, or TeOx, Inorganic phase change recording materials such as Te—Ge, Sn—Te—Ge, Bi—Te—Ge, Sb—Te—Ge, Pb—Sn—Te, Tl—In—Se are used. If desired, an inorganic material such as SiN, SiO, SiO ₂ , Ta ₂ O ₅ is used for the dielectric underlayer provided between the substrate and the optical recording material layer. The inorganic optical recording material layer and the dielectric underlayer are usually formed by known means such as vacuum deposition, sputtering, or ion plating.

  However, when a metal or inorganic compound vapor-deposited film is provided on a plastic substrate in this way, there is a problem that the adhesion between the vapor-deposited film and the plastic substrate is poor, and an improvement thereof has been demanded.

  As a means for improving the adhesion between a metal or inorganic compound vapor-deposited film and a plastic substrate, for example, when forming an antireflection film on a plastic substrate by vacuum vapor deposition, inorganic fine particles, a silane coupling agent, A technique is disclosed in which an adhesion enhancing layer containing a resin component is interposed between the plastic substrate and the antireflection film (see, for example, Patent Document 1).

However, in this technique, polyorganosiloxane sol is not used as the inorganic fine particles, and acrylic organic polymer compound is used as the resin component, but it can be bonded to the metal oxide by hydrolysis in the molecule. It does not have a metal-containing group.
JP 2000-241604 A

  Under such circumstances, the present invention provides a coating agent for forming a coat layer interposed between them in order to improve the adhesion between an organic base material and a metal or inorganic compound vapor-deposited film. A cured coating layer provided on an organic base material using an agent, and a structure having the cured coating layer, particularly a structure in which a metal or inorganic compound vapor deposition film is provided on the cured coating layer It is intended to do.

  As a result of intensive studies to achieve the above object, the inventors of the present invention obtained a specific polyorganosiloxane sol obtained by a sol-gel method and an acrylic organic polymer compound, particularly by hydrolysis into a molecule. Achieving that objective with a coating agent that includes an acrylic monomer having a metal-containing group capable of bonding to a metal oxide and a polymer obtained by copolymerizing an acrylic monomer that does not contain metal The present invention has been found, and the present invention has been completed based on this finding.

That is, the present invention
(1) A coating agent for forming an intermediate layer provided between an organic base material and a metal-based vapor deposition film formed on the base material,
(A) (a-1) General formula (I)

（式中、Ｒは水素原子またはメチル基、Ａは炭素数１〜６のアルキレン基、Ｒ^１およびＲ^２は、それぞれ独立に炭素数１〜１０のアルキル基、ｎは０〜２の整数を示し、Ｒ^１が複数ある場合には、複数のＲ^１はたがいに同一でも異なっていてもよく、ＯＲ^２が複数ある場合には、複数のＯＲ^２はたがいに同一でも異なっていてもよい。）
で表されるシラン化合物またはその部分加水分解物と、（ａ−２）一般式（II）
Ｒ^３ _ｍＳｉ（ＯＲ^４）_４−ｍ …（II）
（式中、Ｒ^３は水素原子、炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基、炭素数７〜１０のアラルキル基またはビニル基、Ｒ^４は炭素数１〜１０のアルキル基、ｍは０〜３の整数を示し、Ｒ^３が複数ある場合には、複数のＲ^３はたがいに同一でも異なっていてもよく、ＯＲ^４が複数ある場合には、複数のＯＲ^４はたがいに同一でも異なっていてもよい。）
で表されるシラン化合物またはその部分加水分解物とを、加水分解・縮合して得られたポリオルガノシロキサンゾル、および（Ｂ）アクリル系有機高分子化合物を含むことを特徴とするコーティング剤、
（２） （Ａ）成分と（Ｂ）成分とを、固形分質量比９５：５〜５：９５の割合で含む上記（１）項に記載のコーティング剤、
（３） （Ａ）成分のポリオルガノシロキサンゾルにおける、原料の（ａ−１）成分と（ａ−２）成分とのモル比が９９：１〜６０：４０である上記（１）または（２）項に記載のコーティング剤、
（４） 一般式（Ｉ）で表されるシラン化合物が、３−メタクリロキシプロピルトリメトキシシランおよび／または３−アクリロキシプロピルトリメトキシシランである上記（１）〜（３）項のいずれか１項に記載のコーティング剤、
（５） 一般式（II）で表されるシラン化合物が、メチルトリメトキシシランである上記（１）〜（４）項のいずれか１項に記載のコーティング剤、
（６） （Ｂ）成分のアクリル系有機高分子化合物が、（ｂ−１）分子中に加水分解により金属酸化物と結合し得る金属含有基を有するアクリル系単量体と、（ｂ−２）金属を含まないアクリル系単量体とを共重合させて得られたものである上記（１）〜（５）項のいずれか１項に記載のコーティング剤、
（７） （ｂ−１）成分のアクリル系単量体が、一般式（Ｉ）

Wherein R is a hydrogen atom or a methyl group, A is an alkylene group having 1 to 6 carbon atoms, R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms, and n is an integer of 0 to 2. shown, when R ¹ is plural, a plurality of R ¹ may be the same with or different from each other, if the OR ² there is a plurality, the plurality of OR ² may be the same with or different from each other. )
And a partial hydrolyzate thereof, (a-2) general formula (II)
R ³ _m Si (OR ⁴ ) _4-m (II)
(In the formula, R ³ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group or vinyl group having 7 to 10 carbon atoms, and R ⁴ is an alkyl having 1 to 10 carbon atoms. group, m represents an integer of 0 to 3, when there are a plurality of R ^3, a plurality of R ³ may be the same with or different from each other, if the OR ⁴ there is a plurality, the plurality of OR ⁴ is They may be the same or different.)
A coating agent comprising: a polyorganosiloxane sol obtained by hydrolysis and condensation with a silane compound represented by formula (1) or a partial hydrolyzate thereof; and (B) an acrylic organic polymer compound,
(2) The coating agent according to the above item (1), which contains the component (A) and the component (B) at a solid content mass ratio of 95: 5 to 5:95,
(3) In the polyorganosiloxane sol as the component (A), the molar ratio of the component (a-1) to the component (a-2) is 99: 1 to 60:40 (1) or (2) ) Coating agent according to paragraph
(4) Any one of the above items (1) to (3), wherein the silane compound represented by the general formula (I) is 3-methacryloxypropyltrimethoxysilane and / or 3-acryloxypropyltrimethoxysilane. Coating agent according to paragraph,
(5) The coating agent according to any one of (1) to (4) above, wherein the silane compound represented by the general formula (II) is methyltrimethoxysilane.
(6) The acrylic organic polymer compound of component (B) is (b-1) an acrylic monomer having a metal-containing group capable of binding to a metal oxide by hydrolysis in the molecule; The coating agent according to any one of the above items (1) to (5), which is obtained by copolymerizing an acrylic monomer not containing a metal)
(7) The acrylic monomer as the component (b-1) is represented by the general formula (I)

（式中、Ｒは水素原子またはメチル基、Ａは炭素数１〜６のアルキレン基、Ｒ^１およびＲ^２は、それぞれ独立に炭素数１〜１０のアルキル基、ｎは０〜２の整数を示し、Ｒ^１が複数ある場合には、複数のＲ^１はたがいに同一でも異なっていてもよく、ＯＲ^２が複数ある場合には、複数のＯＲ^２はたがいに同一でも異なっていてもよい。）
で表されるシラン化合物またはその部分加水分解物である上記（６）項に記載のコーティング剤、
（８） （ｂ−２）成分のアクリル系単量体が、一般式（III）

Wherein R is a hydrogen atom or a methyl group, A is an alkylene group having 1 to 6 carbon atoms, R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms, and n is an integer of 0 to 2. shown, when R ¹ is plural, a plurality of R ¹ may be the same with or different from each other, if the OR ² there is a plurality, the plurality of OR ² may be the same with or different from each other. )
The coating agent according to (6) above, which is a silane compound represented by
(8) The acrylic monomer as the component (b-2) is represented by the general formula (III)

（式中、Ｒ^５は水素原子またはメチル基、Ｒ^６は炭素数１〜１０の炭化水素基を示す。）
で表される化合物である上記（６）または（７）項に記載のコーティング剤、
（９） （ｂ−１）成分のアクリル系単量体が、３−メタクリロキシプロピルトリメトキシシランおよび／または３−アクリロキシプロピルトリメトキシシランである上記（７）または（８）項に記載のコーティング剤、
（１０） （Ｂ）成分のアクリル系有機高分子化合物が、（ｂ−１）成分のアクリル系単量体と、（ｂ−２）成分のアクリル系単量体とを、モル比１：９９〜１５：８５の割合で共重合させて得られたものである上記（６）〜（９）項のいずれか１項に記載のコーティング剤、
（１１） 上記（１）〜（１０）項のいずれか１項に記載のコーティング剤を用いて、有機系基材表面に形成されたことを特徴とする硬化コート層、
（１２） 厚さが０．０１〜１０μｍである上記（１１）項に記載の硬化コート層、
（１３） 上記（１１）または（１２）項に記載の硬化コート層を有することを特徴とする構造体、および
（１４） 硬化コート層上に、物理的気相蒸着法または化学的気相蒸着法により、金属膜および無機化合物膜の中から選ばれる少なくとも１層の薄膜が設けられてなる上記（１３）項に記載の構造体、
を提供するものである。

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents a hydrocarbon group having 1 to 10 carbon atoms.)
The coating agent according to (6) or (7) above, which is a compound represented by:
(9) The acrylic monomer as the component (b-1) is 3-methacryloxypropyltrimethoxysilane and / or 3-acryloxypropyltrimethoxysilane as described in (7) or (8) above Coating agent,
(10) The acrylic organic polymer compound as the component (B) has a molar ratio of 1:99 between the acrylic monomer as the component (b-1) and the acrylic monomer as the component (b-2). The coating agent according to any one of (6) to (9) above, which is obtained by copolymerization at a ratio of ˜15: 85,
(11) A cured coating layer formed on the surface of an organic base material using the coating agent according to any one of (1) to (10) above,
(12) The cured coating layer according to (11), wherein the thickness is 0.01 to 10 μm,
(13) A structure having the cured coating layer described in (11) or (12) above, and (14) physical vapor deposition or chemical vapor deposition on the cured coating layer. The structure according to item (13), wherein a thin film of at least one layer selected from a metal film and an inorganic compound film is provided by a method,
Is to provide.

  According to the present invention, in order to improve the adhesion between an organic base material and a metal or inorganic compound vapor-deposited film, a coating agent for forming a coating layer interposed between them, an organic base using this coating agent It is possible to provide a cured coating layer provided on the material and a structure having the cured coating layer, particularly a structure in which a metal or inorganic compound vapor deposition film is provided on the cured coating layer.

First, the coating agent of the present invention will be described. The coating agent of the present invention is a coating agent for forming an intermediate layer provided between an organic base material and a metal or inorganic compound deposition film formed on the base material. And (B) an acrylic organic polymer compound.
[(A) Polyorganosiloxane sol]
The polyorganosiloxane sol of component (A) has the following (a-1) general formula (I)

で表されるシラン化合物またはその部分加水分解物と、（ａ−２）一般式（II）
Ｒ^３ _ｍＳｉ（ＯＲ^４）_４−ｍ …（II）
で表されるシラン化合物またはその部分加水分解物とを、加水分解・縮合して得られたゾルである。

And a partial hydrolyzate thereof, (a-2) general formula (II)
R ³ _m Si (OR ⁴ ) _4-m (II)
A sol obtained by hydrolyzing and condensing a silane compound represented by the formula (1) or a partial hydrolyzate thereof.

  In the general formula (I) as the component (a-1), R represents a hydrogen atom or a methyl group. A represents an alkylene group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 4 carbon atoms. The alkylene group may be linear or branched, but is linear. For example, an ethylene group and a trimethylene group can be preferably mentioned.

R ¹ and R ² each independently represents an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group may be linear or branched, and examples thereof include a methyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert -A butyl group, various pentyl groups, various hexyl groups, etc. can be mentioned. n represents an integer of 0 to 2, if R ¹ is plural, a plurality of R ¹ may be the same with or different from each other, if the OR ² there is a plurality, the plurality of OR ² are mutually It may be the same or different.

Examples of the group represented by —SiR ¹ _n (OR ² ) _3-n in the general formula (I) include a trimethoxysilyl group, a triethoxysilyl group, a tri-n-propoxysilyl group, and a triisopropoxysilyl group. , Tri-n-butoxysilyl group, triisobutoxysilyl group, tri-sec-butoxysilyl group, tri-tert-butoxysilyl group, dimethylmethoxysilyl group, methyldimethoxysilyl group and the like.

  Examples of the silane compound represented by the general formula (I) include 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltriethoxy. Examples thereof include silane, 2-acryloxyethyltrimethoxysilane, 2-acryloxyethyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropyltriethoxysilane. Among these, 3-methacryloxypropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane are preferable from the viewpoint of the performance of the resulting coating agent.

  In the present invention, as the component (a-1), the silane compound represented by the general formula (I) or a partial hydrolyzate thereof may be used alone or in combination of two or more. Good.

On the other hand, in the general formula (II) as the component (a-2), R ³ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. Or a vinyl group is shown.

  As said C1-C10 alkyl group, a C1-C6 alkyl group is preferable. The alkyl group may be linear or branched, and examples thereof include a methyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert -A butyl group, various pentyl groups, various hexyl groups, etc. can be mentioned.

  Examples of the aryl group having 6 to 10 carbon atoms include phenyl group, tolyl group, xylyl group, and naphthyl group. Examples of the aralkyl group having 7 to 10 carbon atoms include benzyl group, phenethyl group, and phenylpropyl group. Groups and the like.

R ⁴ represents an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. As this alkyl group, the same thing as what was illustrated by description of the alkyl group of said R < ³ > can be mentioned.

m represents an integer of 0 to 3, when there are a plurality of R ^3, a plurality of R ³ may be the same with or different from each other, if the OR ⁴ there is a plurality, the plurality of OR ⁴ each other It may be the same or different.

  m is preferably an integer of 1 to 3, and examples of the silane compound represented by the general formula (II) include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, etc. Among these, methyltrimethoxysilane is preferable from the viewpoint of the performance of the resulting coating agent.

  In the present invention, as the component (a-2), the silane compound represented by the general formula (II) or a partial hydrolyzate thereof may be used alone or in combination of two or more. Good.

  In the present invention, from the viewpoint of the performance of the resulting coating agent, the use ratio of the component (a-1) and the component (a-2) is preferably 99: 1 to 60:40 in terms of molar ratio, and 90:10. ~ 65: 35 is more preferred.

  In the present invention, a desired polyorganosiloxane sol of the component (A) is prepared by hydrolyzing and condensing the mixture of the component (a-1) and the component (a-2).

  For the hydrolysis / condensation reaction, a mixture of the component (a-1) and the component (a-2) is converted into an acid such as hydrochloric acid, sulfuric acid or nitric acid, or a solid acid in a polar solvent such as alcohol, ketone or ether. When the solid acid is used, the cation exchange resin is usually removed at a temperature of −10 to 70 ° C., preferably 10 to 40 ° C., preferably for 5 minutes or more. , (A) component polyorganosiloxane sol is obtained. The concentration of the polyorganosiloxane sol thus obtained is usually about 0.5 to 50% by mass, preferably 1 to 30% by mass.

In this hydrolysis / condensation reaction, the polymerization of the (meth) acryloxy group in the component (a-1) does not substantially occur. When the polymerization of the (meth) acryloxy group occurs, the performance of the resulting coating agent becomes insufficient.
[(B) Acrylic organic polymer compound]
The acrylic organic polymer compound of component (B) includes (b-1) an acrylic monomer having a metal-containing group capable of binding to a metal oxide by hydrolysis in the molecule, and (b-2). It is preferable to use a polymer obtained by copolymerizing an acrylic monomer containing no metal.

  Examples of the acrylic monomer of the component (b-1) include the same silane compound represented by the general formula (I) used as the component (a-1) or a partially hydrolyzed product thereof. Can do.

  In the present invention, as the acrylic monomer of the component (b-1), the silane compound represented by the general formula (I) or a partial hydrolyzate thereof may be used alone or in combination of two or more. May be used in combination. Moreover, the same thing as what was used as (a-1) component may be used, and a different thing may be used. The preferred component (b-1) is 3-methacryloxypropyltrimethoxysilane and / or 3-acryloxypropyltrimethoxysilane.

  On the other hand, the acrylic monomer not containing the metal of component (b-2) is represented by the general formula (III)

で表される化合物を用いることができる。

The compound represented by these can be used.

In the general formula (III), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents a hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group represented by R ⁶ include a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 7 carbon atoms. -10 aralkyl groups can be preferably mentioned. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and various butyl groups, pentyl groups, hexyl groups, octyl groups, and decyl groups. Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and a cyclooctyl group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, and a xylyl group. Examples of the aralkyl group having 7 to 10 carbon atoms, such as a group and a naphthyl group, include a benzyl group, a methylbenzyl group, and a phenethylyl group.

  Examples of the ethylenically unsaturated monomer represented by the general formula (III) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and hexyl (meth). Examples include acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, and benzyl (meth) acrylate. These may be used alone or in combination of two or more.

  In the present invention, if necessary, as an adhesion improver, (b-3) general formula (IV)

（式中、Ｒ^７は水素原子またはメチル基、Ｒ^８はエポキシ基、水酸基、メルカプト基、アミノ基、ハロゲン原子若しくはエーテル結合を有する炭化水素基を示す。）
で表されるアクリル系単量体を適宜用いることができる。

(In the formula, R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents an epoxy group, a hydroxyl group, a mercapto group, an amino group, a halogen atom, or a hydrocarbon group having an ether bond.)
An acrylic monomer represented by the formula can be used as appropriate.

In the acrylic monomer represented by the general formula (IV), the epoxy group, the hydroxyl group, the mercapto group, the amino group, the halogen atom or the hydrocarbon group having an ether bond represented by R ⁸ has 1 to 1 carbon atoms. Preferred examples include 10 linear or branched alkyl groups, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. The halogen atom for the substituent is preferably a chlorine atom or a bromine atom, and the amino group may be any of a free amino group, a monoalkyl-substituted amino group, and a dialkyl-substituted amino group. Specific examples of the hydrocarbon group include the same groups as those exemplified in the description of R ⁶ in the general formula (III).

  Examples of the acrylic monomer represented by the general formula (IV) include glycidyl (meth) acrylate, 3-glycidoxypropyl (meth) acrylate, 2- (3,4-epoxycyclohexyl) ethyl (meth) ) Acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-mercaptoethyl (meth) acrylate, 3-mercaptopropyl (meth) acrylate, 2- Mercaptopropyl (meth) acrylate, 2-aminoethyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 4-dimethylaminobenzyl ( Meta) Acryle DOO, 2-chloroethyl (meth) acrylate, preferably, 2-bromoethyl (meth) acrylate. These may be used alone or in combination of two or more.

  The component (b-1), the component (b-2), and the component (b-3) to be used as necessary are mixed in a suitable solvent such as methyl isobutyl ketone in the presence of a radical polymerization initiator. By polymerization, an acrylic organic polymer compound as the desired component (B) can be obtained.

In the present invention, the acrylic organic polymer compound of the component (B) is a molar ratio of the acrylic monomer of the component (b-1) and the acrylic monomer of the component (b-2). A polymer obtained by copolymerization at a ratio of 1:99 to 15:85 is preferable, and a polymer obtained by copolymerization at a ratio of 2:98 to 10:90 is more preferable. When the component (b-3) is used as necessary, a part of the component (b-2) may be replaced with the component (b-3).
[Coating agent]
The coating agent of the present invention comprises the (A) component polyorganosiloxane sol prepared as described above and the (B) component acrylic organic polymer compound. In view of the above, the solid content mass ratio of the component (A) and the component (B) is preferably in the range of 95: 5 to 5:95, and more preferably in the range of 90:10 to 10:90.

  Examples of the solvent for the coating agent of the present invention include alcohol solvents, ether solvents, cellosolve solvents, ketone solvents, and mixed solvents thereof.

  In addition to the component (A) and the component (B), other components may be added to the coating agent of the present invention as long as the properties of the present invention such as adhesion are not impaired. Examples include monomers and oligomers of acrylic compounds, polymerization initiators, and the like. Examples of monomers and oligomers of acrylic compounds include polyfunctional acrylates. Specifically, (C) a polyfunctional acrylate compound and (D) a thermal polymerization initiator, or (C) a polyfunctional acrylate compound ( E) A photoinitiator can be contained. By adding these, the curing rate can be increased.

  Examples of the polyfunctional acrylate compound of the component (C) include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (Meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified Di (meth) acrylate phosphate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythri Tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propion oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified Examples include dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate. These may be used individually by 1 type and may be used in combination of 2 or more type.

  As the thermal polymerization initiator of the component (D), any conventionally known ones such as various organic peroxides and azo compounds can be appropriately selected and used. On the other hand, as the photopolymerization initiator of the component (E), a conventionally known one such as a benzoin type, an acetophenone type, a benzophenone type, an anthraquinone type, a thioxanthone type or a ketal type is appropriately selected. Can be used.

  When the polyfunctional acrylate compound and the thermal polymerization initiator are contained, the amount of the thermal polymerization initiator used is usually about 0.01 to 50% by mass, preferably 1 to 20% by mass with respect to the total solid components. is there. By containing these, the cured film formation after apply | coating the coating agent of this invention to an organic type base material can be accelerated | stimulated.

  Moreover, when the polyfunctional acrylate compound and the photopolymerization initiator are contained, the amount of the photopolymerization initiator used is usually about 0.01 to 50% by mass, preferably 1 to 20% by mass with respect to the total solid components. %. By containing these, after applying the coating agent of this invention to an organic base material, a cured film can be rapidly formed by irradiating an ultraviolet-ray.

The solid content concentration in the coating agent of the present invention is not particularly limited as long as it is a viscosity at which the coating agent can be applied, and is usually about 0.01 to 50% by mass, preferably 0. .1 to 30% by mass.
[Hardened coat layer]
The cured coating layer of the present invention is a layer formed on the surface of the organic base material using the above-described coating agent of the present invention.

  Examples of the organic base material include polyolefin resins such as polyethylene, polypropylene, poly-4-methylpentene-1 and polybutene-1, polycycloolefin resins such as polynorbornene, polyethylene terephthalate and polyethylene naphthalate. Polyester resin; Polycarbonate resin; Polyphenylene sulfide resin; Polyethersulfone resin; Polyethylene sulfide resin; Polyphenylene ether resin; Styrene resin; Acrylic resin; Polyamide resin; Cellulose resin such as cellulose acetate; Can be mentioned. Among these, acrylic resins, polyester resins, polycarbonate resins, and polycycloolefin resins are preferable from the viewpoints of transparency, heat resistance, low water absorption, economy, and the like. There is no restriction | limiting in particular in the shape of an organic type base material, Any, such as a film form, a sheet form, and plate shape, may be sufficient.

  Moreover, in order to further improve the adhesiveness with the cured coating layer provided on the organic base material, the organic base material can be subjected to a surface treatment by an oxidation method, an unevenness method, or the like, if desired. Examples of the oxidation method include corona discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment and the like, and examples of the unevenness method include sand blast method and solvent treatment method. Is mentioned. These surface treatment methods are appropriately selected according to the type of substrate.

  The cured coating layer of the present invention can be formed by the following method. That is, using the above-described coating agent of the present invention (which may contain a polyfunctional acrylate compound and a thermal polymerization initiator), the dry thickness is usually about 0.01 to 10 μm on the organic base material. Preferably, a known method such as a dip coating method, a spin coating method, a spray coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, or a gravure coating method is used so as to be 0.02 to 3 μm. The cured coating layer of the present invention can be formed by forming a coating film by means and performing a known drying treatment, for example, a heat drying treatment at a temperature of about 50 to 200 ° C.

  When the coating agent of the present invention contains a polyfunctional acrylate compound and a photopolymerization initiator, a coating film is formed on the organic base material in the same manner as described above, and is dried at about 50 to 200 ° C. as necessary. Thereafter, the cured coating layer of the present invention can be formed by irradiating with ultraviolet rays and further aging at a temperature of about 50 to 200 ° C.

The cured coating layer of the present invention formed in this way is excellent in adhesion with an organic base material.
[Structure]
The structure of the present invention is characterized by having the cured coating layer of the present invention provided on an organic base material. The cured coating layer is excellent in adhesion to an organic base material and also excellent in adhesion to a metal or inorganic compound deposited film formed thereon. Therefore, the structure of the present invention is selected from a metal film and an inorganic compound film on the cured coating layer by physical vapor deposition (PDV method) or chemical vapor deposition (CVD). It is preferable that at least one thin film is provided. The PDV method includes a vacuum deposition method, a sputtering method, an ion plating method, and the like.

Examples of the structure of the present invention include the following.
(1) Antireflection film As an antireflection film for preventing screen reflection in flat panel displays such as PDP, CRT, LCD, etc., the cured coating layer of the present invention is provided on a substrate film, and then the PVD method is used. Or CVD method, an antireflection film provided with a low refractive index thin film such as MgF ₂ , or a substance having a high refractive index (ITO, TiO _2, etc.) and a substance having a low refractive index (MgF ₂ , SiO _2, etc.) alternately A laminated antireflection film can be used.
(2) Heat ray reflective film To reflect heat rays (infrared rays) on building windows, vehicle windows, refrigerated and frozen showcase windows to reduce heat and save energy. Examples of the heat ray reflective film to be applied include a heat ray reflective film in which the cured coating layer of the present invention is provided on the surface of the transparent substrate film and a metal thin film such as aluminum, silver, or gold is provided thereon by the PVD method. Can do.
(3) Conductive film As a conductive film used for EL elements, LCD elements, solar cells, resistive touch panels, etc., and used as an electromagnetic shielding film or antistatic film, the present invention is applied to the surface of a plastic film. A hard coat layer is formed on the metal oxide layer such as indium oxide, tin oxide, zinc oxide, cadmium oxide, ITO, gold, platinum, silver, nickel, aluminum, copper by PVD method or CVD method. Examples thereof include a conductive film provided with a thin film made of an inorganic or metallic conductive material such as a metal.
(4) Organic base material provided with an optical recording material layer An optical recording medium is generally an optical recording material layer, a dielectric layer on a transparent organic base material such as a base material such as polycarbonate or polymethyl methacrylate. In addition, a metal reflective layer, an organic protective layer, and the like are sequentially laminated, and a dielectric base layer may be provided between the base material and the optical recording material layer.

  For example, Tb-Fe, Tb-Fe-Co, Dy-Fe-Co, Tb-Dy- are provided on the surface of the light-transmitting organic base material by providing the cured coating layer of the present invention on the surface by PVD or CVD. Inorganic magneto-optical recording material such as Fe—Co, or TeOx, Te—Ge, Sn—Te—Ge, Bi—Te—Ge, Sb—Te—Ge, Pb—Sn—Te, Tl—In—Se Examples thereof include a structure provided with a layer made of an inorganic phase change recording material.

Further, a structure in which a dielectric underlayer made of SiN, SiO, SiO ₂ , Ta ₂ O ₅ or the like is provided in place of the layer made of the magneto-optical recording material or the phase change recording material is mentioned. it can.
(5) Near-infrared absorbing film for PDP It is known that PDP emits near-infrared rays. This near-infrared ray may affect peripheral electronic devices such as cordless phones and video decks that use a near-infrared remote control device, and may interfere with normal operation. It is required to block this near-infrared ray as much as possible. .

  In addition, since PDPs also require electromagnetic wave shielding and antireflection functions, generally at least three functions of (1) an electromagnetic wave shielding film, (2) a near infrared ray absorbing film, and (3) an antireflection film are provided on the display screen. Measures are taken in which a front plate having a protective film is disposed such that the antireflection film is the outermost surface (observer side).

As the near-infrared absorbing film of (2) above, the cured coating layer of the present invention was provided on the surface of the transparent substrate film, and a thin film layer of a metal-based near infrared absorbing agent was formed thereon by the PVD method or the CVD method. A near-infrared absorption film etc. can be mentioned.
In addition, a reflection mirror, an optical lens, an exterior of a mobile phone, a camera cover, and the like are also included.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

In addition, the various characteristics in each example were calculated | required according to the method shown below.
(1) Adhesion In accordance with JIS K5400, a silica-based thin film-coated acrylic substrate and a silica-based thin film-coated acrylic substrate with an antireflection film are attached to the surface with a 100 mm square grid with a rotary cutter. (Registered trademark, manufactured by Kogyo Co., Ltd.) was pressure-bonded and peeled off at once. From the peeled area, the adhesion of the thin film was evaluated according to the following score in accordance with JIS K5400.

10 points: peeling area 0%, 8 points: peeling area within 5%, 6 points: above 5% to 15%, 4 points: above 15% to 35%, 2 points: above 35% to 65%, 0 point: Over 65% (2) Haze value and total light transmittance In accordance with JIS K7361, using a turbidimeter NDH2000 [manufactured by Nippon Denshoku Industries Co., Ltd.], a silica-based thin film coated acrylic base material and antireflection The haze value and total light transmittance of the silica-based thin film-coated acrylic substrate with film were measured.
(3) Transmittance at a wavelength of 600 nm Using a UV-visible near-infrared spectrophotometer “V-670DS” [manufactured by JASCO Corporation], the transmittance of a silica-based thin film-coated acrylic base material at a wavelength of 600 nm was measured.
(4) Environmental resistance After leaving the silica-based thin film-coated acrylic base material with an antireflection film under the following conditions, the adhesiveness was evaluated in the same manner as the above-mentioned adhesive evaluation.

(A) Moisture and heat resistance test: 24 hours under conditions of 60 ° C. and 90% relative humidity (a) Long-term moisture and heat resistance test: 500 hours under conditions of 60 ° C. and 90% relative humidity (c) Low temperature test: −20 ° C. (D) Warm water test: immersed in ion-exchanged water heated to 60 ° C. for 4 hours. This environmental resistance was evaluated for those having adhesion of 6 points or more.
Example 1
(1) Preparation of coating solution 16.25 g of 3-methacryloxypropyltrimethoxysilane (MPTMS) and 3.81 g of methyltrimethoxysilane (MTMS) were added to 38.39 g of MeOH and stirred at 30 ° C. for 15 minutes. .1 mol / L nitric acid 1.17 g, distilled water 8.93 g and MeOH 16.45 g mixed solution was added and stirred at 30 ° C. for 24 hours for hydrolysis and polycondensation to obtain a polyorganosiloxane sol. .

  The MPTMS: MTMS molar ratio was 70:30, and the solid content concentration of the polyorganosiloxane sol was 16% by mass.

  On the other hand, methyl methacrylate (MMA) 23.91 g and MPTMS 3.01 g were added to methyl isobutyl ketone (MIBK) 47.81 g, and MIBK 10.04 g and 2,2′-azobisisobutyronitrile (AIBN) were added thereto. 0.23 g of the mixed solution was added and stirred to obtain a uniform solution. The acrylic organic polymer compound was obtained by making this solution react at 60 degreeC for 30 hours, stirring. To this, 94.47 g of MIBK was added to obtain an acrylic organic polymer compound solution.

  The MPTMS: MMA molar ratio was 5:95, and the solid content concentration of the acrylic organic polymer compound solution was 15% by mass.

  Next, 2.83 g of the above-mentioned acrylic organic polymer compound solution is added to 34.31 g of MIBK, and further, 23.95 g of propylene glycol monomethyl ether (PGM) and 23.91 g of polyorganosiloxane sol are added in this order. A 5 mass% coating solution was prepared.

The solid content mass ratio of the polyorganosiloxane sol: acrylic organic polymer compound solution was 90:10.
(2) Preparation of silica-based thin film and vapor deposition of antireflection film After acrylite (50 mm × 50 mm, t = 2 mm, manufactured by Mitsubishi Rayon Co., Ltd.) of an acrylic substrate was subjected to ultrasonic cleaning for 5 minutes with MeOH, this base The coating solution was applied onto the material by spin coating (600 rpm × 30 seconds). Preheating was performed at 120 ° C. for 1.5 minutes, and aging was performed at 90 ° C. for 18 hours. An antireflection film having a thickness of 0.15 μm was formed on the surface of the obtained silica-based thin film by vacuum deposition of TiO ₂ and SiO ₂ in this order (SYNCRON BMC-1050 type deposition apparatus, center wavelength 550 nm, non-heated).
(3) Characteristic evaluation In the silica-based thin film-coated acrylic base and the silica-based thin film-coated acrylic base with antireflection film prepared as described above, adhesion, haze value, total light transmittance, transmittance (wavelength 600 nm), Environmental resistance was evaluated. As a result, the adhesion of the silica-based thin film-coated acrylic base was as good as 8 points, the haze value was 0.2%, and the total light transmittance was 92.5%, which was transparent. At this time, the transmittance at a wavelength of 600 nm was 92.5%, which was about the same as 92.5% of the acrylic base material alone. The adhesion of the silica-based thin film-coated acrylic base material with the antireflection film was as good as 8 points, the haze value was 0.2%, and the total light transmittance was 94.9% and transparent. Further, the adhesion after the wet heat resistance test was as good as 8 points.

  In addition, the environmental resistance of the silica-based thin film-coated acrylic base material was evaluated. As a result, the adhesion after the long-term moist heat resistance test, the low temperature test, and the hot water test was 8 points, 8 points, 8 points, and 10 points, respectively.

Table 1 shows the composition of the coating solution, and Table 2 shows the results of characteristic evaluation.
Examples 2-4
The same procedure as in Example 1 was performed except that each coating solution was prepared with the composition shown in Table 1. Table 2 shows the characteristic evaluation results.
Example 5
The same procedure as in Example 1 was performed except that 29.13 g of cyclohexanol (CH) and 29.13 g of diacetone alcohol (DAA) were used instead of PGM and MIBK when preparing the coating solution.

Table 1 shows the composition of the coating solution, and Table 2 shows the results of characteristic evaluation.
Example 6
The same procedure as in Example 5 was performed except that the coating liquid was applied on the acrylite by a spray coating method.

Table 1 shows the composition of the coating solution, and Table 2 shows the results of characteristic evaluation.
Example 7
After adding 16.43 g of 3-acryloxypropyltrimethoxysilane (APTMS) and 4.009 g of MTMS to 37.56 g of MeOH and stirring at 30 ° C. for 15 minutes, 1.25 g of 0.1 mol / L nitric acid and distilled water 9 A mixed solution of .58 g and 16.10 g of MeOH was added and stirred at 30 ° C. for 24 hours for hydrolysis and polycondensation to obtain a polyorganosiloxane slurry. The same procedure as in Example 1 was conducted except that this polyorganosiloxane slurry was used in place of the polyorganosiloxane slurry.

  The APTMS: MTMS molar ratio was 70:30, and the solid content concentration of the polyorganosiloxane slurry was 16% by mass.

Table 1 shows the composition of the coating solution, and Table 2 shows the results of characteristic evaluation.
Example 8
2.83 g of an acrylic organic polymer compound solution was added to 34.04 g of MIBK, and 34.04 g of PGM and 11.95 g of polyorganosiloxane sol were added thereto. Furthermore, 1.91 g of “KAYARAD DPHA” (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional acrylate (dipentaerythritol hexaacrylate), and 2,2′-azobis (4-methoxy-2,4) as a thermal polymerization initiator -Dimethylvaleronitrile) 0.21 g was added to prepare a coating solution. Except this, the same procedure as in Example 1 was performed.

  The solid content mass ratio of the polyorganosiloxane sol A: acrylic organic polymer compound solution was 50:50.

Table 1 shows the composition of the coating solution, and Table 2 shows the results of characteristic evaluation.
Example 9
2.83 g of an acrylic organic polymer compound solution was added to 34.04 g of MIBK, and 34.04 g of PGM and 11.95 g of polyorganosiloxane sol were added thereto. Furthermore, 1.91 g of “KAYARAD DPHA” (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional acrylate and 0.21 g of 1-hydroxy-cyclohexyl-phenyl-ketone as a photopolymerization initiator were added to prepare a coating solution. This coating solution was applied onto acrylite by spin coating, then irradiated with ultraviolet rays (illuminance: about 60 mW / cm ² ), and finally aged at 90 ° C. for 1 hour. Except this, the same procedure as in Example 1 was performed.

Table 1 shows the composition of the coating solution, and Table 2 shows the results of characteristic evaluation.
Comparative Example 1
In Example 1, an antireflection film was deposited directly on acrylite without applying a coating solution on acrylite.

Table 2 shows the characteristic evaluation results.
Comparative Example 2
A coating liquid having a solid component concentration of 5% by mass was prepared by adding 21.29 g of PGM and 26.56 g of polyorganosiloxane sol to 37.15 g of MIBK. Except this, the same procedure as in Example 1 was performed.

Table 1 shows the composition of the coating solution, and Table 2 shows the results of characteristic evaluation.
Comparative Example 3
To 8.81 g of MIBK, 28.33 g of an acrylic organic polymer compound solution and 47.86 g of PGM were added in this order to prepare a coating solution having a solid component concentration of 5% by mass. Except this, the same procedure as in Example 1 was performed.

Table 1 shows the composition of the coating solution, and Table 2 shows the results of characteristic evaluation.
Comparative Example 4
16.25 g of MPTMS, 0.32 g of 2,2′-azobis (2,4-dimethylvaleronitrile), and 38.06 g of MeOH were stirred at 70 ° C. for 2 hours to polymerize the methacryloxypropyl group of MPTMS. Thereafter, 3.81 g of MTMS was added and stirred at 30 ° C. for 15 minutes, and then a mixed solution of 1.17 g of 0.1 mol / L nitric acid, 8.93 g of distilled water and 16.45 g of MeOH was added. This was stirred at 30 ° C. for 24 hours to undergo hydrolysis and polycondensation to obtain a polyorganosiloxane sol. The same procedure as in Example 1 was conducted except that this polyorganosiloxane sol was used instead of the polyorganosiloxane sol.

  Table 1 shows the composition of the coating solution, and Table 2 shows the results of characteristic evaluation.

［注］
１）実施例８：コーティング液中に、多官能アクリレート「ＫＡＹＡＲＡＤ ＤＰＨＡ」および熱重合開始剤を含有。

[note]
1) Example 8: The polyfunctional acrylate “KAYARAD DPHA” and a thermal polymerization initiator are contained in the coating solution.

  2) Example 9: The multifunctional acrylate “KAYARAD DPHA” and a photopolymerization initiator are contained in the coating solution.

［注］
１）実施例６：コーティング液をスプレー法にて塗布する。その他の例は、いずれもスピンコート法による塗布である。

[note]
1) Example 6: A coating solution is applied by a spray method. Other examples are all applied by spin coating.

  The coating agent of the present invention is for forming a coating layer interposed between an organic base material and a metal or inorganic compound vapor-deposited film in order to improve the adhesion. Furthermore, it is suitably used for forming an antireflection film, a heat ray reflective film, a conductive film, other functional films, etc. by PVD method or CVD method.

Claims (14)

A coating agent for forming an intermediate layer provided between an organic base material and a metal-based vapor deposition film formed on the base material,
(A) (a-1) General formula (I)

Wherein R is a hydrogen atom or a methyl group, A is an alkylene group having 1 to 6 carbon atoms, R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms, and n is an integer of 0 to 2. shown, when R ¹ is plural, a plurality of R ¹ may be the same with or different from each other, if the OR ² there is a plurality, the plurality of OR ² may be the same with or different from each other. )
And a partial hydrolyzate thereof, (a-2) general formula (II)
R ³ _m Si (OR ⁴ ) _4-m (II)
(In the formula, R ³ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group or vinyl group having 7 to 10 carbon atoms, and R ⁴ is an alkyl having 1 to 10 carbon atoms. group, m represents an integer of 0 to 3, when there are a plurality of R ^3, a plurality of R ³ may be the same with or different from each other, if the OR ⁴ there is a plurality, the plurality of OR ⁴ is They may be the same or different.)
A coating agent comprising: a polyorganosiloxane sol obtained by hydrolyzing and condensing a silane compound represented by the above or a partially hydrolyzed product thereof; and (B) an acrylic organic polymer compound.   The coating agent of Claim 1 which contains (A) component and (B) component in the ratio of solid content mass ratio 95: 5-5: 95.   The coating agent according to claim 1 or 2, wherein in the polyorganosiloxane sol as the component (A), the molar ratio of the component (a-1) to the component (a-2) is 99: 1 to 60:40. .   The coating agent according to any one of claims 1 to 3, wherein the silane compound represented by the general formula (I) is 3-methacryloxypropyltrimethoxysilane and / or 3-acryloxypropyltrimethoxysilane.   The coating agent according to any one of claims 1 to 4, wherein the silane compound represented by the general formula (II) is methyltrimethoxysilane.   (B) component acrylic organic polymer compound (b-1) an acrylic monomer having a metal-containing group capable of binding to a metal oxide by hydrolysis in the molecule, and (b-2) a metal. The coating agent according to any one of claims 1 to 5, which is obtained by copolymerizing an acrylic monomer not contained. The acrylic monomer as component (b-1) is represented by the general formula (I)

Wherein R is a hydrogen atom or a methyl group, A is an alkylene group having 1 to 6 carbon atoms, R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms, and n is an integer of 0 to 2. shown, when R ¹ is plural, a plurality of R ¹ may be the same with or different from each other, if the OR ² there is a plurality, the plurality of OR ² may be the same with or different from each other. )
The coating agent of Claim 6 which is a silane compound represented by these, or its partial hydrolyzate. The acrylic monomer as the component (b-2) is represented by the general formula (III)

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents a hydrocarbon group having 1 to 10 carbon atoms.)
The coating agent of Claim 6 or 7 which is a compound represented by these.   The coating agent according to claim 7 or 8, wherein the acrylic monomer as component (b-1) is 3-methacryloxypropyltrimethoxysilane and / or 3-acryloxypropyltrimethoxysilane.   The (B) component acrylic organic polymer compound comprises a (b-1) component acrylic monomer and a (b-2) component acrylic monomer in a molar ratio of 1:99 to 15: The coating agent according to any one of claims 6 to 9, which is obtained by copolymerization at a ratio of 85.   A cured coating layer formed on the surface of an organic base material using the coating agent according to any one of claims 1 to 10.   The cured coat layer according to claim 11, having a thickness of 0.01 to 10 μm.   A structure having the cured coat layer according to claim 11.   14. The structure according to claim 13, wherein at least one thin film selected from a metal film and an inorganic compound film is provided on the cured coat layer by physical vapor deposition or chemical vapor deposition. .