JP5964202B2 - Coating composition - Google Patents

Description

  The present invention relates to a coating composition.

  A coating composition containing at least one of tetraalkoxysilane and organoalkoxysilane, aminosilane, epoxysilane, organic polymer fine particles containing an ultraviolet absorbing group, a curing catalyst, and a dispersion medium is disclosed (Patent Document 1).

  Also disclosed is a coating composition comprising at least one of tetraalkoxysilane and organoalkoxysilane, aminosilane, epoxysilane, blocked isocyanate silane, organic polymer fine particles containing an ultraviolet absorbing group, a curing catalyst, and a dispersion medium. (Patent Document 2).

  The above coating composition includes double-sided easy-adhesive PET (polyethylene terephthalate) (for example, manufactured by Toray Industries, Inc.), untreated PET (PET that has not been subjected to surface treatment such as corona treatment or UV treatment, or PET that does not have an easy-adhesion layer. ) Was poor.

International Publication No. 2006/022347 Pamphlet International Publication No. 2007/099784 Pamphlet

  The objective of this invention is providing the composition which can manufacture the hardened | cured material excellent in adhesiveness with PET film.

（式中、Ｘは水素原子又は塩素原子、Ｒ^１０は水素原子、メチル基、又は炭素数４〜８の第３級アルキル基、Ｒ^１１は直鎖状又は分岐鎖状の炭素数２〜１０のアルキレン基、Ｒ^１２は水素原子又はメチル基を示し、ｐは０又は１を示す。）

（式中、Ｒ^１３は水素原子又はメチル基、Ｒ^１４は置換又は非置換の直鎖状又は分岐鎖状の炭素数２〜１０のアルキレン基、Ｒ^１５は水素原子又は水酸基、Ｒ^１６は水素原子、水酸基、又は炭素数１〜６のアルコキシ基を示す。）
６．さらに（Ｅ）コロイダルシリカを含む、又は（Ｅ）コロイダルシリカを混合して得られる１〜５のいずれかに記載のコーティング組成物。
７．前記（Ａ−１）テトラアルコキシシランが下記式（１）で表される１〜６のいずれかに記載のコーティング組成物。
Ｓｉ（ＯＲ^１）_４ （１）
（式中、Ｒ^１は、炭素数１〜４のアルキル基又は炭素数１〜４のアルコキシアルキル基である。複数のＲ^１は同一でも異なっていてもよい。）
８．前記（Ａ−２）オルガノアルコキシシランが下記式（２）で表される１〜７のいずれかに記載のコーティング組成物。
Ｒ^２ _ａＳｉ（ＯＲ^３）_４−ａ ・・・（２）
（式中、Ｒ^２は炭素数１〜１０のアルキル基、炭素数１〜１０のフッ素化アルキル基又はフェニル基、Ｒ^３は炭素数１〜４のアルキル基又は炭素数１〜４のアルコキシアルキル基であり、ａは１又は２である。Ｒ^２が複数ある場合、複数のＲ^２は同一でも異なっていてもよく、複数のＯＲ^３は同一でも異なっていてもよい。）
９．前記（Ａ−３）アミノシランが下記式（３）で表される１〜８のいずれかに記載のコーティング組成物。
Ｒ^４ _ｂＳｉ（ＯＲ^５）_４−ｂ ・・・（３）
（式中、Ｒ^４は炭素数１〜４のアルキル基；フェニル基；又はアミノ基、アミノアルキル基及びアルキルアミノ基の中から選ばれる１以上の基で置換された炭素数１〜３のアルキル基であり、Ｒ^４の少なくとも１つは、アミノ基、アミノアルキル基又はアルキルアミノ基のいずれかで置換された炭素数１〜３のアルキル基である。Ｒ^５は炭素数１〜４のアルキル基であり、ｂは１又は２である。Ｒ^４が複数ある場合、複数のＲ^４は同一でも異なっていてもよく、複数のＯＲ^５は同一でも異なっていてもよい。）
１０．前記（Ａ−４）エポキシシランが下記式（４）で表される１〜９のいずれかに記載のコーティング組成物。
Ｒ^６ _ｃＳｉ（ＯＲ^７）_４−ｃ ・・・（４）
（式中、Ｒ^６は炭素数１〜４のアルキル基；フェニル基；又はグリシドキシ基及び３，４−エポキシシクロヘキシル基の中から選ばれる１以上の基で置換された炭素数１〜６のアルキル基であり、Ｒ^６の少なくとも１つは、グリシドキシ基又は３，４−エポキシシクロヘキシル基で置換された炭素数１〜６のアルキル基である。Ｒ^７は炭素数１〜４のアルキル基であり、ｃは１又は２である。Ｒ^６が複数ある場合、複数のＲ^６は同一でも異なっていてもよく、複数のＯＲ^７は同一でも異なっていてもよい。）
１１．前記（Ａ−５）ブロック化イソシアネートシランが下記式（５）で表される１〜１０のいずれかに記載のコーティング組成物。
Ｒ^８ _ｄＳｉ（ＯＲ^９）_４−ｄ ・・・（５）
（式中、Ｒ^８は炭素数１〜４のアルキル基；フェニル基；又はブロック化イソシアネート基で置換された炭素数１〜６のアルキル基であり、Ｒ^８の少なくとも１つは、ブロック化イソシアネート基で置換された炭素数１〜６のアルキル基である。Ｒ^９は炭素数１〜４のアルキル基であり、ｄは１又は２である。Ｒ^８が複数ある場合、複数のＲ^８は同一でも異なっていてもよく、複数のＯＲ^９は同一でも異なっていてもよい。）
１２．前記（Ａ−６）炭素間２重結合を有するシラン化合物が下記式（２０）で表される１〜１１のいずれかに記載のコーティング組成物。
Ｒ^２０ _ｅＳｉ（ＯＲ^２１）_４−ｅ ・・・（２０）
（式中、Ｒ^２０は炭素数１〜４のアルキル基；ビニル基；又はビニル基、アクリル基及びメタクリル基の中から選ばれる１以上の基を有する置換基で置換された炭素数１〜６のアルキル基であり、Ｒ^２０の少なくとも１つは、ビニル基、アクリル基及びメタクリル基の中から選ばれる１以上の基を有する置換基で置換された炭素数１〜６のアルキル基である。Ｒ^２１は炭素数１〜４のアルキル基であり、ｅは１又は２である。Ｒ^２０が複数ある場合、複数のＲ^２０は同一でも異なっていてもよく、複数のＯＲ^２１は同一でも異なっていてもよい。）
１３．前記（Ｃ）硬化触媒が有機酸である１〜１２のいずれかに記載のコーティング組成物。
１４．１〜１３のいずれかに記載のコーティング組成物から得られる硬化物。
１５．下記成分を混合して調製するコーティング組成物の製造方法。
（Ａ−１）テトラアルコキシシラン及び（Ａ−２）オルガノアルコキシシランのうち少なくとも一方、
（Ａ−３）アミノシラン、
（Ａ−４）エポキシシラン、
（Ａ−５）ブロック化イソシアネートシラン、
（Ａ−６）炭素間２重結合を有するシラン化合物、
（Ｂ）有機高分子微粒子、
（Ｃ）硬化触媒、並びに
（Ｄ）分散媒体
１６．（Ａ−１）成分及び（Ａ−２）成分のうち少なくとも一方、（Ａ−４）成分、（Ｂ）成分、（Ｃ）成分、並びに（Ｄ）成分を含む混合液を作製し、（Ａ−５）成分を加え、さらに（Ａ−３）成分を加え、最後に（Ａ−６）成分を加える１５に記載のコーティング組成物の製造方法。
１７．１４に記載の硬化膜を、ポリエチレンテレフタラートフィルム上に形成した積層体。
１８．１〜１３のいずれかに記載のコーティング組成物をポリエチレンテレフタラートフィルム上に塗布し、加熱又は紫外線照射により硬化させる積層体の製造方法。 According to the present invention, the following coating compositions and the like are provided.
1. (A-1) at least one of tetraalkoxysilane and (A-2) organoalkoxysilane,
(A-3) aminosilane,
(A-4) Epoxysilane,
(A-5) blocked isocyanate silane,
(A-6) a silane compound having a double bond between carbons,
(B) organic polymer fine particles,
(C) a curing catalyst, and (D) a coating composition comprising a dispersion medium.
2. (A-1) at least one of tetraalkoxysilane and (A-2) organoalkoxysilane,
(A-3) aminosilane,
(A-4) Epoxysilane,
(A-5) blocked isocyanate silane,
(A-6) a silane compound having a double bond between carbons,
(B) organic polymer fine particles,
(C) a curing catalyst, and (D) a coating composition obtained by mixing a dispersion medium.
3. Including both (A-1) tetraalkoxysilane and (A-2) organoalkoxysilane, or mixing both (A-1) tetraalkoxysilane and (A-2) organoalkoxysilane The coating composition according to 1 or 2 obtained.
4). (B) The coating composition according to any one of 1 to 3, wherein the organic polymer fine particles contain an ultraviolet absorbing group.
5. 5. The coating composition according to 4, wherein the organic polymer fine particle (B) containing the ultraviolet absorbing group is a benzotriazole compound represented by the following formula (8) or a benzophenone compound represented by the following formula (9).

(In the formula, X is a hydrogen atom or a chlorine atom, R ¹⁰ is a hydrogen atom, a methyl group, or a tertiary alkyl group having 4 to 8 carbon atoms, and R ¹¹ is a linear or branched carbon atom having 2 to 10 carbon atoms. And R ¹² represents a hydrogen atom or a methyl group, and p represents 0 or 1.)

Wherein R ¹³ is a hydrogen atom or a methyl group, R ¹⁴ is a substituted or unsubstituted linear or branched alkylene group having 2 to 10 carbon atoms, R ¹⁵ is a hydrogen atom or a hydroxyl group, and R ¹⁶ is hydrogen. An atom, a hydroxyl group, or a C1-C6 alkoxy group is shown.)
6). The coating composition according to any one of 1 to 5, further comprising (E) colloidal silica or obtained by mixing (E) colloidal silica.
7). The coating composition according to any one of 1 to 6, wherein the (A-1) tetraalkoxysilane is represented by the following formula (1).
Si (OR ¹ ) ₄ (1)
(In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 1 to 4 carbon atoms. The plurality of R ¹ may be the same or different.)
8). The coating composition according to any one of 1 to 7, wherein the (A-2) organoalkoxysilane is represented by the following formula (2).
R ² _a Si (OR ³ ) _4-a (2)
(In the formula, R ² is an alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group or phenyl group having 1 to 10 carbon atoms, and R ³ is an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl having 1 to 4 carbon atoms. a radical, a case where 1 or 2 .R ² there is a plurality, the plurality of R ² may be the same or different, the plurality of oR ³ may be the same or different.)
9. The coating composition according to any one of 1 to 8, wherein the (A-3) aminosilane is represented by the following formula (3).
R ⁴ _b Si (OR ⁵ ) _4-b (3)
Wherein R ⁴ is an alkyl group having 1 to ⁴ carbon atoms; a phenyl group; or an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from an amino group, an aminoalkyl group and an alkylamino group. And at least one of R ⁴ is an alkyl group having 1 to 3 carbon atoms substituted with any of an amino group, an aminoalkyl group, or an alkylamino group, and R ⁵ is an alkyl group having 1 to 4 carbon atoms. a group, b if it is 1 or 2 .R ⁴ there are a plurality, the plurality of R ⁴ may be the same or different, the plurality of oR ⁵ may be the same or different.)
10. The coating composition according to any one of 1 to 9, wherein the (A-4) epoxysilane is represented by the following formula (4).
R ⁶ _c Si (OR ⁷ ) _4-c (4)
Wherein R ⁶ is an alkyl group having 1 to 4 carbon atoms; a phenyl group; or an alkyl group having 1 to 6 carbon atoms substituted with one or more groups selected from a glycidoxy group and a 3,4-epoxycyclohexyl group. a group, at least one of R ⁶ are, .R ⁷ is a glycidoxy group or 3,4-epoxy alkyl group having 1 to 6 carbon atoms which is substituted with a cyclohexyl group is an alkyl group having 1 to 4 carbon atoms If c is the .R ⁶ is 1 or 2 are plural, a plurality of R ⁶ may be the same or different, a plurality of oR ⁷ may be the same or different.)
11. The coating composition according to any one of 1 to 10, wherein the (A-5) blocked isocyanate silane is represented by the following formula (5).
R ⁸ _d Si (OR ⁹ ) _4-d (5)
Wherein R ⁸ is an alkyl group having 1 to 4 carbon atoms; a phenyl group; or an alkyl group having 1 to 6 carbon atoms substituted with a blocked isocyanate group, and at least one of R ⁸ is a blocked isocyanate. an alkyl group of 1 to 6 carbons substituted with a group .R ⁹ is an alkyl group having 1 to 4 carbon atoms, if d have a plurality .R ⁸ is 1 or 2, a plurality of ^{R 8} is (It may be the same or different, and a plurality of OR ⁹ may be the same or different.)
12 The coating composition according to any one of 1 to 11, wherein the (A-6) silane compound having a carbon-carbon double bond is represented by the following formula (20).
R ²⁰ _e Si (OR ²¹ ) _4-e (20)
(Wherein R ²⁰ is an alkyl group having 1 to 4 carbon atoms; vinyl group; or 1 to 6 carbon atoms substituted with a substituent having one or more groups selected from vinyl group, acrylic group and methacryl group. And at least one of R ²⁰ is an alkyl group having 1 to 6 carbon atoms substituted with a substituent having one or more groups selected from a vinyl group, an acrylic group, and a methacryl group. R ²¹ is an alkyl group having 1 to 4 carbon atoms, e is ^{if .R 20} is 1 or 2 have multiple, different multiple ^{R 20} may be the same or different, a plurality of ^{oR 21} is the same May be.)
13. The coating composition according to any one of 1 to 12, wherein the (C) curing catalyst is an organic acid.
A cured product obtained from the coating composition according to any one of 14.1 to 13.
15. The manufacturing method of the coating composition prepared by mixing the following component.
(A-1) at least one of tetraalkoxysilane and (A-2) organoalkoxysilane,
(A-3) aminosilane,
(A-4) Epoxysilane,
(A-5) blocked isocyanate silane,
(A-6) a silane compound having a double bond between carbons,
(B) organic polymer fine particles,
(C) curing catalyst, and (D) dispersion medium 16. A mixed liquid containing at least one of the component (A-1) and the component (A-2), the component (A-4), the component (B), the component (C), and the component (D) is prepared. -5) The method for producing a coating composition according to 15, wherein the component is added, the component (A-3) is further added, and finally the component (A-6) is added.
A laminate in which the cured film according to 17.14 is formed on a polyethylene terephthalate film.
The manufacturing method of the laminated body which apply | coats the coating composition in any one of 18.1-13 on a polyethylene-terephthalate film, and is hardened | cured by a heating or ultraviolet irradiation.

  ADVANTAGE OF THE INVENTION According to this invention, the composition which can manufacture the hardened | cured material excellent in adhesiveness with PET film can be provided.

The coating composition of the present invention comprises at least one of (A-1) tetraalkoxysilane and (A-2) organoalkoxysilane, (A-3) aminosilane, (A-4) epoxysilane, (A-5) A blocked isocyanate silane, (A-6) a silane compound having a carbon-carbon double bond, (B) organic polymer fine particles, (C) a curing catalyst, and (D) a dispersion medium. Moreover, Preferably both (A-1) tetraalkoxysilane and (A-2) organoalkoxysilane are included.
The coating composition of the present invention may be obtained from a mixture of the above components.

The components (A-1) to (A-6) may be a hydrolysis condensate, and the hydrolysis condensate is a hydrolysis condensate of a single compound of the components (A-1) to (A-6). Or a hydrolytic condensate of a mixture of any two or more of the components (A-1) to (A-6).
In the present invention, a silane compound containing an alkoxy group is an alkoxysilane compound and / or a partial condensate thereof, and a partial condensate of an alkoxysilane compound is a part of the alkoxysilane compound condensed and siloxane in the molecule. A polyalkoxysilane compound or a polyorganoalkoxysilane compound formed by forming a bond (Si—O bond).
The hydrolyzed condensate of the silane compound containing an alkoxy group may include a silane compound containing the alkoxy group before hydrolytic condensation in addition to the hydrolyzed condensate of the silane compound containing an alkoxy group.

(A-1) Tetraalkoxysilane As the tetraalkoxysilane compound, a tetraalkoxysilane compound or a partial condensate (polyalkoxysilane compound) bonded by a siloxane bond (Si—O bond) can be used. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
The tetraalkoxysilane compound and the partial condensate thereof can be represented, for example, by the following formula (1), and a compound represented by the following formula (6) is particularly preferable.
Si (OR ¹ ) ₄ (1)
[Wherein, R ¹ represents an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 1 to 4 carbon atoms. A plurality of R ¹ may be the same or different. ]

［式中、Ｒ^１は、上記と同じであり、ｎは１〜１５の整数である。］

[Wherein, R ¹ is the same as above, and n is an integer of 1 to 15.] ]

In the formulas (1) and (6), examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and various butyl groups. Examples of OR ¹ in which R ¹ is an alkoxyalkyl group having 1 to 4 carbon atoms include a 2-methoxyethoxy group and a 3-methoxypropoxy group.
Examples of the tetraalkoxysilane compound include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, and tetraisobutoxysilane.
Examples of the polyalkoxysilane compound include “M silicate 51”, “silicate 40”, and “silicate 45” manufactured by Tama Chemical Industry Co., Ltd., and “methyl silicate 51”, “methyl silicate 53A”, and “ethyl silicate 40” manufactured by Colcoat Co., Ltd. "Ethyl silicate 48" etc. are mentioned.

(A-2) Organoalkoxysilane As the organoalkoxysilane compound, an organoalkoxysilane compound or a partial condensate thereof can be used. The organoalkoxysilane compound does not include an amino group, an epoxy group, an isocyanate group, and a group having a carbon-carbon double bond (excluding an aromatic double bond) (for example, a vinyl group, an acrylic group, or a methacryl group). Further, the organoalkoxysilane compound does not contain (A-1) a tetraalkoxysilane compound.
These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

As the organoalkoxysilane compound, the organoalkoxysilane compound and the partial condensate thereof are preferably bifunctional alkoxysilane and trifunctional alkoxysilane, and can be represented by, for example, the following formula (2). The compounds represented are preferred.
R ² _a Si (OR ³ ) _4-a (2)
[Wherein, R ² represents an alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group or phenyl group having 1 to 10 carbon atoms, and R ³ represents an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl having 1 to 4 carbon atoms. And a is 1 or 2. When R ² are a plurality, the plurality of R ² may be the same or different, a plurality of OR ³ may be the same or different. ]

［式中、Ｒ^２及びＲ^３は上記と同じであり、ｍは１〜１５の整数である。］

[Wherein R ² and R ³ are the same as above, and m is an integer of 1 to 15.] ]

In the formulas (2) and (7), the alkyl group having 1 to 10 carbon atoms may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and isopropyl. Groups, various butyl groups, various hexyl groups, various octyl groups, various decyl groups and the like, and examples of the fluorinated alkyl group include a trifluoroethyl group and a trifluoropropyl group. Moreover, as a C1-C3 alkyl group, a methyl group, an ethyl group, n-propyl group, and an isopropyl group are mentioned. The alkyl group or alkoxyalkyl group having 1 to 4 carbon atoms is as described in the above formula (1). Preferably ^{R 2} is an alkyl group having 1 to 4 carbon atoms. R ³ is preferably an alkyl group having 1 to 4 carbon atoms. Preferably a is 1.

  Among the organoalkoxysilane compounds represented by formula (2), trifunctional alkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, and methyl-tris (2-methoxyethoxy). ) Silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, ethyl-tris (2-methoxyethoxy) silane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltripropoxysilane, hexyl Fluorinated amines such as tributoxysilane, decyltrimethoxysilane, decyltriethoxysilane, decyltripropoxysilane, decyltributoxysilane, trifluoropropyltrimethoxysilane, etc. Kill (trialkoxy) silane, phenyl trimethoxy silane, and phenyl triethoxy silane and the like. Moreover, methyldimethoxy (ethoxy) silane, ethyl diethoxy (methoxy) silane, etc. which contain two types of alkoxy groups are also mentioned.

Examples of the bifunctional alkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, bis (2-methoxyethoxy) dimethylsilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like.
Specific examples of the polyorganoalkoxysilane compound include “MTMS-A” manufactured by Tama Chemical Industry Co., Ltd., “SS-101” manufactured by Colcoat Co., Ltd., “AZ-6101” “SR2402” manufactured by Toray Dow Corning Co., Ltd. "AY42-163" and the like.

(A-3) Aminosilane The aminosilane compound is a silane compound containing an amino group, and preferably contains an alkoxy group. Moreover, an epoxy group, an isocyanate group, and a group having a carbon-carbon double bond (excluding an aromatic double bond) (for example, a vinyl group, an acryl group, and a methacryl group) are not included.
As the aminosilane compound, a partial condensate thereof (amino group-containing polyorganoalkoxysilane compound) can also be used. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
As an aminosilane compound, an amino group-containing organoalkoxysilane compound and a partial condensate thereof can be represented, for example, by the following formula (3).
R ⁴ _b Si (OR ⁵ ) _4-b (3)
[Wherein, R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms; a phenyl group; or an amino group (—NH ₂ group), an aminoalkyl group [— (CH ₂ ) _x —NH ₂ group (where x is 1 to An integer of 3)]), an alkylamino group [-NHR group (where R is an alkyl group having 1 to 3 carbon atoms)], and an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from And at least one of R ⁴ is an alkyl group having 1 to 3 carbon atoms substituted with any one of an amino group, an aminoalkyl group and an alkylamino group. R ⁵ is an alkyl group having 1 to 4 carbon atoms, and b is 1 or 2. If R ⁴ is plural, R ⁴ may be the same or different, the plurality of OR ⁵ may be the same or different. ]
In the above formula (3), the alkyl group having 1 to 3 carbon atoms and the alkyl group having 1 to 4 carbon atoms are as described in the above formula (1) or (2). R ⁴ is preferably an alkyl group having 1 to ⁴ carbon atoms or an alkyl group having 1 to 3 carbon atoms substituted with an amino group. R ⁵ is preferably an alkyl group having 1 to 4 carbon atoms. Preferably b is 1.

Specific examples of the amino group-containing organoalkoxysilane compound represented by the formula (3) include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane and N- (2-aminoethyl) -3-aminopropyl. Trimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino Examples include propyltriethoxysilane, N-methylaminopropyltrimethoxysilane, and N-methylaminopropyltriethoxysilane.
Examples of the amino group-containing polyorganoalkoxysilane compound include “KBP-90” manufactured by Shin-Etsu Silicone Co., Ltd.

(A-4) Epoxysilane The epoxysilane compound is a silane compound containing an epoxy group, and preferably contains an alkoxy group. Moreover, the group (for example, vinyl group, acrylic group, methacryl group) which has an amino group, an isocyanate group, and a carbon-carbon double bond (except an aromatic double bond) is not included.
As the epoxysilane compound, a partial condensate thereof (epoxy group-containing polyorganoalkoxysilane compound) can also be used. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

As the epoxysilane compound, an epoxy group-containing organoalkoxysilane compound and a partial condensate thereof can be represented by, for example, the following formula (4).
R ⁶ _c Si (OR ⁷ ) _4-c (4)
[Wherein R ⁶ is an alkyl group having 1 to 4 carbon atoms; a phenyl group; or a glycidoxy group or a 3,4-epoxycyclohexyl group substituted with one or more groups selected from 1 to 6 carbon atoms (preferably Is an alkyl group having 1 to 4 carbon atoms, and at least one of R ⁶ has 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group. It is an alkyl group. R ⁷ is an alkyl group having 1 to 4 carbon atoms, and c is 1 or 2. If R ⁶ is plural, R ⁶ may be the same or different, a plurality of OR ⁷ may be the same or different. ]

In the above formula (4), the alkyl group having 1 to 4 carbon atoms is as described in the above formula (1), and the alkyl group having 1 to 6 carbon atoms has 1 to 10 carbon atoms in the above formula (2). Among these alkyl groups, those having 1 to 6 carbon atoms. R ⁶ preferably has 1 to ⁶ carbon atoms (preferably 1 to 4 carbon atoms) substituted with one or more groups selected from an alkyl group having 1 to 4 carbon atoms, a glycidoxy group, and a 3,4-epoxycyclohexyl group. And more preferably an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) substituted with an alkyl group having 1 to 4 carbon atoms or a glycidoxy group. R ⁷ is preferably an alkyl group having 1 to 4 carbon atoms. Preferably b is 2.

  Specific examples of the epoxy group-containing organoalkoxysilane compound represented by the formula (4) include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxysilane. , 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like.

(A-5) Blocked isocyanate silane A blocked isocyanate silane compound (generally also called a blocked isocyanate silane compound or a blocked isocyanate silane compound) is a silane compound containing a blocked isocyanate group, Preferably, an alkoxy group is included. Further, it does not include an amino group, an epoxy group, and a group having a carbon-carbon double bond (excluding an aromatic double bond) (for example, a vinyl group, an acryl group, or a methacryl group).
As the blocked isocyanate silane compound, a partial condensate thereof (blocked isocyanate group-containing polyorganoalkoxysilane compound) can also be used. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
The blocked isocyanatosilane compound is an isocyanatosilane compound in which an isocyanate group is protected by a blocking agent such as oxime to be inactive, and is deblocked by heating to activate (regenerate) the isocyanate group (general) Also referred to as an isocyanate silane compound).

As the blocked isocyanate silane compound, a blocked isocyanate group-containing organoalkoxysilane compound and a partial condensate thereof can be represented, for example, by the following formula (5).
R ⁸ _d Si (OR ⁹ ) _4-d (5)
[Wherein R ⁸ is an alkyl group having 1 to 4 carbon atoms; a phenyl group; or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) substituted with a blocked isocyanate group, and R ⁸ At least one is an alkyl group having 1 to 6 carbon atoms (preferably having 1 to 4 carbon atoms) substituted with a blocked isocyanate group. R ⁹ is an alkyl group having 1 to 4 carbon atoms, and d is 1 or 2. If R ⁸ is plural, R ⁸ may be the same or different, a plurality of OR ⁹ may be the same or different. ]
In the above formula (5), the alkyl group having 1 to 4 carbon atoms and the alkyl group having 1 to 6 carbon atoms are as described in the above formula (1) or (4). Preferably, R ⁸ is an alkyl group having 1 to 4 carbon atoms (preferably having 1 to 4 carbon atoms) substituted with an alkyl group having 1 to 4 carbon atoms or a blocked isocyanate group. R ⁹ is preferably an alkyl group having 1 to 4 carbon atoms. Preferably d is 1.

  Specific examples of the blocked isocyanate group-containing organoalkoxysilane compound represented by the formula (5) include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, What protected the isocyanate group in compounds, such as 3-isocyanatopropyl methyl diethoxysilane and 3-isocyanatopropyl ethyl diethoxysilane, with the blocking agent is mentioned. Among these, 3-blocked isocyanatopropyltriethoxysilane can be mentioned as a preferable compound.

  Examples of the blocking agent for isocyanate groups include oxime compounds such as acetooxime, 2-butanone oxime, cyclohexanone oxime, methyl isobutyl ketoxime, lactams such as ε-caprolactam, alkylphenols such as monoalkylphenol (cresol, nonylphenol, etc.), Active methylene compounds such as 3,5-xylenol, dialkylphenols such as di-t-butylphenol, trialkylphenols such as trimethylphenol, malonic acid diesters such as diethyl malonate, acetoacetates such as acetylacetone and ethyl acetoacetate , Alcohols such as methanol, ethanol, n-butanol, hydroxyl group-containing ethers such as methyl cellosolve and butyl cellosolve, hydroxyl groups such as ethyl lactate and amyl lactate Esters, mercaptans such as butyl mercaptan and hexyl mercaptan, acid amides such as acetanilide and dimer acid amide, imidazoles such as imidazole and 2-ethylimidazole, pyrazoles such as 3,5-dimethylpyrazole, 1,2 Triazoles such as 1,4-triazole, and acid imides such as succinimide and phthalic imide can be used. In order to control the dissociation temperature of the blocking agent, a catalyst such as dibutyltin dilaurate may be used in combination.

(A-6) Silane compound having a carbon-carbon double bond (A-6) The component is a silane compound containing a group having a carbon-carbon double bond, such as a vinyl group, an acrylic group, or a methacryl group, preferably Contains an alkoxy group. Moreover, an amino group, an epoxy group, and an isocyanate group are not included.
The “carbon-carbon double bond” of the component (A-6) does not include an aromatic double bond. In this specification, the aromatic double bond is a double bond in a cyclic conjugated compound having 4n + 2 (n is an integer of 0 or more) π electrons.

Since the coating composition of the present invention contains (A-6) a silane compound having a carbon-carbon double bond, photocuring (UV curing) and electron beam curing (EB curing) are possible in addition to thermal curing.
As the silane compound having a carbon-carbon double bond, a partial condensate thereof (polyorganoalkoxysilane compound containing a group having a carbon-carbon double bond) can also be used. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

A silane compound having a carbon-carbon double bond and a partial condensate thereof can be represented, for example, by the following formula (20).
R ²⁰ _e Si (OR ²¹ ) _4-e (20)
[Wherein, R ²⁰ represents an alkyl group having 1 to 4 carbon atoms; vinyl group; or 1 to 6 carbon atoms substituted with a substituent having one or more groups selected from vinyl group, acrylic group and methacryl group. (Preferably having 1 to 4 carbon atoms) an alkyl group, and at least one of R ²⁰ is a carbon number substituted with a substituent having one or more groups selected from a vinyl group, an acrylic group and a methacryl group. It is a 1-6 (preferably C1-C4) alkyl group. R ²¹ is an alkyl group having 1 to 4 carbon atoms, and e is 1 or 2. If R ²⁰ there are a plurality, the plurality of R ²⁰ may be the same or different, a plurality of OR ²¹ may be the same or different. ]

In the formula (20), the alkyl group having 1 to 6 carbon atoms and the alkyl group having 1 to 4 carbon atoms are as described in the formula (1) or (4). Preferably, R ²⁰ has 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) substituted with one or more groups selected from an alkyl group having 1 to 4 carbon atoms, or a vinyl group, an acrylic group and a methacryl group. ) Alkyl group. Preferably, e is 1.

  The alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) substituted with a substituent having one or more groups selected from a vinyl group, an acryl group, and a methacryl group is preferably a vinyl group, It is a C1-C6 (preferably C1-C4) alkyl group substituted by one or more groups selected from vinyloxy group, acrylic group, acryloxy group, methacryl group and methacryloxy group, more preferably , An alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) substituted with one or more groups selected from an acrylic group, an acryloxy group, a methacryl group and a methacryloxy group.

  Specific examples of the compound represented by the formula (20) include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. An acrylic silane compound (acrylic group-containing silane compound) such as 3-methacryloxypropyltriethoxysilane, and a vinyl group-containing silane compound such as vinyltrimethoxysilane and vinyltriethoxysilane.

(B) Organic polymer fine particles As the organic polymer fine particles, those composed of a copolymer containing a monomer unit containing an ultraviolet absorbing group (hereinafter sometimes referred to as polymeric ultraviolet absorbing resin fine particles) are preferable.
When it contains an ultraviolet absorbing group, the weather resistance is excellent.

  Examples of the polymer ultraviolet-absorbing resin fine particles include an acrylic monomer (hereinafter referred to as an ultraviolet-absorbing acrylic monomer) containing a skeleton (benzophenone-based, benzotriazole-based, triazine-based, etc.) acting as an ultraviolet absorber in the side chain. And an ethylenically unsaturated compound (acrylic acid, methacrylic acid and derivatives thereof, styrene, vinyl acetate, etc.). While conventional ultraviolet absorbers are generally low molecular weight molecules having a molecular weight of 200 to 700, the weight average molecular weight of the polymer ultraviolet absorbing resin fine particles usually exceeds 10,000. Disadvantages of conventional low molecular weight ultraviolet absorbers such as compatibility with plastics and heat resistance are improved, and weather resistance can be imparted over a long period of time.

  The ultraviolet-absorbing acrylic monomer is not particularly limited as long as it is a compound containing at least one ultraviolet-absorbing group and acryloyl group in the molecule. Examples of such compounds include benzotriazole compounds represented by the following formula (8) and benzophenone compounds represented by the formula (9).

[Wherein, X is a hydrogen atom or a chlorine atom, R ¹⁰ is a hydrogen atom, a methyl group, or a tertiary alkyl group having 4 to 8 carbon atoms, and R ¹¹ is a linear or branched carbon atom having 2 to 10 carbon atoms. An alkylene group, R ¹² represents a hydrogen atom or a methyl group, and p represents 0 or 1. ]

[Wherein, R ¹³ is a hydrogen atom or a methyl group, R ¹⁴ is a substituted or unsubstituted linear or branched alkylene group having 2 to 10 carbon atoms, R ¹⁵ is a hydrogen atom or a hydroxyl group, and R ¹⁶ is hydrogen. An atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms is shown. ]

  Specific examples of the benzotriazole-based compound represented by the above formula (8) include, for example, 2- (2′-hydroxy-5 ′-(meth) acryloxyphenyl) -2H-benzotriazole, 2- (2 ′ -Hydroxy-3′-tert-butyl-5 ′-(meth) acryloxymethylphenyl) -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(2- (meth) acryloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5 '-(2- (meth) acryloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2 And '-hydroxy-3'-methyl-5'-(8- (meth) acryloxyoctyl) phenyl] -2H-benzotriazole.

Specific examples of the benzophenone compound represented by the above formula (9) include 2-hydroxy-4- (2- (meth) acryloxyethoxy) benzophenone and 2-hydroxy-4- (4- (meth)). Acryloxybutoxy) benzophenone, 2,2′-dihydroxy-4- (2- (meth) acryloxyethoxy) benzophenone, 2,4-dihydroxy-4 ′-(2- (meth) acryloxyethoxy) benzophenone, 2, 2 ′, 4-trihydroxy-4 ′-(2- (meth) acryloxyethoxy) benzophenone, 2-hydroxy-4- (3- (meth) acryloxy-2-hydroxypropoxy) benzophenone, 2-hydroxy-4- And (3- (meth) acryloxy-1-hydroxypropoxy) benzophenone.
These ultraviolet-absorbing acrylic monomers may be used alone or in combination of two or more.

The content of the ultraviolet-absorbing acrylic monomer unit in the polymer ultraviolet-absorbing resin fine particles is usually about 5 to 70% by mass from the viewpoint of the ultraviolet absorption ability of the cured film obtained, other physical properties, and economical efficiency. Preferably, it is about 10-60 mass%.
From the viewpoints of manufacturability, dispersibility in the composition, coatability of the composition, transparency of the cured film, and the like, the polymer ultraviolet absorbing resin fine particles preferably have an average particle diameter in the range of 1 to 200 nm. What is in the range of 1-100 nm is more preferable. The average particle diameter of the polymer ultraviolet absorbing resin fine particles can be measured by a laser diffraction scattering method or a dynamic light scattering method.

  In the present invention, the polymer ultraviolet absorbing resin fine particles are preferably used in a form dispersed in a dispersion medium. Examples of the dispersion medium include water, methanol, ethanol, propanol, 1-methoxy-2-propanol, and the like. Preferred examples include lower alcohols and cellosolves such as methyl cellosolve. By using such a dispersion medium, the dispersibility of the polymer ultraviolet absorbing resin fine particles is improved, and sedimentation can be prevented. More preferably, the dispersion medium is water. When the dispersion medium is water, it can also be used for the hydrolysis and condensation reaction of the silane compound in the formation of the matrix containing Si-O bonds derived from the components (A-1) to (A-6) described above.

There is no restriction | limiting in particular in the manufacturing method of a polymeric ultraviolet-absorption resin fine particle, A conventionally well-known method, for example, an emulsion polymerization method, a fine suspension polymerization method, etc. are employable.
In the emulsion polymerization method, a mixture of an ultraviolet-absorbing acrylic monomer as a monomer and an ethylenically unsaturated monomer copolymerized therewith is obtained from an aqueous dispersion medium, an anionic or nonionic surfactant. A method of obtaining a dispersion of fine polymer UV-absorbing resin fine particles by proceeding polymerization in a surfactant micelle layer emulsified into fine droplets and enclosing the monomer mixture using an emulsifier and a water-soluble polymerization initiator It is.
On the other hand, the fine suspension polymerization solution is first premixed in an aqueous medium by adding the monomer mixture, oil-soluble polymerization initiator, emulsifier and other additives as necessary, and homogenized by a homogenizer. Adjust the particle size of the oil droplets. Next, the homogenized liquid is sent to a polymerization vessel and a polymerization reaction is carried out to obtain a dispersion of polymer ultraviolet absorbing resin fine particles.
In any of the above methods, the polymerization temperature is about 30 to 80 ° C.

Examples of the water-soluble polymerization initiator used for emulsion polymerization include water-soluble peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide, these initiators or cumene hydroperoxide, t-butyl hydroperoxide, and the like. Redox initiators that combine hydroperoxides with reducing agents such as acidic sodium sulfite, ammonium sulfite, and ascorbic acid, water-soluble azo compounds such as 2,2′-azobis (2-methylpropionamidine) dihydrochloride, etc. Can be mentioned.
On the other hand, examples of oil-soluble polymerization initiators used for fine suspension polymerization include oil-soluble organic peroxides such as diacyl peroxides, ketone peroxides, peroxyesters, peroxydicarbonates, and the like. Examples include azo compounds such as' -azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile).

As specific examples of the polymer ultraviolet absorbing resin fine particles, on the other hand, the coating polymer ultraviolet absorber ULS-700, ULS-1700, ULS-383MA, ULS-1383MA, ULS-383MG, ULS-385MG manufactured by Yushi Kogyo Co., Ltd. , ULS-1383MG, ULS-1385MG, ULS-635MH, etc., high molecular weight ultraviolet light absorbing resin paints NCI-905-20EM and NCI-905-20EMA manufactured by Nikko Chemical Research Co., Ltd. (copolymerization of styrene monomer and benzotriazole monomer) Polymer ultraviolet absorber made of coalescence) and the like.
The polymer ultraviolet absorbing resin fine particles may be used singly or in combination of two or more.

(C) Curing catalyst The curing catalyst is a catalyst for hydrolyzing and condensing (curing) the above-mentioned silane compounds (A-1) to (A-6). For example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, Inorganic acids such as nitric acid, perchloric acid and sulfamic acid, organic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, citric acid, tartaric acid, succinic acid, maleic acid, glutamic acid, lactic acid and p-toluenesulfonic acid Can be mentioned.

Lithium hydroxide, sodium hydroxide, potassium hydroxide, n-hexylamine, dimethylamine, tributylamine, diazabicycloundecene, ethanolamine acetate, dimethylaniline formate, tetraethylammonium benzoate, sodium acetate, potassium acetate Organic metal salts such as sodium propionate, sodium glutamate, potassium propionate, sodium formate, potassium formate, benzoyltrimethylammonium acetate, tetramethylammonium acetate, tin octylate, tetraisopropyl titanate, tetrabutyl titanate, aluminum triisobutoxide , aluminum triisopropoxide, aluminum _{acetylacetonate,} SnCl _4, TiCl 4, etc. Lewis acids ZnCl ₄ and the like can be mentioned, et al That.

Among these curing catalysts, an organic acid can be preferably used because it can be highly dispersed even if the blending amount of the component (B) and the component (E) described later is increased and the transparency of the resulting film can be improved. In particular, an organic carboxylic acid, preferably acetic acid, can be preferably used.
(C) As a component, the said curing catalyst may be used individually by 1 type, and may be used in combination of 2 or more type.

(D) Dispersion medium The coating composition of the present invention is used in a state where the component particles are dispersed in a dispersion medium. The dispersion medium is not particularly limited as long as it can uniformly mix and disperse the respective component particles. For example, in addition to water, alcohols, aromatic hydrocarbons, ethers, ketones, esters, etc. The organic dispersion medium can be mentioned. Among these organic dispersion media, specific examples of alcohols include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, n- Octyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, 1-methoxy-2-propanol (propylene glycol monomethyl ether), propylene monomethyl ether acetate, diacetone Examples include alcohol, methyl cellosolve, ethyl cellosolve, propyl cellosolve, and butyl cellosolve. That.

Specific examples of other dispersion media include cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, xylene, dichloroethane, toluene, methyl acetate, ethyl acetate, ethoxyethyl acetate. Etc.
Among these dispersion media, water and alcohols are preferable from the viewpoint of performance as a dispersion medium.
(D) As a component, the said dispersion medium may be used individually by 1 type, and may be used in combination of 2 or more type.

(E) Colloidal silica It is preferable that the coating composition of this invention contains (E) colloidal silica in addition to the said component. When colloidal silica is included, the wear resistance is excellent.
Colloidal silica is also called colloidal silica or colloidal silicic acid. In water, it refers to a colloidal suspension of silicon oxide having Si—OH groups on its surface by hydration, and is formed when hydrochloric acid is added to an aqueous solution of sodium silicate. Recently, new preparation methods have been developed one after another, and there are those dispersed in a non-aqueous solution and fine powders made by a gas phase method, and the particle diameters are various from several nm to several μm. The average particle size is preferably about 1 to 200 nm. The composition of the particles is indefinite, and some particles are polymerized by forming siloxane bonds (—Si—O—, —Si—O—Si—). The particle surface is porous and is generally negatively charged in water. The average particle diameter can be measured by a laser diffraction scattering method.

Commercially available products include “Ultra High-Purity Colloidal Silica” Quartron PL Series (product names: PL-1, PL-3, PL-7) manufactured by Fuso Chemical Industry Co., Ltd. "Colloidal silica" (Product name: Snowtex 20, Snowtex 30, Snowtex 40, Snowtex O, Snowtex O-40, Snowtex C, Snowtex N, Snowtex S, Snowtex 20L, Snowtex OL, etc. ) "Or" organosilica sol (product names: methanol silica sol, MA-ST-MS, MA-ST-L, IPA-ST, IPA-ST-MS, IPA-ST-L, IPA-ST-ZL, IPA-ST-) UP, EG-ST, NPC-ST-30, MEK-ST, MEK-ST-MS, MIBK- T, XBA-ST, PMA-ST, DMAC-ST, PGM-ST, etc.) "can be mentioned.
(E) As a component, the said colloidal silica may be used individually by 1 type, and may be used in combination of 2 or more type.

(F) Dispersion stabilizer It is preferable that the coating composition of this invention contains (F) dispersion stabilizer other than the said component.
The dispersion stabilizer stably disperses the reactants of the silane compounds (A-1) to (A-6), the component (B), and the component (E) in the composition, and suppresses aggregation and gelation. Is an additive. In the composition, the fine particles of the components (B) and (E) are preferably maintained in a dispersed state without causing aggregation and precipitation or gelation. For example, it is preferably in a colloidal state that is stably suspended and suspended.

When using a condensation reaction at the time of thermosetting, it is desirable to stop the metal alkoxide in the OH form before coating. Therefore, it is desirable to maintain acidic conditions that promote the hydrolysis reaction and suppress the condensation reaction. Furthermore, since the carboxylic acid itself has not only an effect as an acid but also a coordination effect on a metal and becomes an effective additive for stabilizing an alkoxide, an organic acid, particularly an organic carboxylic acid is preferable as the component (F). Available. For example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and the like can be mentioned. In addition, since the composition forms a cured film by thermosetting, it preferably has a boiling point that does not remain in the cured film during thermosetting, and more preferably acetic acid can be used.
(F) As a component, the said dispersion stabilizer may be used individually by 1 type, and may be used in combination of 2 or more type.

(Optional additive)
In addition to the above-described components, the above-mentioned composition can appropriately contain various known additive components used in conventional compositions as necessary.
Examples of the additive component that can be contained as necessary include leveling agents, flexibility imparting agents, lubricity imparting agents, antioxidants, bluing agents, antistatic agents, and antifoaming agents (antifoaming agents). ), A light stabilizer, a weather resistance imparting agent, a colorant, a fine particle dispersant (anti-settling agent), a fine particle surface activity modifier, and the like.

<Leveling agent>
A leveling agent can be added to the composition in order to improve the smoothness of the resulting cured film and the flowability during coating. Examples of these additives include silicone leveling agents and fluorine leveling agents. , Acrylic leveling agents, vinyl leveling agents, and leveling agents in which fluorine and acrylic are combined. All work on the surface of the coating and reduce the surface tension. Each has its own characteristics and can be used according to the purpose. The ability to lower the surface tension is strong in silicone and fluorine systems, but acrylic and vinyl systems are advantageous in that wetting defects are less likely to occur when recoating.

  As a specific example of the silicone leveling agent, a copolymer of polyoxyalkylene and polydimethylsiloxane can be used. Commercially available silicone leveling agents include FZ-2118, FZ-77, FZ-2161, etc. manufactured by Toray Dow Corning Co., Ltd., KP321, KP323, KP324, KP326, KP340, KP341, etc. manufactured by Shin-Etsu Chemical Co., Ltd., etc. -Performance Materials Japan GK TSF4440, TSF4441, TSF4445, TSF4450, TSF4446, TSF4452, TSF4453, TSF4460, BYK-300, BYK-302, BYK-306, BYK-307, BYK, etc. -320, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-344, BYK-345, BYK-346, BY -348, may be mentioned BYK-377, BYK-378, BYK-UV3500, BYK-3510, BYK-3570 and the like polyether-modified silicone oil (polyoxyalkylene-modified silicone oil) and the like.

  Moreover, when heat resistance of 150 degreeC or more is required, the aralkyl modified silicone oil which has polyester modification and a benzene ring is suitable. As a commercially available product of polyester-modified silicone oil, BYK-310, BYK-315, BYK-370 manufactured by BYK Japan Japan Co., Ltd., as a commercially available product of aralkyl-modified silicone oil having a benzene ring, BYK manufactured by BYK Japan Japan Co., Ltd. -322, BYK-323, and the like.

As the fluorine leveling agent, a copolymer of polyoxyalkylene and fluorocarbon can be used.
Examples of commercially available fluorine leveling agents include MEGAFAC series manufactured by DIC Corporation, FC series manufactured by Sumitomo 3M Corporation, and the like.
Examples of commercially available acrylic leveling agents include BYK-350, BYK-352, BYK-354, BYK-355, BYK358N, BYK-361N, BYK-380N, BYK-382, BYK-392 manufactured by BYK-Chemie Japan. And BYK-340 into which fluorine is introduced.

By blending such a leveling agent, the finished appearance of the cured film is improved and can be uniformly applied as a thin film. The amount of the leveling agent used is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass, based on the total amount of the composition.
As a method of blending the leveling agent, it may be blended when preparing the composition, or may be blended into the composition immediately before forming the cured film, and further, preparation of the composition and formation of the cured film. You may mix | blend in both the last steps.

<Flexibility imparting agent>
The composition can contain a flexibility imparting agent as a stress relaxation agent in order to improve the flexibility of the obtained cured film.
As the flexibility imparting agent, for example, a silicone resin or the like can be used.
As a commercial product of silicone resin, Resin MK series manufactured by Wacker, for example, Belsil PMS MK (a polymer containing a repeating unit (unit T) of CH ₃ SiO _3/2 , up to 1% by mass (CH ₃ )) ₂ SiO _2/2 unit (including unit D), and KR-242A manufactured by Shin-Etsu Chemical Co., Ltd. (including 98% by mass of unit T and 2% by mass of dimethyl unit D and including Si—OH end groups) ), KR-251 (containing 88 mass% unit T and 12 mass% dimethyl unit D and containing Si—OH end groups), KR-220L (comprising unit T of formula CH ₃ SiO _3/2 , And those containing Si-OH (silanol) end groups).

(Content of each component in the coating composition)
Although content of each component in a composition can be selected suitably, it is preferable to select so that content of each component may become the range shown below, for example.
Excluding the dispersion medium of component (D), the content of each component with respect to the total amount of components (A-1) to (A-6), (B) and (C) is expressed in mass%. The component (B) preferably used as the dispersed state is calculated using only the solid content, and the dispersion medium contained in each component is included in the component (D).
(A-1) Content of a component is about 0.01-40 mass% normally, Preferably it is 0.1-20 mass%. (A-2) Content of a component is about 0.1-40 mass% normally, Preferably it is 1-30 mass%. (A-3) Content of a component is about 0.1-30 mass% normally, Preferably it is 0.3-20 mass%. (A-4) Content of a component is about 0.1-30 mass% normally, Preferably it is 0.3-20 mass%. The content of the component (A-5) is usually about 0.1 to 50% by mass, preferably 1 to 40% by mass. The content of the component (A-6) is usually about 0.1 to 50% by mass, preferably 0.3 to 40% by mass.

(B) Content of a component is about 0.1-50 mass% normally, Preferably it is 1-40 mass%.
(C) Content of a component is about 0.001-30 mass% normally, Preferably it is 0.001-20 mass%.
(D) Content of a component is about 5-1000 mass parts normally with respect to the total mass part of (A-1)-(A-6), (B), and (C), Preferably it is 20-800. Part by mass.
When (E) component is included, the content is about 0.1-70 mass% normally, Preferably it is 1-50 mass%.

  The mixing molar ratio of the component (A-3) and the component (A-5) is not particularly limited, but is preferably 1: 1 to 1: 5, more preferably 1: 2 to 1: 4. is there. When the blending molar ratio of the component (A-3) and the component (A-5) is within the above range, the durability of the obtained cured film is further improved.

The coating composition of the present invention contains components other than the above-described (A-1) to (A-6), (B), (C) and (D) as long as the effects of the present invention are not impaired. Or (A-1) to (A-6), (B), (C) and (D) only, or (A-1) to (A-6), (B ), (C) and (D).
Examples of other components include those described above.

Here, “substantially” means that the coating composition is 95% to 100% by weight (preferably 98% to 100% by weight) (A-1) to (A-6), (B). , (C) and (D).
The sintered body used in the present invention contains inevitable impurities in addition to (A-1) to (A-6), (B), (C) and (D) as long as the effects of the present invention are not impaired. Also good.

(Method for preparing coating composition)
The coating composition of the present invention comprises at least one (preferably both) of components (A-1) and (A-2), component (A-4), component (B), component (C), and (D It is preferable to prepare a liquid mixture containing the component (A), add the component (A-5), add the component (A-3), and finally add the component (A-6).
Specifically, a mixture of at least one (preferably both) and (A-4) components among components (A-1) and (A-2), (B) component, (C) component and (D) (A-5) component is added to the reaction product obtained by bringing the components into contact with each other and reacted, then (A-3) component is further added, and (A-6) component is further added and reacted. Is preferred.
Moreover, the mixture containing at least one (preferably both), (A-4) component, (B) component, (C) component, and (D) component among (A-1) component and (A-2) component. (A-5) component is added to the reaction product obtained by heating and reacted, then (A-3) component is further added, and (A-6) component is further added and reacted. Is more preferable.

Specifically, it is desirable to prepare the composition by performing the following operations.
First, a first mixed solution containing at least (A-1), (A-2), (A-4), (C), (D) and, if necessary, the component (B) is prepared, and then If necessary, the component (E) is mixed to prepare a second mixed solution, and then the component (A-5) is further mixed to prepare a third mixed solution. Furthermore, it is preferable to prepare a composition by mixing the component (A-3) and finally adding the component (A-6).
First, a first liquid mixture containing at least the components (A-1), (A-2), (A-4), (B), (C) and (D) is prepared, and then as necessary. The component (E) is mixed to prepare a second mixed solution, and then the component (A-5) is further mixed to prepare a third mixed solution. It is more preferable to further mix the component (A-3) and finally add the component (A-6) to prepare the composition.

Thus, it is preferable to prepare each component separately because the liquid storage stability (such as not gelation) of the composition is improved.
In particular, this effect is more exhibited when the amount of water in the liquid is increased by increasing the amount of the components (B) and (E). For example, after the components (A-1), (A-2), (A-4), (B), (C) and (D) are mixed, the component (E) is added as necessary. Next, the component (A-5) is mixed, and further the component (A-3) and finally the component (A-6) are mixed. In addition, (D) component can dilute a composition by adding, after preparing a composition.

  It is known that the liquid storage stability of a mixed material such as the above composition is liable to affect the liquid pH (for example, “Application of the sol-gel method to nanotechnology / supervision: Sakuo Sakuo” MC Publishing). In the preparation of the composition, since the acidic component is mixed as the component (C) and the basic component is mixed as the component (A-3) and the component (C), the liquid pH changes depending on the mixing order. As the liquid pH value, for example, the liquid pH value evaluated with a portable pH meter (trade name: Checker 1) manufactured by a calibration pH standard solution, the above first mixed liquid and second mixed liquid are It is preferable that pH ≦ 6, the third mixed solution, and the final mixed solution have pH ≦ 7. In particular, when the liquid pH exceeds 8 when the third liquid mixture, that is, the component (A-3) is mixed, the liquid stability may be lowered. The liquid is preferably kept in an acidic state from the start of preparation of the composition to the end of preparation. That is, it is preferable to prepare the composition by a procedure in which such conditions are maintained.

Moreover, it is preferable to heat-process said 1st liquid mixture, 2nd liquid mixture, and 3rd liquid mixture after mixing of each component. The temperature is preferably 30 ° C to 130 ° C, more preferably 50 ° C to 90 ° C, and the heat treatment time is preferably 30 minutes to 24 hours, more preferably 1 hour to 8 hours. The mixing and heating means is not particularly limited as long as it can uniformly mix and heat.
By heating in this way, the condensation reaction of the components (A-1), (A-2), (A-3), (A-4) and (A-5) in the liquid proceeds, and the boiling resistance is increased. And other durability. Reactions of the components (A-1), (A-2), (A-3), (A-4), and (A-5) can be analyzed by solution Si-NMR, thereby achieving a suitable structure. Can design. The reaction is often extremely slow at less than 30 ° C. or less than 30 minutes, and when it exceeds 130 ° C. or more than 24 hours, (A-1), (A-2), (A-3), (A -4) and (A-5) reaction of the component proceeds too much, and the liquid may gel or become highly viscous and may not be applied.

The composition after mixing the component (A-3) is also preferably heat-treated. In the case of mixing at room temperature, it is easily affected by the stirring efficiency, and due to this, when the degree of dispersion of the component (A-3) is low, the transparency of the cured film (decrease in total light transmittance, increase in haze) May fall. The temperature is preferably 30 ° C to 130 ° C, more preferably 50 ° C to 90 ° C, and the time is preferably 5 minutes to 10 hours, more preferably 15 minutes to 6 hours. The mixing and heating means is not particularly limited as long as it can uniformly mix and heat. If the temperature is less than 30 ° C. or less than 5 minutes, the effect of the heat treatment is often poor, and if it exceeds 130 ° C. or more than 10 hours, the liquid may gel or become highly viscous and cannot be applied.
In the examples described later, the evaluation results of the cured film produced using the composition obtained after standing for 1 week are described, but there is no particular limitation on the liquid standing period until the cured film is produced.

(Coated film, cured film)
A coating film is formed by applying the coating composition of the present invention on a substrate. For example, it is applied by a known method such as spraying, dipping, curtain flow, bar coater or roll coating.
The thickness of the coating film depends on what form the cured film to be formed is finally used, but the thickness of the cured film is preferably 0.5 to 30 μm, more preferably 0.5 to 15 μm. Adjust as follows.
Thereafter, the desired cured product (cured) is obtained by heat curing at appropriate curing conditions, usually room temperature to 190 ° C., preferably 80 to 140 ° C., for about 10 minutes to 24 hours, preferably 30 minutes to 3 hours. Membrane). In these thermosetting, it is preferable to add a polymerization initiator.

  Moreover, since the coating composition of this invention contains the silane compound ((A-6) component) which has a carbon-carbon double bond, photocuring (UV hardening) and electron beam hardening (EB hardening) are possible.

In the cured film obtained from the coating composition of the present invention, organic polymer fine particles (component (B)) and colloidal silica (component (C)) are dispersed in the case where colloidal silica (component (C)) is used. doing.
The dispersed state is preferably an inorganic-organic hybrid sea-island structure. The particle size of the organic fine particles corresponding to the islands having a sea-island structure is preferably 200 nm or less, more preferably 100 nm or less, and the particles are uniformly dispersed without agglomeration. The components (A-1) to (A-6) correspond to seas with a sea-island structure.

  The average particle diameter of the organic polymer fine particles in the film is defined as follows. The cross section of the cured film is observed under a condition of an acceleration voltage of 200 kV with a TEM (field emission transmission electron microscope). The value of the biaxial average diameter of each organic polymer fine particle present in 1 μm square is calculated. 10 organic polymer fine particles having a large biaxial average diameter are selected. The number average value of the biaxial average diameter values (that is, the value obtained by dividing the sum of the biaxial average diameters by 10) is defined as the average particle diameter.

  Moreover, the average particle diameter of the colloidal silica in the film is defined in the same manner as the average particle diameter of the organic polymer fine particles in the film. That is, the cross section of the cured film is observed under a condition of an acceleration voltage of 200 kV with a TEM (field emission transmission electron microscope). The value of the biaxial average diameter of each colloidal silica present in a 1 μm square is calculated. Select 10 colloidal silicas with a large biaxial average diameter. The number average value of the biaxial average diameter values (that is, the value obtained by dividing the sum of the biaxial average diameters by 10) is defined as the average particle diameter.

  Examples of the resin that can be used for the substrate include polyethylene, polypropylene, cycloolefin resins (eg, “ARTON” manufactured by JSR Corporation, “ZEONOR” “ZEONEX” manufactured by Nippon Zeon Corporation), and polyolefins such as polymethylpentene. Resins, polyethylene resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, cellulose resins such as diacetylcellulose, triacetylcellulose, acetylcellulose butyrate, polystyrene, syndiotactic polystyrene, acrylonitrile butadiene styrene Styrenic resin such as resin (ABS resin), imide resin such as polyimide, polyetherimide and polyamideimide, polyamide resin such as nylon, polyether , Ketone resins such as polyetheretherketone, sulfone resins such as polysulfone and polyethersulfone, vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride, acrylic resins such as polymethyl methacrylate, polycarbonate resins , Polyphenylene sulfide, polyacetal, modified polyphenylene ether, polyvinyl alcohol, epoxy resin, fluorine resin, plastic lens resin polymethyl methacrylate, alicyclic polyolefin, acrylonitrile styrene copolymer, methacryl styrene copolymer, alicyclic acryl, di Examples include glycol diallyl carbonate, diallyl phthalate, polyurethane, polythiourethane, episulfide, etc., and polymer alloys and polymers in which a plurality of the above polymers are mixed It may be a blend. Further, a laminated structure in which a plurality of the above resins are laminated may be used. Among the above resins, polyester resins (particularly polyethylene terephthalate), polyolefin resins and polycarbonate resins are preferable.

The substrate made of these resins may be transparent or translucent, may be colored, or may be uncolored, and may be appropriately selected according to the use. It is excellent in transparency and preferably has no color. Among the resins, polycarbonates that are excellent in transparency, mechanical properties, heat resistance, and the like are particularly suitable.
There is no restriction | limiting in particular in the thickness of a board | substrate, Although it selects suitably according to a condition, Usually, it is about 5 micrometers-30 mm, Preferably it is 15 micrometers-10 mm.

  The coating composition of the present invention can form a cured film with good adhesion on the substrate, but in order to further improve the adhesion, if desired, at least on the surface of the substrate on which the cured film is formed, Surface treatment can be performed by an oxidation method, an uneven method, or the like. Examples of the oxidation method include corona discharge treatment, plasma treatment such as low pressure plasma method and atmospheric pressure plasma method, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, electron beam treatment, and intro treatment. In addition, examples of the roughening method include a sand blast method and a solvent treatment method. These surface treatment methods are appropriately selected according to the type of the substrate, but in general, the corona discharge treatment method is preferably used from the viewpoints of curing and operability. Further, a surface treatment with a silane coupling agent or a primer layer can be provided. However, since it is not necessary to provide a primer layer in the present invention, the structure can be simplified.

  Moreover, you may provide an inorganic hard material layer, a transparent conductive film, a photocatalyst layer, etc. on the hardened | cured material layer formed on the board | substrate.

Example 1
A sample tube with a volume of 50 ml was charged with 0.80 g of organic polymer fine particles: ULS-1385MG (component (B) + component (D)), and stirred at 500 rpm, 1-methoxy-2-propanol (component (D)) ) 4.25 g, water (component (D)) 0.50 g, acetic acid (component (C)) 0.50 g, M silicate 51 (component (A-1)) 0.40 g, methyltrimethoxysilane ((A- 2) Component) 1.51 g, dimethoxy-3-glycidoxypropylmethylsilane (component (A-4)) 0.55 g, 20 mass% p-toluenesulfonic acid methanol solution (component (C) + component (D) ) In the order of 0.05 g, each was dropped over 1 minute. Subsequently, after stirring for 60 minutes at room temperature and 500 rpm, the mixture was allowed to stand for one day, which was designated as solution A.

A sample tube with a volume of 20 ml was charged with 1.10 g of 3-isocyanatopropyltriethoxysilane and 0.35 g of 2-butanone oxime (isocyanate group blocking agent), stirred at room temperature at 500 rpm for 10 minutes, and then allowed to stand for one day. This was designated as solution C. The blocking of the isocyanate group was confirmed by the disappearance of the isocyanate group signal by ¹³ C-NMR. The total amount of 3-isocyanatopropyltriethoxysilane and 2-butanone oxime was defined as the amount of the blocked isocyanatosilane compound: (A-5) component.

Into a 200 ml three-necked flask equipped with a condenser, put A liquid and a stirring bar, and stir at 500 rpm, and apply 6.50 g of IPA-ST-L (component (E) + component (D)) as liquid B over 5 minutes. The solution was added dropwise and stirred at room temperature for 60 minutes. Then, it heated at 600 rpm and 80 degreeC under nitrogen stream for 3 hours. Then, C liquid was added, and it stirred at 80 degreeC on the same conditions for 4 hours, Then, it left still at room temperature overnight.
Furthermore, 0.40 g of 3-aminopropyltrimethoxysilane ((A-3) component) was added dropwise thereto over 2 minutes as a D solution. After stirring at room temperature for 10 minutes, the mixture was further heated at 700 rpm and 80 ° C. for 3 hours under a nitrogen stream.
Further, 4.7 g of 3-methacryloxypropyltrimethoxysilane (component (A-6)) was added dropwise and stirred at room temperature for 2 hours.
Subsequently, it was left to stand for 1 week to obtain a coating solution.

As a substrate, a polyester (PET) film [manufactured by Toray Industries, Inc., product: Lumirror, product number: U48, thickness: 100 μm] was used. The coating solution obtained above is applied to the surface of the substrate with a bar coater so that the cured film has a thickness of 0.5 μm, and after heat drying at 60 ° C. for 1 minute, the integrated light quantity becomes 500 mJ / cm ^2. A laminate comprising a substrate and a cured film was produced by irradiating with UV rays.

The following evaluation was performed about the obtained laminated body. The results are shown in Table 1.
(1) Film appearance The appearance of the cured film was visually observed to check for foreign matters and mottled patterns.

(2) Total light transmittance The total light transmittance of the laminate was measured with a haze meter (NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.).

(3) Haze The haze value of the board | substrate and the laminated body was measured with the haze meter (Nippon Denshoku Industries Co., Ltd. make, NDH5000).

(4) Adhesiveness In accordance with JIS K 5400, a sample (cured film) was cut with a razor blade in 11 mm vertical and horizontal intervals at 2 mm intervals to make 100 grids, and a commercially available cellophane tape (“CT-24” (Width 24 mm) ”(manufactured by Nichiban Co., Ltd.) was tightly adhered to the belly of the finger, and then peeled off rapidly at an angle of 90 °. The exfoliation (99 to 1/100) was “Δ”, and the exfoliation (0/100) was “x”.

(5) Adhesive strength Measurement was carried out under the following conditions using a Cycus NN-05 type manufactured by Daipura Wintes Co., Ltd. The adhesion (peeling strength) P was calculated from the resistance FH in the horizontal direction applied to the blade obtained by the measurement.
Measurement mode: Constant speed mode (mode in which the blade is moved horizontally and vertically at a constant speed to perform cutting peeling)
Speed: Horizontal: 200 nm / sec, Vertical: 10 nm / sec
Cutting blade: Diamond cutting blade width 0.1mm, squeeze 20 °, Nige 10 °
P = F _H / w (P: adhesion (peel strength), F _H : horizontal resistance applied to the blade, w: blade width of the cutting blade)

(6) Durability Durability tests were performed using a small environmental tester (manufactured by ESPEC Corporation, SH-221) under conditions of 60 ° C., 90% RH, and 500 hours. Durability was evaluated by the adhesion of the cured film after the test. In addition, the evaluation method of adhesiveness is the same as the above.
The sample without peeling (100/100) was marked with “◯”, the sample with partial peeling (99 to 1/100) was marked with “Δ”, and the sample with all peeling (0/100) was marked with “x”.

Example 2
A laminate was prepared and evaluated in the same manner as in Example 1 except that a polyester film [manufactured by Toray Industries, Inc., product: Lumirror, product number: U46, thickness: 100 μm] was used as the substrate. The results are shown in Table 1.

Example 3
A laminate was prepared and evaluated in the same manner as in Example 1 except that a polyester film [manufactured by Toray Industries, Inc., product: Lumirror, product number: T60, thickness: 100 μm] was used as the substrate. The results are shown in Table 1.

Comparative Example 1
A coating solution was obtained in the same manner as in Example 1 except that 3-methacryloxypropyltrimethoxysilane (component (A-6)) was not added. The coating liquid was applied on the polyester film in the same manner as in Example 1, and heat dried at 100 ° C. for 1 minute to produce a laminate. The obtained laminate was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2
A laminate was prepared and evaluated in the same manner as in Comparative Example 1 except that a polyester film [manufactured by Toray Industries, Inc., product: Lumirror, product number: U46, thickness: 100 μm] was used as the substrate. The results are shown in Table 1.

Comparative Example 3
A coating solution and a laminate were prepared and evaluated in the same manner as in Example 1 except that 3-methacryloxypropyltrimethoxysilane (component (A-6)) was not added. The results are shown in Table 1.

Comparative Example 4
A laminate was prepared and evaluated in the same manner as in Comparative Example 3 except that a polyester film [manufactured by Toray Industries, Inc., product: Lumirror, product number: U46, thickness: 100 μm] was used as the substrate. The results are shown in Table 1.

Comparative Example 5
A laminate was prepared and evaluated in the same manner as in Comparative Example 1 except that a polyester film [manufactured by Toray Industries, Inc., product: Lumirror, product number: T60, thickness: 100 μm] was used as the substrate. The results are shown in Table 1.

  The coating composition of the present invention can be used for forming a hard coat layer and an undercoat layer of a functional film used for displays such as plasma, liquid crystal, and organic EL, mobile phone parts, touch panels, solar cells and the like.

Claims (17)

(A-1) tetraalkoxysilane,
(A-2) an organoalkoxysilane containing no amino group, epoxy group, isocyanate group and group having a carbon-carbon double bond,
(A-3) aminosilane,
(A-4) Epoxysilane,
(A-5) blocked isocyanate silane,
(A-6) a silane compound having a carbon-carbon double bond represented by the following formula (20) ,
(B) organic polymer fine particles,
(C) a curing catalyst, and (D) a coating composition comprising a dispersion medium.
R ²⁰ _e Si (OR ²¹ ) _4-e (20)
[Wherein R ²⁰ is an alkyl group having 1 to 4 carbon atoms; vinyl group; or substituted with one or more groups selected from vinyl group, vinyloxy group, acrylic group, acryloxy group, methacryl group and methacryloxy group. A C 1-6 alkyl group, wherein at least one of R ²⁰ is a carbon substituted with one or more groups selected from vinyl group, vinyloxy group, acrylic group, acryloxy group, methacryl group and methacryloxy group It is the alkyl group of number 1-6.
R ²¹ is an alkyl group having 1 to 4 carbon atoms,
e is 1 or 2. If R ²⁰ there are a plurality, the plurality of R ²⁰ may be the same or different, a plurality of OR ²¹ may be the same or different. ] (A-1) tetraalkoxysilane,
(A-2) an organoalkoxysilane containing no amino group, epoxy group, isocyanate group and group having a carbon-carbon double bond,
(A-3) aminosilane,
(A-4) Epoxysilane,
(A-5) blocked isocyanate silane,
(A-6) a silane compound having a carbon-carbon double bond represented by the following formula (20) ,
(B) organic polymer fine particles,
(C) a curing catalyst, and (D) a coating composition obtained by mixing a dispersion medium.
R ²⁰ _e Si (OR ²¹ ) _4-e (20)
[Wherein R ²⁰ is an alkyl group having 1 to 4 carbon atoms; vinyl group; or substituted with one or more groups selected from vinyl group, vinyloxy group, acrylic group, acryloxy group, methacryl group and methacryloxy group. A C 1-6 alkyl group, wherein at least one of R ²⁰ is a carbon substituted with one or more groups selected from vinyl group, vinyloxy group, acrylic group, acryloxy group, methacryl group and methacryloxy group It is the alkyl group of number 1-6.
R ²¹ is an alkyl group having 1 to 4 carbon atoms,
e is 1 or 2. If R ²⁰ there are a plurality, the plurality of R ²⁰ may be the same or different, a plurality of OR ²¹ may be the same or different. ] The coating composition according to claim 1 or 2 , wherein the organic polymer fine particles (B) contain an ultraviolet absorbing group. The coating composition according to claim 3 , wherein the organic polymer fine particles (B) containing the ultraviolet absorbing group are a benzotriazole-based compound represented by the following formula (8) or a benzophenone-based compound represented by the following formula (9). .

(In the formula, X is a hydrogen atom or a chlorine atom, R ¹⁰ is a hydrogen atom, a methyl group, or a tertiary alkyl group having 4 to 8 carbon atoms, and R ¹¹ is a linear or branched carbon atom having 2 to 10 carbon atoms. And R ¹² represents a hydrogen atom or a methyl group, and p represents 0 or 1.)

Wherein R ¹³ is a hydrogen atom or a methyl group, R ¹⁴ is a substituted or unsubstituted linear or branched alkylene group having 2 to 10 carbon atoms, R ¹⁵ is a hydrogen atom or a hydroxyl group, and R ¹⁶ is hydrogen. An atom, a hydroxyl group, or a C1-C6 alkoxy group is shown.) The coating composition according to any one of claims 1 to 4 , further comprising (E) colloidal silica or obtained by mixing (E) colloidal silica. The coating composition according to any one of claims 1 to 5 , wherein the (A-1) tetraalkoxysilane is represented by the following formula (1).
Si (OR ¹ ) ₄ (1)
(In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 1 to 4 carbon atoms. The plurality of R ¹ may be the same or different.) The coating composition according to any one of claims 1 to 6 , wherein the (A-2) organoalkoxysilane is represented by the following formula (2).
R ² _a Si (OR ³ ) _4-a (2)
(In the formula, R ² is an alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group or phenyl group having 1 to 10 carbon atoms, and R ³ is an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl having 1 to 4 carbon atoms. a radical, a case where 1 or 2 .R ² there is a plurality, the plurality of R ² may be the same or different, the plurality of oR ³ may be the same or different.) The coating composition according to any one of claims 1 to 7 , wherein the (A-3) aminosilane is represented by the following formula (3).
R ⁴ _b Si (OR ⁵ ) _4-b (3)
Wherein R ⁴ is an alkyl group having 1 to ⁴ carbon atoms; a phenyl group; or an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from an amino group, an aminoalkyl group and an alkylamino group. And at least one of R ⁴ is an alkyl group having 1 to 3 carbon atoms substituted with any of an amino group, an aminoalkyl group, or an alkylamino group, and R ⁵ is an alkyl group having 1 to 4 carbon atoms. a group, b if it is 1 or 2 .R ⁴ there are a plurality, the plurality of R ⁴ may be the same or different, the plurality of oR ⁵ may be the same or different.) Wherein (A-4) The coating composition according to any one of claims 1 to 8, an epoxy silane represented by the following formula (4).
R ⁶ _c Si (OR ⁷ ) _4-c (4)
Wherein R ⁶ is an alkyl group having 1 to 4 carbon atoms; a phenyl group; or an alkyl group having 1 to 6 carbon atoms substituted with one or more groups selected from a glycidoxy group and a 3,4-epoxycyclohexyl group. a group, at least one of R ⁶ are, .R ⁷ is a glycidoxy group or 3,4-epoxy alkyl group having 1 to 6 carbon atoms which is substituted with a cyclohexyl group is an alkyl group having 1 to 4 carbon atoms If c is the .R ⁶ is 1 or 2 are plural, a plurality of R ⁶ may be the same or different, a plurality of oR ⁷ may be the same or different.) The coating composition according to any one of claims 1 to 9 , wherein the (A-5) blocked isocyanate silane is represented by the following formula (5).
R ⁸ _d Si (OR ⁹ ) _4-d (5)
Wherein R ⁸ is an alkyl group having 1 to 4 carbon atoms; a phenyl group; or an alkyl group having 1 to 6 carbon atoms substituted with a blocked isocyanate group, and at least one of R ⁸ is a blocked isocyanate. an alkyl group of 1 to 6 carbons substituted with a group .R ⁹ is an alkyl group having 1 to 4 carbon atoms, if d have a plurality .R ⁸ is 1 or 2, a plurality of ^{R 8} is (It may be the same or different, and a plurality of OR ⁹ may be the same or different.)   The (A-6) silane compound having a carbon-carbon double bond is 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, or 3-methacryloxypropylmethyl. The coating composition according to claim 1, which is diethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, or vinyltriethoxysilane. Wherein (C) a coating composition according to any of claims 1 to 11 curing catalyst is an organic acid. Cured product obtained from the coating composition according to any one of claims 1 to 12. The manufacturing method of the coating composition prepared by mixing the following component.
(A-1) tetraalkoxysilane,
(A-2) an organoalkoxysilane containing no amino group, epoxy group, isocyanate group and group having a carbon-carbon double bond,
(A-3) aminosilane,
(A-4) Epoxysilane,
(A-5) blocked isocyanate silane,
(A-6) a silane compound having a carbon-carbon double bond represented by the following formula (20) ,
(B) organic polymer fine particles,
(C) a curing catalyst, and (D) a dispersion medium
R ²⁰ _e Si (OR ²¹ ) _4-e (20)
[Wherein R ²⁰ is an alkyl group having 1 to 4 carbon atoms; vinyl group; or substituted with one or more groups selected from vinyl group, vinyloxy group, acrylic group, acryloxy group, methacryl group and methacryloxy group. A C 1-6 alkyl group, wherein at least one of R ²⁰ is a carbon substituted with one or more groups selected from vinyl group, vinyloxy group, acrylic group, acryloxy group, methacryl group and methacryloxy group It is the alkyl group of number 1-6.
R ²¹ is an alkyl group having 1 to 4 carbon atoms,
e is 1 or 2. If R ²⁰ there are a plurality, the plurality of R ²⁰ may be the same or different, a plurality of OR ²¹ may be the same or different. ] A liquid mixture containing both the component (A-1) and the component (A-2), the component (A-4), the component (B), the component (C), and the component (D) is prepared, and (A-5 15. The method for producing a coating composition according to claim 14 , wherein the component (A-3) is added, and the component (A-6) is added. A laminate in which the cured film according to claim 13 is formed on a polyethylene terephthalate film. The coating composition according to any one of claims 1 to 12 coated on a polyethylene terephthalate film, a manufacturing method of a laminate is cured by heating or UV irradiation.