TW201922842A - Composition - Google Patents

Abstract

A coating formed from a composition including a compound that has a perfluoropolyether structure may be exposed to chemicals such as alcohols, depending on the application, and in such cases is required to be capable of maintaining excellent performance even after exposure to the chemical. The present invention provides a composition including a compound that has a perfluoropolyether structure, wherein the composition is capable of realizing a chemical-resistant coating. The present invention is a composition including an organic silicon compound (A) represented by formula (a1), an organic silicon compound (B) represented by formula (b1), and an organic silicon compound (C) represented by formula (c1). In formula (a1), Rfa1 is a divalent perfluoropolyether structure in which both ends are oxygen atoms.

Description

Composition

The present invention relates to a composition.

A film formed of a composition containing a compound having a perfluoropolyether structure has a very small free energy on the surface, and is therefore used in display devices such as touch panel displays, optical elements, semiconductor elements, building materials, automobiles, and buildings. Used in various fields such as window glass as an antifouling coating or a water- and oil-repellent coating.

For example, Patent Document 1 describes a first organic silicon compound (A) including a fluorine atom and a hydrolyzable group having a perfluoroalkyl group or a perfluoropolyether group bonded to a free end side of a silicon atom, and A water- and oil-repellent coating layer composition containing a hydrolyzable silane oligomer or a second organic silicon compound (B) containing a fluorocarbon group and a hydrolyzable group bonded to a silicon atom. [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2016/076245

[Problems to be Solved by the Invention] A film formed from a composition containing a compound having a perfluoropolyether structure may be exposed to chemicals such as alcohol depending on the application. In such a case, exposure to a chemical is required. Good performance (water repellency, etc.) can also be maintained after the product (hereinafter referred to as chemical resistance).

Therefore, an object of the present invention is to provide a composition containing a compound having a perfluoropolyether structure, which can realize a film having chemical resistance. [Means for solving problems]

The present invention achieving the above-mentioned problems is as follows.

[1] A composition comprising an organosilicon compound (A) represented by formula (a1), an organosilicon compound (B) represented by formula (b1), and an organosilicon compound (C) represented by formula (c1) . [Chemical 1] In the formula (a1), Rf ^a1 is a divalent perfluoropolyether structure having oxygen atoms at both ends, and R ¹¹ , R ¹² and R ¹³ are each independently an alkyl group having 1 to 20 carbon atoms. in the case of R ^11, a plurality of R ¹¹ may be different from each other, in a case where a plurality of R ^12, R ¹² may be each a plurality of different, in a case where a plurality of R ^13, R ¹³ s may be different from each other, E ¹ , E ² , E ³ , E ^4, and E ⁵ are each independently a hydrogen atom or a fluorine atom. In the case where there is a plurality of E ¹ , the plurality of E ¹ may be different from each other, and in the case where there is a plurality of E ² , , the plurality of E ² may be different from each other, in a case where there are a plurality of E ^3, E ³ may be different from each other plurality, in the case where there is a plurality of E ^4, E ⁴ may be different from each other plurality, G and ^{G. 1 2} are each independently a divalent to 10-valent organosiloxy group having a siloxane bond, and J ¹ , J ^2, and J ³ are each independently a hydrolyzable group _or- (CH ₂ ) _e6 -Si (OR ¹⁴ ) _3, e6 is 1 ~ 5, R ¹⁴ is methyl or ethyl, in the presence of a plurality of J ^1, J ¹ respectively a plurality of different, in a case where there are a plurality of J ^2, J ² a plurality of It may be different from each other, in a case where there are a plurality of J ^3, multiple J ³ may be different from each other, L ¹ and L ² each independently may contain an oxygen atom, a nitrogen atom, a carbon number of fluorine atoms, a divalent linking group having 1 to 12, in the case where there is a plurality of L ^1, a plurality of L ¹ may be different from each other, in a case where a plurality of L ^2, a plurality of L ² may be different from each other, D11 of 1 ~ 9, d12 of 0 ~ 9, a10 and a14 each independently 0 ~ 10, a11 and a15, respectively, They are independently 0 or 1, a12 and a16 are independently 0-9, a13 is 0 or 1, a21, a22, and a23 are independently 0-2, and e1, e2, and e3 are independently 1-3. [Chemical 2] In the formula (b1), Rf ^b10 is an alkyl or fluorine atom having 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced with fluorine atoms, and R ^b11 , R ^b12 , R ^b13, and R ^b14 are each independently hydrogen. atom or a C 1-4 alkyl group, in the case where there are plural R ^b11 and R ^b11 may be different from each other plurality, in the case where there are plural R ^b12 and R ^b12 may be different from each plurality, the presence of multiple a case where R ^b13 and R ^b13 may be respectively a plurality of different, in a case where there are plural R ^b14 and R ^b14 may be respectively a plurality of ^{different, Rf b11, Rf b12, Rf} b13 and Rf ^b14 each independently represent a more When a hydrogen atom is replaced by a fluorine atom having 1 to 20 carbon atoms or a fluorine atom, when a plurality of Rf ^b11 is present, the plurality of Rf ^b11 may be different from each other, and when a plurality of Rf ^b12 is present, the Rf ^b12 respectively different one, in a case where there are a plurality of Rf ^b13, respectively different plurality Rf ^b13, in the case where there are a plurality of Rf ^b14, respectively different plurality Rf ^b14, R ^b15 is a C 1 ~ 20 alkyl group, in the presence of multiple R ^b15 , multiple R ^b15 may be different, A ¹ is -O-, -C (= O) -O-, -OC (= O)-, -NR -, -NRC (= O)-or -C (= O) NR-, wherein R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluorine-containing alkyl group having 1 to 4 carbon atoms, in the presence of multiple A ¹ in the case where a plurality of a ¹ may be different from each other, a ² is a hydrolyzable group, in the presence of a plurality of a ^2, a ² may be respectively a plurality of different, b11, b12, b13, b14 and b15 are each independently An integer from 0 to 100, and c is an integer from 1 to 3. Regarding Rf ^b10- , -Si (A ² ) _c (R ^b15 ) _3-c , and b11-{C (R ^b11 ) (R ^b12 )}-, b12pcs- (C (Rf ^b11 ) (Rf ^b12 ))-, b13pcs- (Si ( ^Rb13 ) ( ^Rb14 ))-, b14pcs- (Si (Rf ^b13 ) ( ^Rfb14 ))-b15 -A ^1- , as long as Rf ^b10- , -Si (A ² ) _c (R ^b15 ) _3-c are terminal, no perfluoropolyether structure is formed, and -O- is not linked to -O- or -F, The bonds can be arranged in any order. [Chemical 3] In the formula (c1), R ^x1 , R ^x2 , R ^x3 , and R ^x4 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When multiple R ^x1 are present, multiple R ^x1 may be are different, in a case where a plurality of R ^x2, R ^x2 plurality may be different from each other, in a case where a plurality of R ^x3, R ^x3 may be different from each other a plurality of, in a case where a plurality of R ^x4, multiple Each R ^x4 may be different, and Rf ^x1 , Rf ^x2 , Rf ^x3 , and Rf ^x4 are each independently one or more carbon atoms of 1 to 20 carbon atoms or fluorine atoms in which a hydrogen atom is replaced by a fluorine atom, and there are multiple Rf in the case of ^{x1, x1} an Rf plurality of respectively different, in a case where there are a plurality of Rf ^x2, a plurality of different Rf ^x2 respectively, in a case where there are a plurality of Rf ^x3, a plurality of different Rf ^x3 respectively, in When there are multiple Rf ^x4 , multiple Rf ^x4 may be different, and R ^x5 is an alkyl group having 1 to 20 carbons. When there are multiple R ^x5 , multiple R ^x5 may be different, and X is hydrolysis In the case of multiple Xs, multiple Xs may be different, and Y is -O-, -NH-, or -S-. In the case of multiple Ys, multiple Ys may be different. Z Vinyl, α-methylvinyl, styryl, methacryl, acryl, amine, isocyanate, isocyanurate, epoxy, sulfonylurea, or mercapto, p1 is 1 An integer of -20, p2, p3, and p4 are each independently an integer of 0-10, p5 is an integer of 0-10, and p6 is an integer of 1-3. About Z-, -Si (X) _p6 (R ^x5 ) _3-p6 , p1-(C (R ^x1 ) (R ^x2 ))-, p2-(C (Rf ^x1 ) (Rf ^x2 ))-, p3-(Si (R ^x3 ) (R ^x4 )) -, P4-{Si (Rf ^x3 ) (Rf ^x4 )}-, p5 -Y-, as long as Z- and -Si (X) _p6 (R ^x5 ) _3-p6 are terminal and -O- and -O -If not connected, the bonds can be arranged in any order.

[2] The composition according to the above [1], wherein the organosilicon compound (C) is 0.1% by mass or more and 1% by mass or less in the total mass of the composition.

[3] The composition according to the above [1] or [2], wherein the organosilicon compound (C) is represented by the following formula (c2). [Chemical 4] In the formula (c2), X ¹ is a methoxy group or an ethoxy group. When a plurality of X ¹ are present, the plurality of X ¹ may be different, and Y ¹ is -NH-, -CH ₂ -or- case O-, Z ¹ is a group or a mercapto group, R ^x51 alkyl group having 1 to 20 carbon atoms, in the presence of a plurality of R ^x51, respectively, a plurality of different R ^x51, P61 is an integer of 1 to 3, q Is an integer of 2 to 5, and r is an integer of 0 to 5.

[4] A surface-treated resin substrate having a film including the composition according to any one of [1] to [3] on a surface of the resin substrate.

[5] The surface-treated resin substrate according to the above [4], wherein the resin substrate is an acrylic resin substrate.

[6] A method for producing a surface-treated resin substrate, applying the composition according to any one of [1] to [3] on the surface of the resin substrate, and subjecting the composition to normal temperature hardening. [Effect of the invention]

According to the composition of the present invention, since the predetermined organosilicon compound (A) having a perfluoropolyether structure is included, and the other two other organosilicon compounds (B) and (C) are also prescribed, the resistance of the obtained film is Improved chemical properties.

Hereinafter, the organic silicon compound (A), the organic silicon compound (B), and the organic silicon compound (C) will be described in this order.

1. Organic silicon compound (A) The organic silicon compound (A) is represented by the following formula (a1).

[Chemical 5]

In the formula (a1), Rf ^a1 is a divalent perfluoropolyether structure having oxygen atoms at both ends, and R ¹¹ , R ¹² and R ¹³ are each independently (ie, R ¹¹ and R ¹² and R ¹³ may be the same, or different from each other) is an alkyl group having 1 to 20 carbon atoms, and in the case where there is a plurality of R ^11, R ¹¹ may be respectively different plurality of, in a case where a plurality of R ^12, R ¹² may be each a plurality of different , in the case where there are a plurality of R ^13, R ¹³ s may be different from each ^{other, E 1, E 2, E} 3, E 4 and E ⁵ are each independently a hydrogen atom or a fluorine atom, in the presence of a plurality of E ¹ case, a plurality of E ¹ may be different from each other, in the case where there is a plurality of E ^2, E ² may be different from each other plurality, in the case where there are a plurality of E ^3, E ³ may be different from each plurality, the presence of multiple a case where E ^4, and E ⁴ may be different from each other plurality, G ¹ and G ² are each independently a divalent to 10-valent organic silicon oxygen silicon alkyl siloxane bonds, J ^1, J ² and J ³ Each is independently a hydrolyzable group _or- (CH ₂ ) _e6 -Si (OR ¹⁴ ) ₃ , e6 is 1 to 5, R ¹⁴ is a methyl group or an ethyl group, and when a plurality of J ¹ are present, a plurality of J ¹ may be different from each other, in the case where there is a plurality of J ^2, multiple J ² may be different from each other, in a case where there are a plurality of J ^3, a plurality of J ³ may be different from each other, L ¹ and L ² each independently may contain an oxygen atom, a nitrogen atom, a fluorine atom having a carbon number of 1 to 12 a divalent linking group, in the presence of a plurality of L ^1, a plurality of L ¹ may be different from each other, in a case where a plurality of L ^2, a plurality of L ² may be different from each other, D11 of 1 ~ 9, d12 0 ~ 9, a10 and a14 are independently 0 to 10, a11 and a15 are independently 0 or 1, a12 and a16 are independently 0 to 9, a13 is 0 or 1, a21, a22, and a23 are independently It is 0 to 2, and e1, e2, and e3 are independently 1 to 3.

The organosilicon compound (A) has a perfluoropolyether structure represented by Rf ^a1 as shown in the formula (a1), and has at least one hydrolyzable group represented by J ² _or- (CH ₂ ) _e6 -Si ( OR ¹⁴ ) ₃ (wherein R ¹⁴ is methyl or ethyl). The perfluoropolyether structure is a structure in which all the hydrogen atoms of polyoxyalkylene are replaced with fluorine atoms. It can also be called perfluorooxyalkylene, which can impart water repellency to the obtained film. . Further, the compound is as follows: by J ^2, an organic silicon compound (A) or using a polymerization reaction (especially condensation (polycondensation reaction) The reaction) with one another for other single bond together with an amount thereof, and the coating film can be obtained Matrix.

Rf ^{a1 is} preferably -O- (CF ₂ CF ₂ O) _e4- , or -O- (CF ₂ CF ₂ CF ₂ O) _e5- . Both e4 and e5 are 15 to 80.

R ¹¹ , R ¹² and R ¹³ are each preferably an alkyl group having 1 to 10 carbon atoms.

L ¹ and L ² are each preferably a divalent linking group having 1 to 5 carbon atoms containing a fluorine atom.

G ¹ and G ² are each preferably a divalent to pentavalent organosiloxy group having a siloxane bond.

J ¹ , J ² and J ^{3 are} preferably each independently a methoxy group, an ethoxy group, or — (CH ₂ ) _e6 -Si (OR ¹⁴ ) ₃ .

a10 is preferably 0 to 5 (more preferably 0 to 3), a11 is preferably 0, a12 is preferably 0 to 7 (more preferably 0 to 5), and a14 is preferably 1 to 6 (more preferably 1) ~ 3), a15 is preferably 0, a16 is preferably 0 to 6, a21 to a23 are each preferably 0 or 1 (more preferably, all 0), and d11 is preferably 1 to 5 (more preferably, 1) ~ 3), d12 is preferably 0 ~ 3 (more preferably 0 or 1), and e1 ~ e3 are preferably all 3. In addition, a13 is preferably 1.

As the compound (A), it is preferable to use the following compound: Rf ^a1 of the formula (a1) is -O- (CF ₂ CF ₂ CF ₂ O) _e5- , e5 is 35 to 50, and both L ¹ and L ² are Perfluoroalkylene having 1 to 3 carbon atoms, E ¹ , E ² and E ³ are hydrogen atoms, E ⁴ and E ⁵ are hydrogen atoms or fluorine atoms, and J ¹ , J ² and J ³ are methoxy groups. Or ethoxy (especially methoxy), a10 is 1 to 3, a11 is 0, a12 is 0 to 5, a13 is 1, a14 is 2 to 5, a15 is 0, a16 is 0 to 6, and a21 ~ A23 are independently 0 or 1 (more preferably, all of a21 ~ a23 are 0), d11 is 1, d12 is 0 or 1, and e1 to e3 are all 3.

In addition, if the compound a used as the compound (A) in the examples described later is represented by the formula (a1), Rf ^a1 is -O- (CF ₂ CF ₂ CF ₂ O) _43- , L ¹ and L ² is-(CF ₂ )-, E ¹ , E ² and E ³ are hydrogen atoms, E ⁵ is a fluorine atom, J ¹ and J ² are methoxy groups, a10 is 2, a11 is 0, and a12 0 to 5, a13 is 1, a14 is 3, a15 is 0, a16 is 0, a21 and a22 are 0, d11 is 1, d12 is 0, and e1 and e2 are 3.

As the compound (A), it is also preferable to use the following compound: Rf ^a1 of the formula (a1) is -O- (CF ₂ CF ₂ CF ₂ O) _e5- , e5 is 25 to 40, and L ¹ is fluorine-containing A divalent linking group having 3 to 6 carbon atoms and an oxygen atom, L ² is a perfluoroalkylene group having 1 to 3 carbon atoms, E ² and E ³ are both hydrogen atoms, E ⁵ is a fluorine atom, and J ² is -(CH ₂ ) _e6 -Si (OCH ₃ ) ₃ , e6 is 2 to 4, a10 is 1 to 3, a11 is 0, a12 is 0, a13 is 0, a14 is 2 to 5, a15 is 0, and a16 is 0, a21 to a23 are each independently 0 or 1 (more preferably, all of a21 to a23 are 0), d11 is 1, d12 is 0, and e2 is 3.

The organosilicon compound (A) is also preferably a compound represented by the following formula (a2-1).

[Chemical 6]

In the formula (a2-1), Rf ^a21 is an alkyl or fluorine atom having 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced with fluorine atoms, and Rf ^a22 , Rf ^a23 , Rf ^a24 and Rf ^a25 are each independently An alkyl group or a fluorine atom having 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced with fluorine atoms. When a plurality of Rf ^a22 are present, the plurality of Rf ^a22 may be different from each other, but when a plurality of Rf ^a23 are present. In the following, multiple Rf ^a23 may be different. In the case where there is multiple Rf ^a24 , multiple Rf ^a24 may be different. In the case where there is multiple Rf ^a25 , multiple Rf ^a25 may be different. R ²⁰ , R ²¹ , R ²² and R ²³ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ^In the case where a plurality of R ²⁰ are present, the plurality of R ²⁰ may be different from each other. In the case where a plurality of R ²¹ are present, , a plurality of R ²¹ may be different from each other, in a case where a plurality of R ^22, R ²² may be respectively a plurality of different, in a case where a plurality of R ^23, R ²³ may be respectively different plurality, R ²⁴ is a C an alkyl group having 1 to 20, in the case where there is a plurality of R ^24, R ²⁴ may be different from each plurality, M ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the presence of multiple The case of M ^1, M ¹ may be different from each other plurality, M ² is a hydrogen atom or a halogen atom, M ³ is -O -, - C (= O ) -O -, - OC (= O) -, - NR -, -NRC (= O)-or -C (= O) NR- (where R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluorine-containing alkyl group having 1 to 4 carbon atoms). case ^3, a plurality of M ³ may be different from each other, M ⁴ is a hydrolyzable group, in the presence of a plurality of M ^4, a plurality of M ⁴ may be different from each other, f11, f12, f13, f14 and f15 are each independently Is an integer from 0 to 600, the total value of f11, f12, f13, f14, and f15 is 13 or more, f16 is an integer from 1 to 20, f17 is an integer from 0 to 2, g1 is an integer from 1 to 3, and Rf ^a21 -, M ^2- , f11-(C (R ²⁰ ) (R ²¹ ))-, f12-(C (Rf ^a22 ) (Rf ^a23 ))-, f13-(Si (R ²² ) (R ²³ )}-, ^F14- (Si (Rf ^a24 ) (Rf ^a25 ))-, f15-M ^3- , and f16- [CH ₂ C (M ¹ ) {(CH ₂ ) _f17 -Si (M ⁴ ) _g1 (R ²⁴ ) _3-g1 }]-, as long as Rf _a21 -and M ² -are terminal, they are arranged in order of forming at least a part of the perfluoropolyether structure and -O- is not connected to -O- or -F, then The bonds can be arranged in any order. That is, formula (a2-1) does not necessarily have the following meanings: f11-{C (R ²⁰ ) (R ²¹ )}-continuous, f12-{C (Rf ^a22 ) (Rf ^a23 )}-continuous, f13- {Si (R ²² ) (R ²³ )}-continuous, f14 ^pcs- {Si (Rf ^a24 ) (Rf ^a25 )}-continuous, f15 pcs-M ^{3 -continuous} , f16 ^pcs- [CH ₂ C (M ¹ ) {(CH ₂ ) _f17 -Si (M ⁴ ) _g1 (R ²⁴ ) _3-g1 }]-continuous and arranged in order; can be -C (R ²⁰ ) (R ²¹ ) -Si (Rf ^a24 ) (Rf ^a25 ) -CH ₂ C (M ¹ ) {(CH ₂ ) _f17 -Si (M ⁴ ) _g1 (R ²⁴ ) _3-g1 ) -C (Rf ^a22 ) (Rf ^a23 ) -M ³ -Si (R ²² ) ( R ²³ ) -C (Rf ^a22 ) (Rf ^a23 ) ^-are arranged in an arbitrary order.

Rf ^{a21 is} preferably an alkyl group having 1 to 10 carbon atoms substituted with one or more fluorine atoms, more preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and even more preferably a perfluoroalkyl group having 1 to 5 carbon atoms.

Rf ^a22 , Rf ^a23 , Rf ^a24, and Rf ^a25 are each preferably a fluorine atom or an alkyl group having 1 to 2 carbon atoms in which one or more hydrogen atoms are replaced with fluorine atoms, and more preferably all fluorine atoms.

R ²⁰ , R ²¹ , R ^22, and R ²³ are each preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably all of them are hydrogen atoms.

R ^{24 is} preferably an alkyl group having 1 to 5 carbon atoms.

M ^{1 is} preferably each independently a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably all of them are hydrogen atoms.

M ^{2 is} preferably a hydrogen atom.

M ^{3 is} preferably -C (= O) -O-, -O-, -OC (= O)-, and more preferably all -O-.

M ^{4 is} preferably an alkoxy group or a halogen atom, more preferably a methoxy group, an ethoxy group, or a chlorine atom.

It is preferable that f11, f13, and f14 are each 1/2 or less of f12, more preferably 1/4 or less, still more preferably f13 or f14 is 0, and even more preferably, f13 and f14 are 0.

f15 is preferably 1/5 or more of the total value of f11, f12, f13, and f14 and less than the total value of f11, f12, f13, and f14.

f12 is preferably 20 to 600, more preferably 20 to 200, and even more preferably 50 to 200 (more preferably 30 to 150, particularly preferably 50 to 150, and most preferably 80 to 140). f15 is preferably 4 to 600, more preferably 4 to 200, and even more preferably 10 to 200 (more preferably 30 to 60). The total value of f11, f12, f13, f14, and f15 is preferably 20 to 600, more preferably 20 to 200, and even more preferably 50 to 200.

f16 is preferably 1 to 18. More preferably, it is 1 to 15. Further preferably, it is 1 to 10.

f17 is preferably 0 to 1.

g1 is preferably 2 to 3, and more preferably 3.

About f11-{C (R ²⁰ ) (R ²¹ )}-, f12--(C (Rf ^a22 ) (Rf ^a23 ))-, f13--(Si (R ²² ) (R ²³ ))-, f14 The order ^of- {Si (Rf ^a24 ) (Rf ^a25 )}-and f15 -M ³ -is arbitrary in the formula as long as it is arranged in the order that at least a part of the perfluoropolyether structure is formed, but it is preferably the most The fixed unit side (the side bonded to the silicon atom) with the repeating unit enclosed in parentheses with f12 (ie,-{C (Rf ^a22 ) (Rf ^a23 )}-) is compared to the freest side The repeating unit enclosed in parentheses with f11 (ie,-{C (R ²⁰ ) (R ²¹ )}-) is located on the free end side, more preferably the most fixed end side is attached with f12 and f14 And the repeating units enclosed in parentheses (ie,-{C (Rf ^a22 ) (Rf ^a23 )}- ^and- {Si (Rf ^a24 ) (Rf ^a25 )}-) are f11 and f13 and the repeating unit enclosed in parentheses (that is,-{C (R ²⁰ ) (R ²¹ )}-and-{Si (R ²² ) (R ²³ )}-) are located on the free end side.

In the formula (a2-1), it is preferable that Rf ^a21 is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ^a22 , Rf ^a23 , Rf ^a24 , and Rf ^{a25 are} all fluorine atoms, and M ^{3 is} all -O- M ^{4 is} all methoxy, ethoxy, or chlorine atoms (especially methoxy or ethoxy), M ¹ and M ² are hydrogen atoms, f11 is 0, and f12 is 30 to 150 (more preferably 80 to 140), f15 is 30 to 60, f13 and f14 are 0, f17 is 0 to 1 (especially 0), g1 is 3, and f16 is 1 to 10.

In addition, regarding the compound a used as the compound (A) in the examples described later, if represented by the formula (a2-1), Rf ^a21 is C ₃ H _7- , and Rf ^a22 and Rf ^a23 are both fluorine atoms. F11 = f13 = f14 = 0, f12 is 131, f15 is 44, f16 is 1 to 6, f17 is 0, M ¹ and M ² are hydrogen atoms, M ³ is -O-, and M ⁴ is methoxy, g1 is 3.

The organosilicon compound (A) is also preferably a compound represented by the following formula (a2-2).

[Chemical 7]

In the formula ^{(a2-2), Rf a26, Rf} a27, Rf a28 and Rf ^a29 are each independently a hydrogen atom or more carbon atoms is substituted with a fluorine atom or an alkyl group having 1 to 20 fluorine atoms, in the presence of Rf ^a26 case where a plurality of the plurality may be different from each Rf ^a26, in case where there is a plurality of Rf ^a27, the plurality may be different from each Rf ^a27, in a case where there are a plurality of Rf ^a28, respectively, a plurality of Rf ^a28 Different, when multiple Rf ^a29 are present, multiple Rf ^a29 may be different, R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ²⁵ is a case where a plurality of R ²⁵ may be different from each other, in the presence of a plurality of R ^26, a plurality of R ²⁶ may be different from each other, in a case where a plurality of R ^27, R ²⁷ may be each a plurality of different , in the presence of a plurality of R ^28, R ²⁸ may be respectively different plurality, R ²⁹ and R ³⁰ are each independently alkyl having 1 to 20, in the case where there is a plurality of R ^29, a plurality of R ²⁹ may be different from each other, in a case where a plurality of R ^30, R ³⁰ may be each a plurality of different, M ⁷ is -O -, - C (= O ) -O -, - OC (= O) -, - NR -, -NRC (= O)-or -C (= O) NR- Said R is a hydrogen atom, alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4, in the case where there is a plurality of M ^7, M ⁷ may be different from each other plurality, M ^5, M ⁹ They are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and in the presence of a plurality of M ^5, M ⁵ may be respectively a plurality of different, in the presence of a plurality of M ^9, M ⁹ may be respectively a plurality of Differently, M ⁶ and M ¹⁰ are each independently a hydrogen atom or a halogen atom, and M ⁸ and M ¹¹ are each independently a hydrolyzable group. In the case where there is a plurality of M ⁸ , a plurality of M ⁸ may be different from each other. a case where a plurality of M ^11, M ¹¹ may be different from each other plurality, f21, f22, f23, f24 and f25 are each independently an integer of 0 to 600, the sum f21, f22, f23, f24 and f25 value of 13 or more , F26 and f28 are each independently an integer of 1 to 20, f27 and f29 are each independently an integer of 0 to 2, g2 and g3 are each independently an integer of 1 to 3, and M ^10- , M ^6- , f21 a ^{- {C (R 25) (} R 26)} -, f22 a ^{- {C (Rf a26) (} Rf a27)} -, f23 a ^{- {Si (R 27) (} R 28)} -, f24 a - (Si (Rf ^a28 ) (Rf ^a29 ))-, f25 pieces -M ^7- , f26 pieces-[CH ₂ C (M ⁵ ) {(CH ₂ ) _f27 -Si (M ⁸ ) _g2 (R ²⁹ ) _3-g2 }] and f28-[CH ₂ C (M ⁹ ) {(CH ₂ ) _f29 -Si (M ¹¹ ) _g3 (R ³⁰ ) _3-g3 }], as long as M ^10- , M ⁶ -is a terminal, and is arranged in an order in which at least a part of the perfluoropolyether structure is formed, and -O- and -O- are discontinuous, and the bonds can be arranged in an arbitrary order. The arrangement of the bonds in an arbitrary order is the same as that described in the formula (a2-1), and is not limited to that the repeating units are arranged continuously and in the order as described in the formula (a2-2). Meaning.

In the formula (A2-2), is preferably Rf ^a26, Rf ^a27, Rf ^a28 and Rf ^a29 are all fluorine atoms, M ⁷ are all -O-, M ⁸ and M ¹¹ are all methoxy, ethoxy Group or chlorine atom (especially methoxy or ethoxy group), M ⁵ , M ⁶ , M ⁹ and M ¹⁰ are all hydrogen atoms, f21 is 0 and f22 is 30 to 150 (more preferably 80 to 140), f25 is 30 to 60, f23 and f24 are 0, f27 and f29 are 0 to 1 (preferably 0), g2 and g3 are 3, and f26 and f28 are 1 to 10.

As a compound (A), the compound of the following formula (a3) is mentioned more specifically.

[Chemical 8]

In the formula (a3), R ³⁰ is a perfluoroalkyl group having 2 to 6 carbon atoms, R ³¹ and R ³² are each independently a perfluoroalkylene group having 2 to 6 carbon atoms, and R ³³ is 2 to 6 carbon atoms. A trivalent saturated hydrocarbon group of 6, and R ³⁴ is an alkyl group having 1 to 3 carbon atoms. The carbon numbers of R ³⁰ , R ³¹ , R ³² , and R ³³ are each preferably independently 2 to 4, and more preferably 2 to 3. h1 is 5 to 70, h2 is 1 to 5, and h3 is 1 to 10. h1 is preferably 10 to 60, more preferably 20 to 50, h2 is preferably 1 to 4, more preferably 1 to 3, h3 is preferably 1 to 8, and more preferably 1 to 6.

Examples of the compound (A) include compounds represented by the following formula (a4).

[Chemical 9]

In the formula (a4), R ⁴⁰ is a perfluoroalkyl group having 2 to 5 carbon atoms, R ⁴¹ is a perfluoroalkylene group having 2 to 5 carbon atoms, and R ⁴² is an alkylene group having 2 to 5 carbon atoms. Part of the hydrogen atom is substituted with fluorine fluoroalkylene, R ⁴³ and R ⁴⁴ are each independently an alkylene having 2 to 5 carbon atoms, and R ⁴⁵ is methyl or ethyl. k1, k2, and k3 are each independently an integer of 1 to 5.

The number average molecular weight of the organosilicon compound (A) is preferably 2,000 or more, more preferably 4,000 or more, even more preferably 6,000 or more, particularly preferably 7,000 or more, more preferably 40,000 or less, more preferably 20,000 or less, and further preferably Below 15,000.

2. Organosilicon compound (B) The organosilicon compound (B) is represented by the following formula (b1).

[Chemical 10]

In the formula (b1), Rf ^b10 is an alkyl or fluorine atom having 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced with fluorine atoms, and R ^b11 , R ^b12 , R ^b13 , and R ^b14 are each independently hydrogen atom or a C 1-4 alkyl group, in the case where there are plural R ^b11 and R ^b11 may be different from each other plurality, in the case where there are plural R ^b12 and R ^b12 may be different from each plurality, the presence of multiple a case where R ^b13 and R ^b13 may be respectively a plurality of different, in a case where there are plural R ^b14 and R ^b14 may be respectively a plurality of ^{different, Rf b11, Rf b12, Rf} b13, Rf b14 each independently represent a more When a hydrogen atom is replaced by a fluorine atom having 1 to 20 carbon atoms or a fluorine atom, when a plurality of Rf ^b11 is present, the plurality of Rf ^b11 may be different from each other, and when a plurality of Rf ^b12 is present, the Rf ^b12 respectively different one, in a case where there are a plurality of Rf ^b13, respectively different plurality Rf ^b13, in the case where there are a plurality of Rf ^b14, respectively different plurality Rf ^b14, R ^b15 is a C 1 ~ 20 alkyl group, in the presence of multiple R ^b15 , multiple R ^b15 may be different, A ¹ is -O-, -C (= O) -O-, -OC (= O)-, -NR - -NRC (= O) -, or -C (= O) NR-, wherein R is a hydrogen atom, alkyl having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4, in the presence of a plurality of A ¹ In the case of a plurality of A ¹ may be different, A ² is a hydrolyzable group, in the case of the existence of multiple A ² , the multiple A ² may be different, b11, b12, b13, b14, b15 are independently An integer from 0 to 100, c is an integer from 1 to 3, Rf ^b10- , -Si (A ² ) c (R ^b15 ) _3-c , b11-{C (R ^b11 ) (R ^b12 )}-, b12- (C (Rf ^b11 ) (Rf ^b12 ))-, b13- (Si (R ^b13 ) (R ^b14 ))-, b14- (Si (Rf ^b13 ) (Rf ^b14 ))-, b15 -A ^1- , as long as Rf ^b10- , -Si (A ² ) c (R ^b15 ) _3-c is terminal, no perfluoropolyether structure is formed, and -O- is not connected to -O- or -F, then The bonds can be arranged in any order.

Rf ^{b10 is} preferably each independently a fluorine atom or a perfluoroalkyl group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms).

R ^b11 , R ^b12 , R ^b13 and R ^{b14 are} preferably a hydrogen atom.

R ^{b15 is} preferably an alkyl group having 1 to 5 carbon atoms.

A ^{1 is} preferably -O-, -C (= O) -O-, or -OC (= O)-.

A ^{2 is} preferably an alkoxy group or a halogen atom having 1 to 4 carbon atoms, and more preferably a methoxy group, an ethoxy group, or a chlorine atom.

b11 is preferably 1 to 30, more preferably 1 to 25, still more preferably 1 to 10, particularly preferably 1 to 5, and most preferably 1 to 2.

b12 is preferably from 0 to 15, more preferably from 0 to 10.

b13 is preferably 0 to 5, more preferably 0 to 2.

b14 is preferably 0 to 4, more preferably 0 to 2.

b15 is preferably 0 to 4, more preferably 0 to 2.

c is preferably 2 to 3, and more preferably 3.

The total value of b11, b12, b13, b14, and b15 is preferably 3 or more, more preferably 5 or more, more preferably 80 or less, more preferably 50 or less, and even more preferably 20 or less.

In particular, Rf ^b10 is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, R ^b11 and R ^b12 are both hydrogen atoms, A ² is a methoxy group or an ethoxy group, and b11 is 1 to 5; b12 is 0 to 5, b13, b14, and b15 are all 0, and c is 3.

Furthermore, in the examples described later, if FAS13E used as the compound (B) is represented by the formula (b1), it is defined that R ^b11 and R ^b12 are both hydrogen atoms, b11 is 2, b13, b14 and b15 are all 0, c is 3, A ² is ethoxy, and Rf ^b10- {C (Rf ^b11 ) (Rf ^b12 )} _b12 -is a terminal and becomes C ₆ F _13- .

Specific examples of the compound represented by the formula (b1) include CF ₃ -Si- (OCH ₃ ) ₃ and C _j F _{2j + 1} -Si- (OC ₂ H ₅ ) ₃ (j is 1 to 12). An integer), particularly preferably C ₄ F ₉ -Si- (OC ₂ H ₅ ) ₃ , C ₆ F ₁₃ -Si- (OC ₂ H ₅ ) ₃ , C ₇ F ₁₅ -Si- (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ -Si- (OC ₂ H ₅ ) ₃ . Examples include CF ₃ CH ₂ O (CH ₂ ) _k SiCl ₃ , CF ₃ CH ₂ O (CH ₂ ) _k Si (OCH ₃ ) ₃ , CF ₃ CH ₂ O (CH ₂ ) _k Si (OC ₂ H ₅ ) ₃ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) _k SiCl ₃ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) _k Si (OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) _k Si (OC ₂ H ₅ ) ₃ , CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) _k SiCl ₃ , CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) _k Si (OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) _k Si (OC ₂ H ₅ ) ₃ , CF ₃ COO (CH ₂ ) _k SiCl ₃ , CF ₃ COO (CH ₂ ) _k Si (OCH ₃ ) ₃ , CF ₃ COO (CH ₂ ) _k Si (OC ₂ H ₅ ) ₃ (k are both 5-20, It is preferably 8 to 15). In addition, CF ₃ (CF ₂ ) _m- (CH ₂ ) _n SiCl ₃ , CF ₃ (CF ₂ ) _m- (CH ₂ ) _n Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) _m- (CH ₂ ) _n Si (OC ₂ H ₅ ) ₃ (m is 1 to 10, preferably 3 to 7, and n is 1 to 5, preferably 2 to 4). CF ₃ (CF ₂ ) _p- (CH ₂ ) _q -Si- (CH ₂ CH = CH ₂ ) ₃ (p is 2-10, preferably 2-8, q is 1-5, It is preferably 2 to 4). Furthermore, CF ₃ (CF ₂ ) _p- (CH ₂ ) _q SiCH ₃ Cl ₂ , CF ₃ (CF ₂ ) _p- (CH ₂ ) _q SiCH ₃ (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) _p -(CH ₂ ) _q SiCH ₃ (OC ₂ H ₅ ) ₂ (p is 2 to 10, preferably 3 to 7, and q is 1 to 5, preferably 2 to 4).

Among the compounds represented by the formula (b1), preferred are compounds represented by the following formula (b2).

[Chemical 11]

In the formula (b2), R ⁶⁰ is a perfluoroalkyl group having 3 to 8 carbons, R ⁶¹ is an alkylene group having 1 to 5 carbons, and R ⁶² is an alkyl group having 1 to 3 carbons.

3. Organic silicon compound (C) The organic silicon compound (C) is represented by the following formula (c1).

[Chemical 12]

In a case where the formula ^{(c1), R x1, R} x2, R x3 and R ^x4 each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and in the presence of a plurality of R ^x1, R ^x1 may be a plurality of are different, in a case where a plurality of R ^x2, R ^x2 plurality may be different from each other, in a case where a plurality of R ^x3, R ^x3 may be different from each other a plurality of, in a case where a plurality of R ^x4, multiple Each R ^x4 may be different, and Rf ^x1 , Rf ^x2 , Rf ^x3, and Rf ^x4 are each independently one or more hydrogen atoms substituted with fluorine atoms of 1 to 20 carbon or fluorine atoms. In the presence of multiple Rf in the case of ^{x1, x1} an Rf plurality of respectively different, in a case where there are a plurality of Rf ^x2, a plurality of different Rf ^x2 respectively, in a case where there are a plurality of Rf ^x3, a plurality of different Rf ^x3 respectively, in When there are multiple Rf ^x4 , multiple Rf ^x4 may be different, and R ^x5 is an alkyl group having 1 to 20 carbons. When there are multiple R ^x5 , multiple R ^x5 may be different, and X is hydrolysis In the case of multiple Xs, multiple Xs may be different, and Y is -O-, -NH-, or -S-. In the case of multiple Ys, multiple Ys may be different. Z is Vinyl, α-methylvinyl, styryl, methacryl, acryl, amine, isocyanate, isocyanurate, epoxy, sulfonylurea, or mercapto, p1 is 1 An integer of -20, p2, p3, and p4 are each independently an integer of 0-10, p5 is an integer of 0-10, and p6 is an integer of 1-3. About Z-, -Si (X) _p6 (R ^x5 ) _3-p6 , p1-(C (R ^x1 ) (R ^x2 ))-, p2-(C (Rf ^x1 ) (Rf ^x2 ))-, p3-(Si (R ^x3 ) (R ^x4 )) -, P4-{Si (Rf ^x3 ) (Rf ^x4 )}-and p5 -Y-, as long as Z- and -Si (X) _p6 (R ^x5 ) _3-p6 are terminal and -O- and -O -If not connected, the bonds can be arranged in any order.

R ^x1 , R ^x2 , R ^x3 and R ^{x4 are} preferably hydrogen atoms.

Rf ^x1 , Rf ^x2 , Rf ^x3, and Rf ^x4 are each independently an alkyl or fluorine atom having 1 to 10 carbon atoms in which one or more hydrogen atoms are replaced with fluorine atoms.

R ^{x5 is} preferably an alkyl group having 1 to 5 carbon atoms.

X is preferably an alkoxy group, a halogeno group, a cyano group, or an isocyanate group, more preferably an alkoxy group, and even more preferably a methoxy group or an ethoxy group.

Y is preferably -NH-.

Z is preferably a methacrylfluorenyl group, an acrylfluorenyl group, a mercapto group, or an amine group, more preferably a mercapto group or an amine group, and even more preferably an amine group.

p1 is preferably from 1 to 15, more preferably from 2 to 10.

It is preferable that p2, p3, and p4 are independently 0 to 5, and it is more preferable that all of them are 0 to 2.

p5 is preferably 1 to 5, and more preferably 1 to 3.

p6 is preferably 2 to 3, and more preferably 3.

As the organosilicon compound (C), preferably used in the formula (c1), R ^x1 and R ^x2 are both hydrogen atoms, Y is -NH-, and X is an alkoxy group (especially a methoxy group or an ethyl group) (Oxy), a compound in which Z is an amine group or a mercapto group, p is 1 to 10, p2, p3, and p4 are all 0, p5 is 1 to 5 (preferably 1 to 3), and p6 is 3.

Furthermore, if N-2- (aminoethyl) -3-aminopropyltrimethoxysilane is used as the compound (C) in the examples described later as the formula (c1), then Z Is an amine group, R ^x1 and R ^x2 are both hydrogen atoms, p1 is 5, p2, p3, and p4 are 0, Y is -NH-, p5 is 1, p6 is 3, and X is methoxy.

The organosilicon compound (C) is preferably represented by the following formula (c2).

[Chemical 13]

In the formula (c2), X ¹ is a hydrolyzable group. When a plurality of X ¹ are present, the plurality of X ¹ may be different, and Y ¹ is -NH-, -CH _2- , or -O-, Z ¹ is a case where the amine or mercapto group, R ^x51 is an alkyl group having 1 to 20 carbon atoms, in the presence of a plurality of R ^x51, respectively, a plurality of different R ^x51, P61 is an integer of 1 to 3, q is 2 to 5 Is an integer of 0 to 5.

X ^{1 is} preferably an alkoxy group, a halogen group, a cyano group, or an isocyanate group, and more preferably an alkoxy group.

Y ^{1 is} preferably -NH-.

Z ^{1 is} preferably an amine group.

R ^{x51 is} preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

p61 is preferably an integer of 2 to 3, and more preferably 3.

q is preferably an integer of 2 to 3, and r is preferably an integer of 2 to 4.

The content of the organosilicon compound (A) in 100% by mass of the composition of the present invention is, for example, 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.5% by mass or less, and more preferably 0.3% by mass. the following.

The content of the organosilicon compound (B) in 100% by mass of the composition of the present invention is, for example, 0.01% by mass or more, preferably 0.03% by mass or more, and more preferably 0.3% by mass or less, more preferably 0.2% by mass. the following.

The content of the organosilicon compound (C) in 100% by mass of the composition of the present invention is, for example, 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 1% by mass or less, and more preferably 0.6% by mass. Hereinafter, it is more preferably 0.4% by mass or less.

The total amount of the organic silicon compound (A), the organic silicon compound (B), and the organic silicon compound (C) is 100% by mass of the composition of the present invention, preferably 0.15% by mass or more, and more preferably 0.3% by mass or more. In addition, it is preferably 1.5% by mass or less, more preferably 0.7% by mass or less, and still more preferably 0.6% by mass or less.

The quality of the organosilicon compound (B) relative to the organosilicon compound (A) is more preferably 0.2 or more, more preferably 0.4 or more, more preferably 3 or less, and even more preferably 1.5 or less.

The total mass of the organosilicon compound (A) and the organosilicon compound (B) relative to the mass of the organosilicon compound (C) is preferably 0.1 or more, more preferably 0.2 or more, more preferably 1.5 or less, and more preferably 1 or less. It is more preferably 0.75 or less.

The composition of the present invention generally contains the solvent (D) in addition to the organosilicon compound (A), the organosilicon compound (B), and the organosilicon compound (C). As the solvent (D), a fluorine-based solvent is preferably used. For example, a fluorinated ether-based solvent, a fluorinated amine-based solvent, a fluorinated hydrocarbon-based solvent, and the like can be used, and a boiling point of 100 ° C or higher is particularly preferred. The fluorinated ether-based solvent is preferably a hydrofluoroether such as a fluoroalkyl group (especially a perfluoroalkyl group having 2 to 6 carbon atoms) -alkyl (especially methyl or ethyl) ether, and examples thereof include ethyl Nonafluorobutyl ether or ethyl nonafluoroisobutyl ether. Examples of ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether include Novec (registered trademark) 7200 (manufactured by 3M Corporation, molecular weight of about 264). The fluorinated amine-based solvent is preferably an amine in which at least one hydrogen atom of ammonia is substituted with a fluoroalkyl group, and more preferably a tertiary amine in which all hydrogen atoms of ammonia are substituted with a fluoroalkyl group (especially a perfluoroalkyl group). Specific examples include tris (heptafluoropropyl) amine, and Fluorinert (registered trademark) FC-3283 (manufactured by 3M Corporation, molecular weight of about 521) corresponds to it. Examples of the fluorinated hydrocarbon-based solvent include fluorinated aliphatic hydrocarbon-based solvents such as 1,1,1,3,3-heptafluorobutane, and fluorinated aromatic hydrocarbons such as 1,3-bis (trifluoromethylbenzene). Department of solvents. Examples of 1,1,1,3,3-heptafluorobutane include Solve 55 (manufactured by Solex Corporation) and the like.

As the fluorine-based solvent, in addition to the above, hydrochlorofluorocarbons such as asahiklin (registered trademark) AK225 (manufactured by Asahi Glass Co., Ltd.), asahiklin (registered trademark) AC2000 ( Asahi Glass Co., Ltd.) and other HFCs.

As the solvent (D), at least an amine fluoride-based solvent is preferably used. The solvent (D) preferably contains two or more fluorine-based solvents, and preferably contains a fluorinated amine-based solvent and a fluorinated hydrocarbon-based solvent (especially a fluorinated aliphatic hydrocarbon-based solvent).

The composition of the present invention may contain a silanol condensation catalyst, an antioxidant, a rust inhibitor, an ultraviolet absorber, a light stabilizer, a mold inhibitor, an antibacterial agent, and a biological adhesion preventive agent within a range not hindering the effects of the present invention. , Deodorant, pigment, flame retardant, antistatic agent and other additives.

The composition of the present invention can be applied to a substrate and dried to form a film on the substrate. Examples of the method for applying the composition of the present invention include a dip coating method, a roll coating method, a bar coating method, a spin coating method, a spray coating method, a die coating method, and a gravure coating method.

The conditions after coating the composition of the present invention on a substrate are not particularly limited, and they may be left to stand at room temperature and in the air, for example, for 1 hour or more. In the present invention, the normal temperature refers to 5 ° C to 60 ° C, and it is preferable that a film can be formed by standing still in a temperature range of 15 ° C to 40 ° C. After that, it may be further heated (simmered) at a temperature of 50 ° C to 300 ° C, preferably 100 ° C to 200 ° C, for about 10 minutes to 60 minutes.

The thickness of the film formed from the composition of the present invention is, for example, 0.1 nm to 100 nm. The film has water repellency, and a water contact angle (initial contact angle) measured by a liquid droplet method (analysis method: θ / 2 method) at a liquid volume of 3 μL is, for example, 105 ° or more, and more preferably 110 ° or more, and For example, it is 120 ° or less. In addition, after performing the chemical resistance test in the examples described later, the water contact angle (contact angle after the chemical resistance test) was measured by the liquid droplet method (analysis method: θ / 2 method) at a liquid amount of 3 μL. For example, it is 82.0 ° or more, preferably 90 ° or more, and more preferably 100 ° or more (especially 106 ° or more). The upper limit is, for example, 115 ° or less, and may be 110 ° or less.

The material of the substrate to which the composition of the present invention is applied is not particularly limited, and may be any one of an organic material and an inorganic material. The shape of the substrate may be any of a flat surface and a curved surface. These shapes are combined. Examples of the organic material include acrylic resin, polycarbonate resin, polyester resin, styrene resin, acrylic-styrene copolymer resin, cellulose resin, polyolefin resin, and vinyl resin (polyethylene, polyvinyl chloride, Polystyrene, vinyl benzyl chloride (Vinylbenzyl chloride) resin, polyvinyl alcohol, etc .; thermoplastic resins; phenol resins, urea resins, melamine resins, epoxy resins, unsaturated polyesters, silicone resins, amino methyl esters Thermosetting resins such as ester resins. Examples of the inorganic materials include metals such as iron, silicon, copper, zinc, and aluminum, or alloys containing these metals, ceramics, and glass. Among them, an organic material is particularly preferred, and a surface-treated resin substrate having a film including the composition of the present invention on the surface of the resin substrate is also included in the present invention. Among the resin substrates, at least one of an acrylic resin, a benzyl chloride-based resin, an epoxy resin, a silicone resin, and a urethane resin is preferred, and an acrylic resin is particularly preferred.

The substrate to which the composition of the present invention is applied may be subjected to an easy adhesion treatment. Examples of the easy adhesion treatment include hydrophilization treatments such as corona treatment, plasma treatment, and ultraviolet treatment. By performing easy subsequent treatment such as plasma treatment, OH groups can be formed on the surface of the substrate (especially when the substrate is an epoxy resin) or COOH groups (especially when the substrate is an acrylic resin) When such functional groups are formed on the surface of the substrate, the adhesion between the film formed from the composition of the present invention and the substrate can be further improved.

In a preferred form, it can be used on a protective layer (hereinafter, sometimes referred to as a hard coat layer) for protecting articles from damage in applications requiring abrasion resistance such as a display of an electronic device. The coating of the composition of the present invention to form a film can constitute a laminate of a hard coat layer and a coating layer formed of the composition of the present invention.

The hard coat layer is a layer having a surface hardness, and the hardness is, for example, 2H or more in terms of pencil hardness. The hard coating layer may have a single-layer structure or a multilayer structure. The hard coat layer includes a hard coat resin. Examples of the hard coat resin include acrylic resin, epoxy resin, urethane resin, vinyl benzyl chloride resin, vinyl resin, and silicone. UV-curable, electron-beam-curable, or thermo-curable resins such as resins or these mixed resins. In particular, the hard coat layer preferably contains an acrylic resin in order to exhibit high hardness. Since the adhesiveness with the film layer formed from the composition of this invention is seen to be favorable, it is preferable to contain an epoxy resin.

The hard coat layer may further include an ultraviolet absorber, and may also include a metal oxide such as silicon dioxide or aluminum oxide, or an inorganic filler such as polyorganosiloxane. By including the said inorganic filler, the adhesiveness with the film layer formed from the composition of this invention can be improved. The thickness of the hard coat layer is, for example, 1 μm to 100 μm.

The laminated body of the hard coat layer and the film layer formed of the composition of the present invention preferably further includes a resin layer, and the film layer, the hard coat layer, and the resin layer of the composition of the present invention are sequentially formed from the surface of the laminated body. Order. The resin component of the resin layer is not particularly limited, and from the viewpoint of easily improving the adhesion with the hard coat layer, polyacrylate resins, polyamide resins, polyimide resins, and polyamines are preferred. Fluorene resin, polyurethane resin, polyester resin, polycarbonate resin, polyether fluorene resin, ethyl cellulose resin, cycloolefin resin, polyvinyl alcohol resin, etc. Among them, polyimide resins and polyimide resins are more preferred. The thickness of the resin layer is, for example, 10 μm to 500 μm. In addition, it may be a laminate of a hard coat layer and an anti-reflection layer, and the hard coat layer may also function as an anti-reflection layer.

An undercoat layer may be provided between the resin layer and the hard coat layer. Examples of the primer include primers such as an ultraviolet curing type, a thermosetting type, and a two-liquid curing type epoxy-based compound. Preferably, the compound contained in the undercoat layer is chemically bonded to a resin component contained in the resin layer or a silicon material contained as required. In addition, as the primer, polyamic acid can be used, which can improve the adhesion between the resin layer and the hard coat layer. Furthermore, examples of the primer include a silane coupling agent, and chemical bonding with a silicon material contained in the resin base material as necessary may be performed by a condensation reaction. The thickness of the undercoat layer is, for example, 0.1 μm to 20 μm. [Example]

Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples, and it is needless to say that the present invention can be implemented by appropriately applying changes within a range suitable for the gist described below, which are included in the technical scope of the present invention.

Example 1 A compound (hereinafter, compound a) represented by the following formula (1) as an organosilicon compound (A), and FAS13E (C ₆ F ₁₃ -C ₂ H _4- ) as an organosilicon compound (B) Si (OC ₂ H ₅ ) ₃ , manufactured by Tokyo Chemical Industry Co., Ltd.), FC-3283 (C ₉ F ₂₁ N, Fluorinert, manufactured by 3M) as a solvent (D), mixed at room temperature After being stirred for a predetermined time, KBM-603 (Shin-Etsu Chemical Industry Co., Ltd.) (organic silicon compound (C)) was added dropwise so as to be 0.125% by mass based on the total amount of compound (A), compound (B), and solvent (D). N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, manufactured by Co., Ltd.). Then, it stirred at room temperature for predetermined time, and obtained the film-forming solution. In this solution, the ratio of the compound (A) was 0.085% by mass, and the ratio of the compound (B) was 0.05% by mass. The obtained solution was applied using a spray coater manufactured by Apeiros Co., Ltd. to a solution having an activated surface treated with an atmospheric piezoelectric slurry device (manufactured by Fuji Machinery Manufacturing Co., Ltd.). Acrylic hard-coated substrate. Thereafter, it was calcined at 120 ° C for 20 minutes to obtain a transparent film on the acrylic hard coat layer. In addition, the conditions for spray coating were scanning speed: 600 mm / sec, pitch: 5 mm, liquid volume: 6 cc / min, atomizing air: 350 kPa, and gap: 70 mm. [Chemical 14]

The compound a represented by the formula (1) was synthesized by the method described in Synthesis Example 1 and Synthesis Example 2 of Japanese Patent Application Laid-Open No. 2014-15609. R is 43, and s is an integer from 1 to 6, The number average molecular weight is about 8000.

Example 2 The same as Example 1, except that the ratio of the compound (C) to be added was set to 0.25% by mass based on the total amount of the compound (A), the compound (B), and the solvent (D). A transparent coating is obtained on a hard coat substrate.

Example 3 The same as Example 1, except that the proportion of the compound (C) to be added was 0.5% by mass based on the total amount of the compound (A), compound (B), and solvent (D). A transparent film was obtained on the hard coating substrate.

Example 4 Except that the proportion of the compound (C) to be added was 1% by mass based on the total amount of the compound (A), the compound (B), and the solvent (D), it was the same as in Example 1 for acrylic acid. A transparent film was obtained on the hard coating substrate.

Comparative Example 1 The compound a as the organosilicon compound (A), FAS13E (C ₆ F ₁₃ -C ₂ H ₄ -Si (OC ₂ H ₅ ) ₃ ) as the organosilicon compound (B), and Tokyo Chemical Industry Co., Ltd. Co., Ltd.), and FC-3283 (C ₉ F ₂₁ N, Fluorinert, 3M) as a solvent (D) were mixed and stirred at room temperature for a predetermined time to obtain a solution for forming a film. In this solution, the ratio of the compound (A) was 0.085% by mass, and the ratio of the compound (B) was 0.05% by mass. The obtained solution was applied using a spray coater manufactured by Apeiros Co., Ltd. to a hard coat layer whose surface was activated using an atmospheric piezoelectric slurry device (manufactured by Fuji Machinery Manufacturing Co., Ltd.) on. Thereafter, it was sintered at 120 ° C for 20 minutes to obtain a transparent film on the acrylic hard coat substrate.

The coatings obtained in the examples and comparative examples were subjected to the following measurements.

(1) Measurement of water contact angle (initial contact angle) 3 μL of water droplets were dripped onto the obtained film, and a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., DM700) was used and the droplet method (analysis method: θ / 2) Measure the contact angle of water.

(2) Measurement of water contact angle after chemical resistance test The obtained film was subjected to a load of 1000 g under a state where the rubber was in contact with the film using a scratch device having a rubber made by Minoan. About 2.5 ml of ethanol was added dropwise thereto, and the rubber was allowed to travel back and forth on the membrane at a speed of 40 r / min (40 round trips per minute) to perform a chemical resistance test. The contact angle of water was measured after the rubber had traveled back and forth on the membrane 3000 times.

The results are shown in Table 1.

[Table 1]

The water contact angles after the chemical resistance test of Examples 1 to 4 using the organosilicon compound (A), organosilicon compound (B), and organosilicon compound (C) of the present invention were all 82 ° or more, which was good. In contrast, the water contact angle after the chemical resistance test of Comparative Example 1 not containing the organosilicon compound (C) decreased. [Industrial availability]

The composition of the present invention can be used in display devices such as touch panel displays, optical elements, semiconductor elements, construction materials, nano-imprint technology, solar cells, window glass of automobiles or buildings, metal products such as cooking utensils, and ceramic products such as tableware. Films are preferably formed on automobile parts made of plastic, etc., and are industrially useful. In addition, it can also be preferably used in kitchens, bathrooms, washstands, mirrors, articles of various components around the toilet, goggles, glasses, and the like.

no

no

Claims (6)

A composition comprising: an organosilicon compound (A) represented by formula (a1), an organosilicon compound (B) represented by formula (b1), and an organosilicon compound (C) represented by formula (c1); In the formula (a1), Rf ^a1 is a divalent perfluoropolyether structure having oxygen atoms at both ends, and R ¹¹ , R ¹² and R ¹³ are each independently an alkyl group having 1 to 20 carbon atoms. in the case of R ^11, a plurality of R ¹¹ may be different from each other, in a case where a plurality of R ^12, R ¹² may be each a plurality of different, in a case where a plurality of R ^13, R ¹³ s may be different from each other, E ¹ , E ² , E ³ , E ^4, and E ⁵ are each independently a hydrogen atom or a fluorine atom. In the case where there is a plurality of E ¹ , the plurality of E ¹ may be different from each other, and in the case where there is a plurality of E ² , , the plurality of E ² may be different from each other, in a case where there are a plurality of E ^3, E ³ may be different from each other plurality, in the case where there is a plurality of E ^4, E ⁴ may be different from each other plurality, G and ^{G. 1 2} are each independently a divalent to 10-valent organosiloxy group having a siloxane bond, and J ¹ , J ^2, and J ³ are each independently a hydrolyzable group _or- (CH ₂ ) _e6 -Si (OR ¹⁴ ) _3, e6 is 1 ~ 5, R ¹⁴ is methyl or ethyl, in the presence of a plurality of J ^1, J ¹ respectively a plurality of different, in a case where there are a plurality of J ^2, J ² a plurality of It may be different from each other, in a case where there are a plurality of J ^3, multiple J ³ may be different from each other, L ¹ and L ² each independently may contain an oxygen atom, a nitrogen atom, a carbon number of fluorine atoms, a divalent linking group having 1 to 12, in the case where there is a plurality of L ^1, a plurality of L ¹ may be different from each other, in a case where a plurality of L ^2, a plurality of L ² may be different from each other, D11 of 1 ~ 9, d12 of 0 ~ 9, a10 and a14 each independently 0 ~ 10, a11 and a15, respectively, Independently 0 or 1, a12 and a16 are independently 0-9, a13 is 0 or 1, a21, a22, and a23 are independently 0-2, and e1, e2, and e3 are independently 1-3; In the formula (b1), Rf ^b10 is an alkyl or fluorine atom having 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced with fluorine atoms, and R ^b11 , R ^b12 , R ^b13, and R ^b14 are each independently hydrogen. atom or a C 1-4 alkyl group, in the case where there are plural R ^b11 and R ^b11 may be different from each other plurality, in the case where there are plural R ^b12 and R ^b12 may be different from each plurality, the presence of multiple a case where R ^b13 and R ^b13 may be respectively a plurality of different, in a case where there are plural R ^b14 and R ^b14 may be respectively a plurality of ^{different, Rf b11, Rf b12, Rf} b13 and Rf ^b14 each independently represent a more When a hydrogen atom is replaced by a fluorine atom having 1 to 20 carbon atoms or a fluorine atom, when a plurality of Rf ^b11 is present, the plurality of Rf ^b11 may be different from each other, and when a plurality of Rf ^b12 is present, the Rf ^b12 respectively different one, in a case where there are a plurality of Rf ^b13, respectively different plurality Rf ^b13, in the case where there are a plurality of Rf ^b14, respectively different plurality Rf ^b14, R ^b15 is a C 1 ~ 20 alkyl group, in the presence of multiple R ^b15 , multiple R ^b15 may be different, A ¹ is -O-, -C (= O) -O-, -OC (= O)-, -NR -, -NRC (= O)-or -C (= O) NR-, wherein R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluorine-containing alkyl group having 1 to 4 carbon atoms, in the presence of multiple A ¹ in the case where a plurality of a ¹ may be different from each other, a ² is a hydrolyzable group, in the presence of a plurality of a ^2, a ² may be respectively a plurality of different, b11, b12, b13, b14 and b15 are each independently An integer from 0 to 100, c is an integer from 1 to 3, Rf ^b10- , -Si (A ² ) _c (R ^b15 ) _3-c , b11-{C (R ^b11 ) (R ^b12 )}-, b12- (C (Rf ^b11 ) (Rf ^b12 ))-, b13- (Si (R ^b13 ) (R ^b14 ))-, b14- (Si (Rf ^b13 ) (Rf ^b14 ))-, b15 -A ^1- , as long as Rf ^b10- , -Si (A ² ) _c (R ^b15 ) _3-c are terminal, no perfluoropolyether structure is formed, and -O- is not connected to -O- or -F, then Arrange bonds in any order; In the formula (c1), R ^x1 , R ^x2 , R ^x3 , and R ^x4 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When multiple R ^x1 are present, multiple R ^x1 may be are different, in a case where a plurality of R ^x2, R ^x2 plurality may be different from each other, in a case where a plurality of R ^x3, R ^x3 may be different from each other a plurality of, in a case where a plurality of R ^x4, multiple Each R ^x4 may be different, and Rf ^x1 , Rf ^x2 , Rf ^x3 , and Rf ^x4 are each independently one or more carbon atoms of 1 to 20 carbon atoms or fluorine atoms in which a hydrogen atom is replaced by a fluorine atom, and there are multiple Rf in the case of ^{x1, x1} an Rf plurality of respectively different, in a case where there are a plurality of Rf ^x2, a plurality of different Rf ^x2 respectively, in a case where there are a plurality of Rf ^x3, a plurality of different Rf ^x3 respectively, in When there are multiple Rf ^x4 , multiple Rf ^x4 may be different, and R ^x5 is an alkyl group having 1 to 20 carbons. When there are multiple R ^x5 , multiple R ^x5 may be different, and X is hydrolysis In the case of multiple Xs, multiple Xs may be different, and Y is -O-, -NH-, or -S-. In the case of multiple Ys, multiple Ys may be different. Z Vinyl, α-methylvinyl, styryl, methacryl, acryl, amine, isocyanate, isocyanurate, epoxy, sulfonylurea, or mercapto, p1 is 1 An integer of -20, p2, p3, and p4 are each independently an integer of 0-10, p5 is an integer of 0-10, and p6 is an integer of 1-3. About Z-, -Si (X) _p6 (R ^x5 ) _3-p6 , p1-(C (R ^x1 ) (R ^x2 ))-, p2-(C (Rf ^x1 ) (Rf ^x2 ))-, p3-(Si (R ^x3 ) (R ^x4 )) -, P4-{Si (Rf ^x3 ) (Rf ^x4 )}-, p5 -Y-, as long as Z- and -Si (X) _p6 (R ^x5 ) _3-p6 are terminal and -O- and -O -If not connected, the bonds can be arranged in any order. The composition according to item 1 of the scope of patent application, wherein the organosilicon compound (C) is 0.1% by mass or more and 1% by mass or less in the total mass of the composition. The composition according to claim 1 or claim 2, wherein the organosilicon compound (C) is represented by the following formula (c2); In the formula (c2), X ¹ is a methoxy group or an ethoxy group. When a plurality of X ¹ are present, the plurality of X ¹ may be different, and Y ¹ is -NH-, -CH ₂ -or- case O-, Z ¹ is a group or a mercapto group, R ^x51 alkyl group having 1 to 20 carbon atoms, in the presence of a plurality of R ^x51, respectively, a plurality of different R ^x51, P61 is an integer of 1 to 3, q Is an integer of 2 to 5, and r is an integer of 0 to 5. A surface-treated resin substrate having a film including the composition according to any one of claims 1 to 3 on the surface of the resin substrate. The surface-treated resin substrate according to item 4 of the scope of patent application, wherein the resin substrate is an acrylic resin substrate. A method for manufacturing a surface-treated resin substrate is to coat the surface of a resin substrate with the composition according to any one of claims 1 to 3 of the scope of patent application, and harden the composition at normal temperature.