KR20210148082A - Laminate and its manufacturing method - Google Patents

Abstract

A water-repellent layer (r) and a resin base layer (s) are laminated through a layer (c), wherein the layer (c) is an organosilicon compound (C1) represented by the following formula (c11) and/ or two or more of the organosilicon compounds (C1) are formed from a mixed composition (cc) of an organosilicon compound (C2) in which at least one of the ^{following X 1 to X 4 is condensed and bonded, wherein the water repellent layer (r) comprises:} A laminate, which is a layer formed from a mixed composition (ca) of an organosilicon compound (A) having a hypovalent perfluoropolyether structure. In the formula (c11), Z ¹ and Z ² are each independently a reactive functional group other than a hydrolyzable group and a hydroxyl group.

Description

Laminate and its manufacturing method

The present invention relates to a laminate and a method for manufacturing the same.

Since the surface free energy of a film formed from a composition in which a compound having a perfluoropolyether structure is mixed is very small, display devices such as touch panel displays, optical elements, semiconductor elements, building materials, automobiles and buildings In various fields, such as window glass, it is used as an antifouling|stain-resistant coating, a water-oil-repellent coating, etc.

When applying a composition in which a compound having a perfluoropolyether structure is mixed to a substrate, for the purpose of improving adhesion, etc., after forming other layers such as a primer layer on the substrate in advance, the composition is applied to An antifouling coating or a water and oil repellent coating may be formed.

For example, in Patent Document 1, a hard coat film in which a hard coat layer (X), a primer layer (Y) and a surface layer (Z) are sequentially laminated on at least one surface of a substrate, the surface layer (Z) A hard coating film having a water contact angle of 110° or more is disclosed. In order to form the surface layer (Z), it is preferable to use a fluorine-based compound having a polyperfluoropolyether chain, and to form the primer layer (Y), 3-acryloxypropyltrimethoxysilane, etc. It is described that silane compounds are preferred.

Japanese Patent Laid-Open No. 2015-120253

A laminate in which a water-repellent layer formed from a composition in which a compound having a perfluoropolyether structure is mixed on a substrate such as a resin is laminated may be exposed to chemicals such as alcohol, depending on the use. In this case, it is required to maintain good performance (water repellency, etc.) even after exposure to chemicals (hereinafter referred to as chemical resistance).

However, the said patent document 1 did not examine about chemical-resistance. Therefore, an object of the present invention is to provide a laminate in which a water-repellent layer formed from a composition in which a compound having a perfluoropolyether structure is mixed on a resin substrate is laminated, the laminate having excellent chemical resistance.

The present invention is as follows.

[1] A laminate in which a water-repellent layer (r) and a resin substrate layer (s) are laminated through a layer (c),

In the layer (c), the organosilicon compound (C1) represented by the following formula (c11) and/or two or more organosilicon compounds (C1) are condensed and bonded to at least one of the ^{following X 1 to X 4 .} formed from a mixed composition (cc) of compound (C2),

The said water-repellent layer (r) is a layer formed from the mixed composition (ca) of the organosilicon compound (A) represented by following formula (a1), The laminated body characterized by the above-mentioned.

[Formula 1]

In the above formula (c11),

Z ¹ , Z ² are each independently a reactive functional group other than a hydrolyzable group and a hydroxy group,

R ^x1, R ^x2, R ^x3, R ^x4 each independently, in the case of a hydrogen atom or 1 to 4 carbon atoms is an alkyl group, R ^x1 is a plurality exist a plurality of R ^x1 is different respectively, R ^x2 is a plurality when there are a plurality of different, each R ^x2, R ^x3 in this case, there is a plurality of the plurality of R ^x3 are respectively different, are a plurality of different R ^x4 each R ^x4 if a plurality is present,

Rf ^{x1, x2} Rf, Rf ^{x3, x4} Rf are, each independently, an alkyl group or a fluorine atom of 1 to 20 carbon atoms substituted with at least one hydrogen atom with a fluorine atom, Rf is a plurality of Rf ^{x1 x1} if there is a plurality each of which is different, Rf if ^x2 plurality existence is different, each a plurality of Rf ^x2, Rf ^x3 this is different each of a plurality of Rf ^x3, are a plurality of Rf ^x4 when Rf ^x4 the plurality, if any plurality presence may be different from each other,

Y is -NH-, -N(CH ₃ )- or -O-, and when there are a plurality of Y, a plurality of Y may be different,

X ¹ , X ² , X ³ , X ⁴ are each independently —OR ^c (R ^c is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an amino C _1-3 alkyldi C _1-3 alkoxysilyl group) and, if X ¹ is a plurality exist a plurality of X ¹ are different, respectively, when X ² is a plurality presence are a plurality of X ² different respectively, if X ³ is multiple presence each of the plurality of X ³ It is different, are a plurality of different X ⁴ X ⁴ each if a plurality is present,

p11 is an integer from 0 to 20, p12, p13, and p14 are each independently an integer from 0 to 10, p15 is an integer from 0 to 5, p16 is an integer from 1 to 10, p17 is 0 or 1,

The organosilicon compound (C1) has ^{p11 -{C(R x1} )(R ^x2 )}-, p12 as long as -O- is not connected with -O-, ^{and ends are Z 1} - and Z ^{2 -.} -{C(Rf ^x1 )(Rf ^x2 )}-, p13 -{Si(R ^x3 )(R ^x4 )}-, p14 -{Si(Rf ^x3 )(Rf ^x4 )}-, p15 - Y-, p16 pieces of -{Si(X ¹ )(X ² )-O}-, and p17 pieces of -{Si(X ³ )(X ⁴ )}- are combined side by side in an arbitrary order to form a structure.

[Formula 2]

In the above formula (a1),

Rf ^a1 is a divalent perfluoropolyether structure in which both ends are oxygen atoms,

R ^11, R ^12, and R ¹³ are each independently an alkyl group having a carbon number of 1~20, R ¹¹ are different are each a plurality of R ^11, R is a plurality of R ^12, if a plurality, if any plurality presence and ¹² are different, respectively, are a plurality of R ¹³ to R ¹³ are different, respectively, if a plurality is present,

E ^1, E ^2, E ^3, E ^4, and E ⁵ are each independently a hydrogen atom or a fluorine atom, when E ¹ a plurality exist a plurality of E ¹ are different respectively, E to ^second multiple presence If different each is a plurality of E ^2, E ³ if there is a plurality a plurality of different E ^3, respectively, in the case where E ⁴ is present a plurality a plurality of different E ^4, respectively,

G ¹ and G ² are each independently a 2- to 10-valent organosiloxane group having a siloxane bond,

J ¹ , J ² , and J ³ are each independently a hydrolysable 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 J when the ^first plurality present are different, each with a plurality of J ^1, when J ² is a plurality presence are a plurality of J ² different, respectively, when J ³ a plurality presence are a plurality of J ³ different respectively,

L ¹ and L ² are, each independently, an oxygen atom, a nitrogen atom, or carbon atoms and a divalent linking group of 1 to 12 which may contain a fluorine atom, if L ¹ is a multiple presence or different, each a plurality of L ¹ and, a plurality of L ² are different each case a plurality of L ² is present,

d11 is 1 to 9,

d12 is 0-9,

a10 and a14 are each independently 0-10,

a11 and a15 are each independently 0 or 1,

a12 and a16 are each independently 0-9,

a13 is 0 or 1,

a21, a22, and a23 are each independently 0-2,

e1, e2, and e3 are each independently 1 to 3.

[2] The organosilicon compound (C2) is

A compound having two or more structures (c21-1) represented by the following formula (c21-1), wherein the structures (c21-1) are chained or cyclically bonded by the following *3 or *4, the following *3 Or the bond by *4 is due to the condensation of ^{X 1} or X ^{2 of two or more of the organosilicon compounds (C1),}

In *1 and *2 of the following formula (c21-1), at least one type of unit bound by p11, p12, p13, p14, p15, (p16)-1, and p17 of the following formula (c21-2), respectively A group bonded in any order and having a terminal Z- is bonded, and in each of the plurality of structures (c21-1), the groups bonding to *1 and *2 may be different,

The laminate according to [1], wherein *3, which is a terminal when a plurality of the structures (c21-1) are chained together, is a hydrogen atom, and *4 is a hydroxyl group.

[Formula 3]

[Formula 4]

In the above formula (c21-2),

Z is a reactive functional group other than a hydrolyzable group and a hydroxy group,

R ^x1 , R ^x2 , R ^x3 , R ^x4 , Rf ^x1 , Rf ^x2 , Rf ^x3 , Rf ^x4 , Y, X ¹ , X ² , X ³ , X ⁴ , p11 to p17 are those in the formula (c11) sign and agreement.

[3] The laminate according to [1] or [2], wherein the composition (ca) is mixed with an organosilicon compound (B) represented by the following formula (b1).

[Formula 5]

In the above formula (b1),

Rf ^b10 is an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom or a fluorine atom,

R ^b11, R ^b12, R ^b13 and R ^b14 each independently is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, a plurality of R if R ^{b11 b11} there are multiple different respectively, R ^b12 is a plurality when there are a plurality of R ^b12 are each different, R ^b13 is if there is a plurality a plurality of R ^b13 are different, respectively, when R ^b14 there is a plurality or different, each a plurality of R ^b14,

Rf ^{b11, b12} Rf, Rf ^b13 and ^b14 Rf are, each independently, an alkyl group or a fluorine atom of 1 to 20 carbon atoms substituted with at least one hydrogen atom with a fluorine atom, Rf is a plurality of Rf ^{b11 b11} if there is a plurality each of which is different, Rf if ^b12 multiple presence are a plurality of Rf ^b12 different, respectively, Rf ^b13 if this plurality there is a plurality of Rf ^b13 are different, respectively, Rf if ^b14 plurality exist a plurality of Rf ^b14 may be different from each other,

R ^b15 is different is each a plurality of R ^b15, and if the carbon number is 1 to 20. The alkyl group, R ^b15 is a plurality is present,

A ¹ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, wherein R is a fluorinated alkyl group of the alkyl group having 1 to 4 carbon atoms or a hydrogen atom, a group having 1 to 4 carbon atoms, a ¹ is the case that there is a plurality a plurality of a ¹ or different, respectively,

A ² is a hydrolyzable group, and when ^two or more A 2 are present, a plurality of A ² may be different from each other,

b11, b12, b13, b14 and b15 are each independently an integer of 0 to 100;

c is an integer of 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 -, Rf ^b10 -, -Si(A ^{2 )} ) _c (R ^b15 ) _3-c is terminated, does not form a perfluoropolyether structure, and bonds side by side in any order, unless -O- is connected with -O- to -F.

[4] The laminate according to any one of [1] to [3], wherein the composition (cc) is mixed with at least the organosilicon compound (C1).

[5] The laminate according to any one of [1] to [4], wherein the resin base layer (s) is a hard coat layer.

[6] A method for producing the laminate according to any one of [1] to [5], comprising:

A step of forming a layer (c) by applying the composition (cc) to the resin base layer (s);

A step of applying the composition (ca) to the layer (c) and curing it at room temperature to form the water-repellent layer (r);

A method of manufacturing a laminate comprising a.

[7] Production of the laminate according to [6], wherein in the step of forming the layer (c), plasma treatment is performed on the resin base layer (s), and the composition (cc) is applied to the plasma-treated surface Way.

ADVANTAGE OF THE INVENTION According to this invention, the laminated body excellent in chemical-resistance can be provided.

A laminate in which a water-repellent layer (r) formed from a mixed composition (ca) of a compound having a perfluoropolyether structure is laminated on a resin base layer (s), in order to realize a laminate excellent in chemical resistance, the present invention As a result of repeated studies by the inventors, the resin base layer (s) and the water-repellent layer (r) are formed from a mixed composition (cc) of a specific organosilicon compound (C1) and/or organosilicon compound (C2) It was discovered that a laminate excellent in chemical resistance could be realized when laminated through the layer (c) used. Hereinafter, it demonstrates in order of a layer (c), a water-repellent layer (r), and a resin base material layer (s). The mixed composition (ca) is a composition in which the organosilicon compound (A) is mixed, is obtained by mixing the organosilicon compound (A), and when components other than the organosilicon compound (A) are mixed is obtained by mixing the organosilicon compound (A) with other components. The mixed composition (cc) is a composition in which the organosilicon compound (C1) and/or the organosilicon compound (C2) are mixed, and is obtained by mixing the organosilicon compound (C1) and/or the organosilicon compound (C2); When components other than an organosilicon compound (C1) and (C2) are mixed, it is obtained by mixing an organosilicon compound (C1) and/or an organosilicon compound (C2), and another component. The mixed composition (ca) and the mixed composition (cc) include those that have undergone a reaction after mixing, for example, during storage.

1. Layer (c)

The layer (c) is an organosilicon compound (C1) represented by the following formula (c11) and/or an organosilicon compound (C2) in which two or more organosilicon compounds (C1) are condensed and bonded by the ^{following X 1} or X ^{2 )} It is a layer formed from the mixed composition (cc) of Hereinafter, the organosilicon compound (C1) and (C2) may be collectively called an organosilicon compound (C).

1-1. organosilicon compound (C1)

The organosilicon compound (C1) is represented by the following formula (c11).

[Formula 6]

In the above formula (c11),

Z ¹ and Z ² are each independently a reactive functional group other than a hydrolysable group and a hydroxyl group. Examples of the reactive functional group include a vinyl group, α-methylvinyl group, styryl group, methacryloyl group, acryloyl group, amino group, epoxy group, ureido group, and mercapto group. As Z ¹ , Z ² , an amino group, a mercapto group, or a methacryloyl group is preferable, and an amino group is particularly preferable.

R ^x1, R ^x2, R ^x3, R ^x4 each independently, in the case of a hydrogen atom or 1 to 4 carbon atoms is an alkyl group, R ^x1 is a plurality exist a plurality of R ^x1 is different respectively, R ^x2 is a plurality when there are a plurality of different, each R ^x2, R ^x3 if there is a plurality of different respective plurality of R ^x3 is, if R ^x4 are each different plurality there is a plurality of R ^{x4. R x1, R x2, R x3} , R x4 is preferred that the alkyl group is a hydrogen atom or 1 to 2 carbon atoms, more preferably a hydrogen atom.

Rf ^{x1, x2} Rf, Rf ^{x3, x4} Rf are, each independently, an alkyl group or a fluorine atom of 1 to 20 carbon atoms substituted with at least one hydrogen atom with a fluorine atom, Rf is a plurality of Rf ^{x1 x1} if there is a plurality each of which is different, Rf if ^x2 plurality existence is different, each a plurality of Rf ^x2, Rf ^x3 this is different each of a plurality of Rf ^x3, are a plurality of Rf ^x4 when Rf ^x4 the plurality, if any plurality presence may be different from each other. Rf ^x1 , Rf ^x2 , Rf ^x3 , and Rf ^x4 are preferably an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom or a fluorine atom.

Y is -NH-, -N(CH ₃ )-, or -O-, and when two or more Y exist, a plurality of Ys may be respectively different. Y is preferably -NH-.

X ¹ , X ² , X ³ , X ⁴ are each independently —OR ^c (R ^c is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an amino C _1-3 alkyldi C _1-3 alkoxysilyl group) and, if X ¹ is a plurality exist a plurality of X ¹ are different, respectively, when X ² is a plurality presence are a plurality of X ² different respectively, if X ³ is multiple presence each of the plurality of X ³ It is different, and if X ⁴ is present is different plurality each with a plurality of X ^4. X ¹ , X ² , X ³ , and X ⁴ are preferably ^{-OR c in which R c} is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, ^{and more preferably R c} is a hydrogen atom.

p11 is an integer from 0 to 20, p12, p13, and p14 are each independently an integer from 0 to 10, p15 is an integer from 0 to 5, p16 is an integer from 1 to 10, and p17 is 0 or 1. As for p11, 1-15 are preferable, More preferably, it is 3-13, More preferably, it is 5-10. As for p12, p13, and p14, respectively independently, 0-5 are preferable, More preferably, all are 0-2. As for p15, 1-5 are preferable, More preferably, it is 1-3. As for p16, 1-5 are preferable, More preferably, it is 1-3. As for p17, 1 is preferable.

The organosilicon compound (C1) has ^{p11 -{C(R x1} )(R ^x2 )}-, p12 as long as -O- is not connected with -O-, ^{and ends are Z 1} - and Z ^{2 -.} -{C(Rf ^x1 )(Rf ^x2 )}-, p13 -{Si(R ^x3 )(R ^x4 )}-, p14 -{Si(Rf ^x3 )(Rf ^x4 )}-, p15 - Y-, p16 pieces of -{Si(X ¹ )(X ² )-O}-, and p17 pieces of -{Si(X ³ )(X ⁴ )}- are combined side by side in an arbitrary order to form a structure. p11 pieces of -{C(R ^x1 )(R ^x2 )}- do not need to be continuously bonded to -{C(R ^x1 )(R ^x2 )}-, even if they are bonded through other units in the middle and it may be p11 in total. The same applies to units bound by p12 to p17.

In the organosilicon compound (C1), Z ¹ and Z ² are amino groups, R ^x1 and R ^x2 are hydrogen atoms, p11 is 3 to 13 (preferably 5 to 10), and R ^x3 and R ^x4 are both hydrogen. atom, Rf ^{x1 to Rf x4} are all alkyl groups having 1 to 10 carbon atoms or fluorine atoms in which one or more hydrogen atoms are substituted with fluorine atoms, p12 to p14 are all 0 to 5, Y is -NH-, p15 is 0 and to 5 (preferably 0~3), X ¹ and ~X ⁴ are both -OH, and p16 is 1 to 5 (preferably 1 to 3), the p17 is 1, compounds are preferred.

In KBP90 used in Examples to be described later, in the formula (c11), ^{both Z 1} and Z ² are amino groups, R ^x1 and R ^x2 are both hydrogen atoms, p11 is 6, p12 to p15 are all 0, , X ¹ , X ² , X ³ and X ⁴ are all —OH, and p16 and p17 are both 1.

In KBP64 used in Examples to be described later, in the formula (c11), Z ¹ and Z ² are both amino groups, R ^x1 and R ^x2 are both hydrogen atoms, p11 is 10, and p12 to p14 are all 0; , p15 is 2, Y is NH, X ¹ , X ² , X ³ and X ⁴ are all —OH, and p16 and p17 are both 1.

The organosilicon compound (C1) is preferably represented by the following formula (c12).

[Formula 7]

In the formula (c12), Z ¹ , Z ² , X ¹ , X ² , X ³ , X ⁴ , and Y are synonymous with those in the formula (c11), and p21 to p24 are each independently an integer of 1 to 6 and p25 and p26 are each independently 0 or 1.

In the formula (c12), Z ¹ and Z ² are preferably an amino group, a mercapto group, or a methacryloyl group, and particularly preferably an amino group. ^{X 1, X 2, X 3} , X 4 is, R ^c is preferably an -OR ^c is a hydrogen atom, an alkyl group or 1 to 2 carbon atoms, and more preferably R ^c is a hydrogen atom. Y is preferably -NH-. 2 or more are preferable, and, as for p21-p24, 5 or less are preferable and 4 or less are more preferable. It is preferable that both p25 and p26 are 0, or that both p25 and p26 are 1, and it is more preferable that both p25 and p26 are 0.

1-2. organosilicon compound (C2)

The organosilicon compound (C2) is a compound in which two or more organosilicon compounds (C1) are ^{condensed and bonded by at least any one of X 1 to X 4} , and two or more organosilicon compounds (C1) are chained together. Or you may combine them in a phantom. The organosilicon compound (C2) is formed from, for example, the organosilicon compound (C1) in the composition (cc).

Examples of the organosilicon compound (C2) include ^{those condensed by the aforementioned X 1} or X ² , and specifically have two or more structures (c21-1) represented by the following formula (c21-1) , wherein the structures (c21-1) are chained or cyclically bonded by the following *3 or *4, and the bonding by the following *3 or *4 is X ^{1 of two or more organosilicon compounds (C1)} Or by the condensation of ^{X 2 ,}

In *1 and *2 of the following formula (c21-1), at least one type of unit bound by p11, p12, p13, p14, p15, (p16)-1, and p7 of the following formula (c21-2), respectively and compounds to which a group bonded in any order and a Z-terminal end is bonded. For each of the plurality of structures (c21-1), the groups bonded to *1 and *2 may be different, and *3, which is a terminal when the plurality of structures (c21-1) are chain-bonded, is a hydrogen atom; *4 is a hydroxyl group.

[Formula 8]

[Formula 9]

In the above formula (c21-2),

Z is a reactive functional group other than a hydrolyzable group and a hydroxy group,

R ^x1 , R ^x2 , R ^x3 , R ^x4 , Rf ^x1 , Rf ^x2 , Rf ^x3 , Rf ^x4 , Y, X ¹ , X ² , X ³ , X ⁴ , p11 to p17 are those in the formula (c11) It is synonymous with a code|symbol, and it is the same also about these preferable aspects.

As for the number of bonds of the organosilicon compound (C1) at the time of forming an organosilicon compound (C2), 2-10 are preferable, More preferably, it is 3-8. Moreover, although two or more organosilicon compounds (C1) constituting the organosilicon compound (C2) may be different from each other, all of them are preferably the same.

When the organosilicon compound (C1) is a compound represented by the formula (c12), as the organosilicon compound (C2), for example, a structure represented by the following formula (c22) is a chain or cyclically bonded compounds are mentioned. When the structures represented by the following formula (c22) are chained together, *3 is a hydrogen atom, and *4 is a hydroxyl group.

[Formula 10]

All the signs in the formula (c22) have the same meaning as the signs in the formula (c11).

It is preferable that the organosilicon compound (C2) is a compound in which the structure represented by the said Formula (c22) couple|bonded 2-10 (preferably 3-8).

At least one of the organosilicon compound (C1) and the organosilicon compound (C2) is mixed with the composition (cc), and it is preferable that at least the organosilicon compound (C1) is mixed.

The thickness of the said layer (c) is about 1-1000 nm, for example.

2. Water-repellent layer (r)

The water-repellent layer (r) is a layer formed from the mixed composition (ca) of the organosilicon compound (A) represented by the following formula (a1), that is, has a structure derived from the organosilicon compound (A). As described later, the organosilicon compound (A) has a hydrolyzable group, and since -SiOH groups of the organosilicon compound (A) generated by hydrolysis undergo dehydration condensation, the water repellent layer (r) is usually an organosilicon compound It has the condensed structure derived from (A).

[Formula 11]

In the above formula (a1),

Rf ^a1 is a divalent perfluoropolyether structure in which both ends are oxygen atoms,

R ^11, R ^12, and R ¹³ are each independently (and that is, R ¹¹ and R ¹² and R ¹³ may be the same, are different from each other) an alkyl group of 1 to 20 carbon atoms, when R ¹¹ is present with a plurality being different with a plurality of R ^11, respectively, when R ¹² is plural, and the plurality of R ¹² are present or different, respectively, are different, each a plurality of R ¹³ to R ^13, if a plurality is present,

E ^1, E ^2, E ^3, E ^4, and E ⁵ are each independently a hydrogen atom or a fluorine atom, when E ¹ a plurality exist a plurality of E ¹ are different respectively, E to ^second multiple presence If different each is a plurality of E ^2, E ³ if there is a plurality a plurality of different E ^3, respectively, in the case where E ⁴ is present a plurality a plurality of different E ^4, respectively,

G ¹ and G ² are each independently a 2- to 10-valent organosiloxane group having a siloxane bond,

J ¹ , J ² , and J ³ are each independently a hydrolysable 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 J when the ^first plurality present are different, each with a plurality of J ^1, when J ² is a plurality presence are a plurality of J ² different, respectively, when J ³ a plurality presence are a plurality of J ³ different respectively,

L ¹ and L ² are, each independently, an oxygen atom, a nitrogen atom, or carbon atoms and a divalent linking group of 1 to 12 which may contain a fluorine atom, if L ¹ is a multiple presence or different, each a plurality of L ¹ and, a plurality of L ² are different each case a plurality of L ² is present,

d11 is 1 to 9,

d12 is 0-9,

a10 and a14 are each independently 0-10,

a11 and a15 are each independently 0 or 1,

a12 and a16 are each independently 0-9,

a13 is 0 or 1,

a21, a22, and a23 are each independently 0-2,

e1, e2, and e3 are each independently 1 to 3.

The organosilicon compound (A) has a perfluoropolyether structure represented by ^{Rf a1} as represented by the formula (a1), and a hydrolyzable group represented by ^{J 2} _{or -(CH 2} ) _e6 - Si(OR ¹⁴ ) ₃ (provided that R ¹⁴ has at least one methyl group or an ethyl group). The perfluoropolyether structure is a structure in which all hydrogen atoms of the polyoxyalkylene group are substituted with fluorine atoms, can also be referred to as a perfluorooxyalkylene group, and can impart water repellency to the resulting film. Further, a, a compound which by binding via the organosilicon compound (A) with each other, or a polymerization reaction with other monomer (in particular the polycondensation reaction), to be in a matrix of the coating film obtained by the J ^2.

Rf ^a1 is preferably -O-(CF ₂ CF ₂ O) _e4 - or -O-(CF ₂ CF ₂ CF ₂ O) _e5 -. e4 and e5 are both 15-80.

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

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

G ¹ and G ² are each independently preferably a di to pentavalent organosiloxane group having a siloxane bond.

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

0-5 are preferable (more preferably 0-3) as for a10, 0 are preferable, as for a11, 0-7 are preferable (more preferably 0-5), and, as for a14, 1-6 are preferable. and (more preferably 1 to 3), a15 is preferably 0, a16 is preferably 0 to 6, a21 to a23 are all preferably 0 or 1 (more preferably all 0), and d11 is 1 -5 are preferable (more preferably, 1-3), d12 has preferable 0-3 (more preferably, 0 or 1), and all of e1-e3 have preferable 3. Moreover, as for a13, 1 is preferable.

As the compound (A), in the formula (a1), Rf ^a1 is -O-(CF ₂ CF ₂ CF ₂ O) _e5 -, e5 is 35 to 50, and L ¹ and L ² both have 1 to 3 carbon atoms. a perfluoroalkylene group, E ¹ , E ² , and E ³ are all a hydrogen atom, E ⁴ , and E ⁵ are a hydrogen atom or a fluorine atom, and J ¹ , J ² , and J ³ are all a methoxy group or an ethoxy group (particularly a methoxy group), wherein a10 is 1 to 3, a11 is 0, a12 is 0 to 5, a13 is 1, a14 is 2 to 5, a15 is 0, and a16 is 0 to 6 and a21 to a23 are each independently 0 or 1 (more preferably a21 to a23 are all 0), d11 is 1, d12 is 0 or 1, and it is preferable to use a compound in which all of e1 to e3 are 3 do.

In addition, when the compound a used as the compound (A) in the Examples below is represented by the above formula (a1), Rf ^a1 is -O-(CF ₂ CF ₂ CF ₂ O) ₄₃ -, and L ₁ and L ₂ are all are -(CF ₂ )-, E ¹ , E ² , and E ³ are all hydrogen atoms, E ⁵ is a fluorine atom, J ¹ , J ² are all methoxy groups, a10 is 2, a11 is 0, a12 is 0 to 5, a13 is 1, a14 is 3, a15 is 0, a16 is 0, a21 and a22 are all 0, d11 is 1, d12 is 0, e1, e2 are all 3.

In the compound (A), in the formula (a1), Rf ^a1 is -O-(CF ₂ CF ₂ CF ₂ O) _e5 -, e5 is 25 to 40, and L ¹ is a fluorine atom and an oxygen atom. is a divalent linking group of 3 to 6, 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 a21 to a23 are all 0), d11 is 1, d12 is 0, and e2 is 3 It is also preferable to use a compound. .

Moreover, it is also preferable that an organosilicon compound (A) is a compound represented by a following formula (a2-1).

[Formula 12]

In the above formula (a2-1),

Rf ^a21 is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted with a fluorine atom;

Rf ^{a22, a23} Rf, Rf ^{a24, a25,} and Rf are, each independently, an alkyl group or a fluorine atom of 1 to 20 carbon atoms substituted with at least one hydrogen atom with a fluorine atom, Rf if there is a plurality ^{a22 a22} plurality of Rf when the different is, Rf ^a23 multiple presence each is a different respective plurality of Rf ^a23, Rf if ^a24 plurality existence is different, each a plurality of Rf ^a24, a plurality of Rf if Rf ^a25 multiple presence ^a25 may be different,

R ^20, R ^21, R ^22, and R ²³ are, each independently, in the case of a hydrogen atom or an alkyl group having a carbon number of 1~4, R ²⁰ is a plurality exist a plurality of R ²⁰ are different, respectively, R ²¹ is a plurality when there are a plurality of different, each R ^21, R ²² if a plurality is present, and the plurality of R ²² each different, are a plurality of R ²³ are different, each R ²³ if a plurality is present,

R ²⁴ is an alkyl group of 1 to 20 carbon atoms, are a plurality of R ²⁴ to R ²⁴ are different, respectively, if a plurality is present,

M ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, is different, each with a plurality of M ¹ M ¹ if a plurality is present,

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-(R is hydrogen atom, an alkyl group or a fluorinated alkyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms), or different, and a plurality of M ³ is when M ³ to the multiple presence, respectively,

M ⁴ is a hydrolyzable group, are a plurality of M ⁴ to M ⁴ different each case a plurality is present,

f11, f12, f13, f14, and f15 are each independently an integer of 0 to 600, and the sum 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 of 1 to 3,

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 }]- is ^{arranged in an order in which Rf a21} -, M ² - end, at least partially form a perfluoropolyether structure, and -O- is -O Join side by side in any order, unless linked with - to -F. That is, in formula (a2-1), f11 pieces of -{C(R ²⁰ )(R ²¹ )}- are always continuous, f12 pieces of -{C(Rf ^a22 )(Rf ^a23 )}- are continuous, and f13 consecutive -{Si(R ²² )(R ²³ )}-, f14 consecutive -{Si(Rf ^a24 )(Rf ^a25 )}-, f15 consecutive -M ³ -, f16 consecutive - [CH ₂ C(M ¹ ){(CH ₂ ) _f17 -Si(M ⁴ ) _g1 (R ²⁴ ) _3-g1 }]- does not mean that they are consecutive, in this order, -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 )-, etc., may each be 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, still more preferably a perfluoroalkyl group having 1 to 5 carbon atoms. It is a roalkyl group.

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

R ²⁰ , R ²¹ , R ²² , and R ²³ are each independently 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, more preferably all hydrogen atoms.

M ² is preferably a hydrogen atom.

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

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

Preferably f11, f13, and f14 each are 1/2 or less of f12, more preferably 1/4 or less, still more preferably f13 or f14 is 0, particularly preferably f13 and f14 are 0 am.

f15 is preferably 1/5 or more of the sum of f11, f12, f13, and f14, and less than or equal to the sum of f11, f12, f13, and f14.

As for f12, 20-600 are preferable, More preferably, it is 20-200, More preferably, it is 50-200 (more preferably 30-150, especially 50-150, Most preferably 80-140). As for f15, 4-600 are preferable, More preferably, it is 4-200, More preferably, it is 10-200 (more preferably 30-60). 20-600 are preferable, as for the total value of f11, f12, f13, f14, f15, 20-200 are more preferable, 50-200 are still more preferable.

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

f17 is preferably 0 to 1.

2-3 are preferable and, as for g1, 3 is more preferable.

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 pieces of -M ³ - is arbitrary in the formula as long as they are arranged in the order in which at least a part forms a perfluoropolyether structure, but preferably is the repeating unit enclosed in parentheses with f12 on the most fixed end side (the side bonding to the silicon atom) (i.e., -{C(Rf ^a22 )(Rf ^a23 )}-), f11 on the free end side It is located on the free end rather than the repeating unit enclosed in parentheses (that is, -{C(R ²⁰ )(R ²¹ )}-), and more preferably the repeating unit enclosed in parentheses by attaching f12 and f14 on the most fixed end side (i.e., -{C(Rf ^a22 )(Rf ^a23 )}-, and -{Si(Rf ^a24 )(Rf ^a25 )}-) are repeating units enclosed in parentheses with f11 and f13 at the most free end (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), Rf ^a21 is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ^a22 , Rf ^a23 , Rf ^a24 , Rf ^a25 are all fluorine atoms, M ³ are all -O-; All M ⁴ is a methoxy group, an ethoxy group, or a chlorine atom (particularly a methoxy group or an ethoxy group), M ¹ , M ² are both a hydrogen atom, f11 is 0, f12 is 30 to 150 (more preferably 80 to 140) ), f15 is preferably 30 to 60, f13 and f14 are 0, f17 is 0 to 1 (particularly 0), g1 is 3, and f16 is 1 to 10.

In addition, when compound a used as compound (A) in Examples below is represented by the above formula (a2-1), Rf ^a1 is C ₃ F ₇ -, Rf ^a22 and Rf ^a23 are both fluorine atoms, and 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-, M ⁴ is a methoxy group, g1 is 3 is

Moreover, it is also preferable that an organosilicon compound (A) is a compound represented by a following formula (a2-2).

[Formula 13]

In the above formula (a2-2),

Rf ^{a26, a27} Rf, Rf ^{a28, a29,} and Rf are, each independently, is 1 or more hydrogen atoms are substituted with a fluorine atom or an alkyl group having a carbon number of 1~20 fluorine atom, Rf is a plurality of Rf ^{a26 a26} When multiple presence are different, respectively, Rf ^a27 this is a plurality of Rf ^a27 are different, respectively, Rf ^a28 if this plurality there are different respectively, a plurality of Rf ^a28, a plurality of Rf if Rf ^a29 the plurality, if any plurality presence ^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, when R ²⁵ is plural there are a plurality of R ²⁵ each different, R ²⁶ is a plurality when there are a plurality of different R ^26, respectively, when R ²⁷ is plural there is a plurality of R ²⁷ are different, respectively, are a plurality of R ²⁸ to R ²⁸ are different, respectively, if a plurality is present,

R ^29, and R ³⁰ are, each independently, an alkyl group having a carbon number of 1~20, R ²⁹ is the case that there is a plurality, and the plurality of R ²⁹ each different, R ³⁰ is a plurality exist a plurality of R ³⁰ when the Each may be different,

M ⁷ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NR ^C (=O)-, or -C(=O)NR-, wherein R is a fluorinated alkyl group of the alkyl group having 1 to 4 carbon atoms or a hydrogen atom, a group having 1 to 4 carbon atoms, and M ⁷ are different are a plurality of M ⁷ if present each plurality,

M ^5, M ⁹ are, each independently, a hydrogen atom or an alkyl group having a carbon number of 1~4, if M ⁵ is present a plurality a plurality of different M ^5, respectively, a plurality of M if M ⁹ a plurality presence ⁹ may be different from each other,

M ⁶ , and M ¹⁰ are each independently a hydrogen atom or a halogen atom,

M ^8, and M ¹¹ are each independently a hydrolyzable group, when a plurality M ⁸ there are a plurality of different M ^8, respectively, is a plurality of M ¹¹ to M ¹¹ are different respectively, if a plurality is present,

f21, f22, f23, f24, and f25 are each independently an integer of 0 to 600, and the sum of f21, f22, f23, f24, and f25 is 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,

M ¹⁰ -, M ⁶ -, f21 -{C(R ²⁵ )(R ²⁶ )}-, f22 -{C(Rf ^a26 )(Rf ^a27 )}-, f23 -{Si(R ²⁷ )( R ^{28 )}-, f24} -{Si(Rf ^a28 )(Rf a29 )}-, f25 -M ⁷ -, f26 -[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 }] are M ¹⁰ -, M ⁶ - are terminal, lined up in order to form a perfluoropolyether structure at least in part, and -O- is joined side by side in any order, unless -O- is continuous. Combining side by side in an arbitrary order is the same as that described in the above formula (a2-1), and is not limited to the meaning that each repeating unit is successively arranged in the order as described in the above formula (a2-2).

In the formula (a2-2), Rf ^a26 , Rf ^a27 , Rf ^a28 , and Rf ^a29 are all fluorine atoms, M ⁷ are all -O-, M ⁸ and M ¹¹ are both a methoxy group, an ethoxy group, or a chlorine atom (especially a methoxy group or an ethoxy group), M ⁵ , M ⁶ , M ⁹ , and M ¹⁰ are all hydrogen atoms, f21 is 0, f22 is 30 to 150 (more preferably 80 to 140), f25 It is preferable that 30-60, f23 and f24 are 0, f27 and f29 are 0-1 (particularly preferably 0), g2 and g3 are 3, and f26 and f28 are 1-10.

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

[Formula 14]

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 a perfluoroalkylene group having 2 to 6 carbon atoms. It is a trivalent saturated hydrocarbon group of 2-6, and R ³⁴ is a C1-C3 alkyl group. ^{R 30, R 31, R 32} , the number of carbon atoms of R ³³ are, each independently, is preferably 2 to 4, more preferably 2 to 3 a. h1 is 5 to 70, h2 is 1 to 5, and h3 is 1 to 10. 10-60 are preferable, as for h1, 20-50 are more preferable, 1-4 are preferable, as for h2, 1-3 are more preferable, 1-8 are preferable and, as for h3, 1-8 are more preferable. .

As compound (A), the compound represented by a following formula (a4) is also mentioned.

[Formula 15]

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 hydrogen of an alkylene group having 2 to 5 carbon atoms. a fluoroalkylene group partially substituted with fluorine, R ⁴³ and R ⁴⁴ are each independently an alkylene group having 2 to 5 carbon atoms, and R ⁴⁵ is a methyl group or an ethyl group. k1, k2, and k3 are each independently an integer of 1-5.

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

In the composition (ca) for forming the water-repellent layer (r), the organosilicon compound (B) represented by the following formula (b1) is preferably mixed with the organosilicon compound (A) described above. The organosilicon compound (B) has a hydrolysable group as described later, and the -SiOH group of the organosilicon compound (B) generated by hydrolysis is usually -SiOH of the organosilicon compound (A) generated by hydrolysis. Since dehydration condensation with the group and/or the -SiOH group of the organosilicon compound (B) generated by hydrolysis, in a preferred embodiment, the water-repellent layer (r) together with the condensed structure derived from the organosilicon compound (A) is formed of organic silicon It has a condensed structure derived from compound (B).

[Formula 16]

In the above formula (b1),

Rf ^b10 is an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom or a fluorine atom,

R ^b11, R ^b12, R ^b13, R ^b14 each independently is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, a plurality of R if R ^{b11 b11} there are multiple different respectively, R ^b12 is a plurality when there are a plurality of R ^b12 are each different, R ^b13 is if there is a plurality a plurality of R ^b13 are different, respectively, when R ^b14 there is a plurality or different, each a plurality of R ^b14,

Rf ^{b11, b12} Rf, Rf ^{b13, b14} Rf are, each independently, an alkyl group or a fluorine atom of 1 to 20 carbon atoms substituted with at least one hydrogen atom with a fluorine atom, Rf is a plurality of Rf ^{b11 b11} if there is a plurality each of which is different, Rf if ^b12 multiple presence are a plurality of Rf ^b12 different, respectively, Rf ^b13 if this plurality there is a plurality of Rf ^b13 are different, respectively, Rf if ^b14 plurality exist a plurality of Rf ^b14 may be different from each other,

R ^b15 is an alkyl group, R ^b15 if there are a plurality of a plurality of different R ^b15 are each from 1 to 20 carbon atoms,

A ¹ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, wherein R is a fluorinated alkyl group of the alkyl group having 1 to 4 carbon atoms or a hydrogen atom, a group having 1 to 4 carbon atoms, a ¹ is the case that there is a plurality a plurality of a ¹ or different, respectively,

A ² is a hydrolyzable group, and when ^two or more A 2 are present, a plurality of A ² may be different from each other,

b11, b12, b13, b14, and b15 are each independently an integer from 0 to 100;

c is an integer of 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 - are Rf ^b10 -, -Si(A ² ) _c (R ^b15 ) _3-c becomes terminal, does not form a perfluoropolyether structure, and bonds side by side in any order, unless -O- is connected with -O- to -F.

Rf ^b10 is each independently preferably 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 having 1 to 4 carbon atoms or a halogen atom, more preferably a methoxy group, an ethoxy group, or a chlorine atom.

1-30 are preferable, as for b11, 1-25 are more preferable, 1-10 are still more preferable, 1-5 are especially preferable, Most preferably, it is 1-2.

As for b12, 0-15 are preferable, More preferably, it is 0-10.

As for b13, 0-5 are preferable, More preferably, it is 0-2.

As for b14, 0-4 are preferable, More preferably, it is 0-2.

As for b15, 0-4 are preferable, More preferably, it is 0-2.

As for c, 2-3 are preferable, More preferably, it is 3.

As for the total value of b11, b12, b13, b14, and b15, 3 or more are preferable, 5 or more are preferable, 80 or less are preferable, More preferably, it is 50 or less, More preferably, it is 20 or less.

In particular, Rf ^b10 is 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 and b12 is It is preferable that 0-5, b13, b14, and b15 are all 0, and c is 3.

In addition, when FAS13E used as compound (B) in the following examples is represented by the above formula (b1), R ^b11 and R ^b12 are both hydrogen atoms, b11 is 2, b13, b14, and b15 are all 0, and c is 3, A ² is an ethoxy group, Rf ^b10 -{C(Rf ^b11 )(Rf ^b12 )} _b12 - is a terminal, and it is determined to be _{C 6} F _{13 -.}

Specifically, as the compound represented by the formula (b1), CF ₃ -Si-(OCH ₃ ) ₃ , C _j F _2j+1 -Si-(OC ₂ H ₅ ) ₃ (j is an integer of 1 to 12) Among them, 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 is preferred. Also, 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 is all 5-20 and 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 may also be mentioned (m is all 1-10, preferably 3-7, all n are 1-5, Preferably it is 2-4). CF ₃ (CF ₂ ) _p -(CH ₂ ) _q- Si-(CH ₂ CH=CH ₂ ) ₃ may be mentioned (p is all 2 to 10, preferably 2 to 8, and q is all 1 -5, preferably 2-4). Also, 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 all 2 to 10, preferably 3 to 7, q is all 1 to 5, preferably 2 to 4) .

Among the compounds represented by the formula (b1), the compound represented by the following formula (b2) is preferable.

[Formula 17]

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

The thickness of the water-repellent layer (r) is, for example, about 1-1000 nm.

3. Resin base layer (s)

The material of the resin base layer (s) of the present invention is not particularly limited, and any of an organic material and an inorganic material may be used. Examples of organic materials include acrylic resins, polycarbonate resins, polyester resins, styrene resins, acrylic-styrene copolymer resins, cellulose resins, polyolefin resins, vinyl resins (polyethylene, polyvinyl chloride, polystyrene, vinylbenzyl chloride resins, polyvinyl alcohol). etc.), such as thermoplastic resins; Thermosetting resins, such as a phenol resin, a urea resin, a melamine resin, an epoxy resin, unsaturated polyester, a silicone resin, and a urethane resin, etc. are mentioned. Examples of the inorganic material include metals such as iron, silicon, copper, zinc, and aluminum, or alloys, ceramics, and glass containing these metals. Among these, an organic type material is especially preferable. 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 preferable, and an acrylic resin is particularly preferable.

The resin base layer (s) in the present invention is preferably a protective layer (hereinafter, sometimes referred to as a hard coat layer) provided in order to protect an article from scratches in applications requiring abrasion resistance such as a display of an electronic device. And, it is more preferable that this protective layer is an acrylic resin type.

The hard coat layer is a layer having surface hardness, and the hardness is usually B or more in terms of pencil hardness, preferably HB or more, more preferably H or more, and particularly preferably 2H or more. A single layer structure may be sufficient as a hard-coat layer, and a multilayer structure may be sufficient as it. The hard coat layer is, for example, a cured layer of an ultraviolet curable resin. The hard coat layer includes a hard coat layer resin, and the hard coat layer resin includes, for example, an acrylic resin, an epoxy resin, a urethane resin, an amide resin, a vinyl benzyl chloride resin, a vinyl resin, or a silicone resin, or these resins. and resins of an ultraviolet curing type, electron beam curing type, or thermosetting type, such as mixed resin. In particular, it is also preferable that a hard-coat layer contains an acrylic resin in order to express high hardness. Since the tendency for adhesiveness with the said water-repellent layer (r) via the said layer (c) to become favorable is seen, it is preferable to contain an epoxy resin.

The hard-coat layer may contain the additive. The additive is not limited, and inorganic fine particles, organic fine particles, or mixtures thereof are exemplified. Examples of the additive include an ultraviolet absorber, a metal oxide such as silica and alumina, and an inorganic filler such as polyorganosiloxane. By including an inorganic filler, adhesiveness with the said water-repellent layer (r) via the said layer (c) can be improved. The thickness of a hard-coat layer is 1-100 micrometers, for example.

In the laminate of the present invention, as long as the water-repellent layer (r), the layer (c) and the resin base layer (s) are arranged in this order, between the water-repellent layer (r) and the layer (c), the layer (c) The other layer may be included on the surface side of the layer (s) between the layer (s) and the resin base layer (s), but it is preferable that there is no other layer between the layer (r) and the layer (c). Moreover, when a resin base material layer (s) is a hard-coat layer, it is preferable that there is no other layer between a resin base material layer (s) and a layer (c). It is preferable that the laminate of the present invention further contains a resin layer (s2) different from the resin substrate layer (s), and in order from the surface of the laminate, the water repellent layer (r), the layer (c), the resin substrate What is necessary is just to just set it in order of a layer (s) and a resin layer (s2).

In particular, when the resin base layer (s) is a hard coat layer, it is preferable that a resin layer (s2) different from the resin base layer (s) which is a hard coat layer is laminated|stacked. The resin base layer (s) which is a hard-coat layer, and the resin layer (s2) laminated|stacked may be a film shape or plate shape, and if it is a thing which can transmit light, it is preferable as a member for displays, such as a display. The laminate containing the resin base layer (s) and the resin layer (s2) which are hard-coat layers can be used for a flexible display as a front plate of an image display apparatus.

Examples of the resin constituting the resin layer (s2) include triacetyl cellulose, acetyl cellulose butyrate, ethylene-vinyl acetate copolymer, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, polyester, polystyrene, polyamide. , polyetherimide, poly(meth)acrylic, polyimide, polyethersulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone , polyether ether ketone, polyether sulfone, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, a film formed of a polymer such as polyamideimide. These polymers can be used individually or in mixture of 2 or more types. From the viewpoint of making both strength and transparency, such as bending resistance, preferable, it is a resin film formed from polymer|macromolecule, such as polyimide, polyamide, and polyamideimide. The thickness of the resin layer (s2) may be, for example, 10 µm or more and 500 µm or less, preferably 20 µm or more and 200 µm or less, more preferably 30 µm or more and 150 µm or less, and may be 100 µm or less.

The laminated body which has a resin layer (s2), Preferably it is used as a front plate in a flexible image display apparatus, The said front plate may be called a window film. The said flexible image display apparatus consists of the laminated body for flexible image display apparatuses, and an organic electroluminescent display panel, The laminated body for flexible image display apparatuses is arrange|positioned on the visual recognition side with respect to an organic electroluminescent display panel, and it can bend. Consists of. As a laminate for flexible image display devices, a polarizing plate, preferably a circularly polarizing plate, and a touch sensor may be further contained, and the order of lamination thereof is arbitrary, but a window film, a polarizing plate, a touch sensor or a window film, and a touch sensor from the viewer side , it is preferable to laminate in the order of the polarizing plate. When a polarizing plate exists on the visual recognition side rather than a touch sensor, since the pattern of a touch sensor becomes difficult to visually recognize and the visibility of a display image improves, it is preferable. Each member may be laminated using an adhesive, an adhesive, or the like. In addition, a light-shielding pattern formed on at least one surface of any layer of the window film, the polarizing plate, and the touch sensor may be provided.

You may provide a primer layer between the resin layer (s2) and the resin base layer (s) (particularly a hard-coat layer). As a primer agent, there exist primer agents, such as an epoxy-type compound of an ultraviolet curing type, a thermosetting type, or a two-component curing type, for example. It is preferable that the compound mixed in the primer layer is chemically bonded to the resin component mixed in the resin layer (s2) or the silicon material to be mixed if necessary. Moreover, as a primer agent, a polyamic acid may be used and the adhesiveness of a resin layer (s2) and resin base material layer (s) (particularly a hard-coat layer) can be improved. Moreover, as a primer agent, a silane coupling agent is mentioned, You may chemically bond with the silicon material mixed with the resin base material as needed by a condensation reaction. The thickness of the primer layer is, for example, 0.1 to 20 µm.

In the laminate of the present invention, the water contact angle (initial contact angle) measured at a liquid volume: 3 µL by the droplet method (analysis method: θ/2 method) is, for example, 105° or more, more preferably 110° or more , and is, for example, 120° or less. In addition, after performing the chemical resistance test performed in the examples to be described later, the water contact angle (contact angle after chemical resistance test) measured at a liquid volume: 3 µL by the droplet method (analysis method: θ/2 method) is, for example, 82.0 ° or more, preferably 85 ° or more, more preferably 90 ° or more, and the upper limit is, for example, 110 ° or less, and may be 100 ° or less.

Next, the manufacturing method of the laminated body of this invention is demonstrated.

The method of manufacturing the laminated body of this invention includes the process of (i) forming a layer (c) on a resin base material layer (s), (ii) a process of forming a water-repellent layer (r).

In the process of forming the said layer (c), the mixed composition (cc) of an organosilicon compound (C1) and/or an organosilicon compound (C2) is apply|coated to the resin base material layer (s). As for the composition (cc), it is preferable that the solvent (E) is mixed.

When the total amount of the composition (cc) is 100 mass%, the total amount of the organosilicon compound (C1) and the organosilicon compound (C2) is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, , More preferably, it is 0.1 mass % or more, and 5 mass % or less is preferable, More preferably, it is 3 mass % or less, More preferably, it is 2 mass % or less. The quantity of said organosilicon compound (C1) and (C2) can be adjusted at the time of preparation of a composition. You may calculate the quantity of the said organosilicon compound (A) from the analysis result of a composition. In addition, in this specification, when the range of the quantity, mass ratio, or molar ratio of each component is described, the said range can be adjusted at the time of preparation of a composition similarly to the above.

The solvent (E) preferably has an sp value [(cal/cm 3 ) ^1/2 ] of 9.00 or more, and more preferably an sp value of 10 or more, for example. As such a solvent (E), water, ethanol, isopropanol, etc. are mentioned, Especially, it is preferable that sp value is 15 or more, and water is the most preferable.

In this manual, the sp value (Solubility Parameter, solubility parameter) is "R. F. Fedors, Polym. Eng. Sci., 14 [2], 147-154 (1974)". In the Fedors method, the sp value is defined by the square root of the cohesive energy density. Specifically, the sp value is defined by the following formula.

δ = (ΔE/V) ^1/2 (1)

In the above formula (1), δ is the sp value ((cal/cm 3 ) ^1/2 ), ΔE is the cohesive energy (cal/mol), and V is the mole molecule of the solvent (cm 3 /mol). do.

In the Fedors method, it is considered that both of the above-described cohesive energy and molar molecules depend on the type and number of substituents contained in the solvent. Accordingly, the cohesive energy is calculated in consideration of the number of substituents from the cohesive energy and molecules of each substituent (shown in Table 1 below).

[Table 1]

For example, isopropanol is used as the solvent (E) in the embodiment to be described later is, two or a -CH _3, -CH <1 to a solvent having one to -OH.

The cohesive energy ΔE of isopropanol is

ΔE(cal/mol) = 1125×2+820+7120

is calculated as

In addition, V for mole molecules of isopropanol is,

V(cm3/mol)=33.5×2+(-1)+10

is calculated as

Accordingly, by using these values in the formula (1), the sp value of isopropanol can be calculated as ^{11.58 (cal/cm 3 ) 1/2.}

As a method of applying the composition (cc), for example, a dip coating method, a roll coating method, a bar coating method, a spin coating method, a spray coating method, a die coating method, a gravure coating method, etc. are mentioned, especially the spin coating method This is preferable.

Before applying the composition (cc), it is preferable to perform an easy-adhesion treatment on the resin base layer (s). Examples of the easily bonding treatment include hydrophilic treatment such as corona treatment, plasma treatment, and ultraviolet treatment, and plasma treatment is more preferred. By performing an easily adhesive treatment such as plasma treatment, functional groups such as OH groups (especially when the base material is an epoxy resin) and COOH groups (especially when the base material is an acrylic resin) can be formed on the surface of the base material, and on the surface of the base material When such a functional group is formed, especially the adhesiveness of a layer (c) and a resin base material layer (s) can be improved more.

After forming the layer (c), the water-repellent layer (r) can be formed by applying the mixed composition of the organosilicon compound (A) and curing it at room temperature.

As for the mixed composition of the said organosilicon compound (A), it is preferable that the said organosilicon compound (B) is mixed, and the solvent (D) is mixed normally. As the solvent (D), it is preferable to use a fluorine-based solvent, for example, a fluorinated ether-based solvent, a fluorinated amine-based solvent, or a fluorinated hydrocarbon-based solvent can be used. In particular, it is preferable that the boiling point is 100°C or higher. As the fluorinated ether solvent, hydrofluoroethers such as fluoroalkyl (especially perfluoroalkyl group having 2 to 6 carbon atoms)-alkyl (especially methyl group or ethyl group) ether are preferable, for example, ethylnonafluorobutyl ether or and ethyl nonafluoroisobutyl ether. As ethyl nonafluorobutyl ether or ethyl nonafluoro isobutyl ether, Novec (trademark) 7200 (made by 3M, molecular weight about 264) is mentioned, for example. The fluorinated amine solvent is preferably an amine in which at least one hydrogen atom of ammonia is substituted with a fluoroalkyl group, and a tertiary amine in which all hydrogen atoms of ammonia are substituted with a fluoroalkyl group (especially a perfluoroalkyl group) Preferably, tris(heptafluoropropyl)amine is mentioned specifically, Florinert (trademark) FC-3283 (made by 3M, molecular weight about 521) corresponds to this. Examples of the fluorinated hydrocarbon-based solvent include a fluorinated aliphatic hydrocarbon-based solvent such as 1,1,1,3,3-pentafluorobutane, and a fluorinated aromatic hydrocarbon-based solvent such as 1,3-bis(trifluoromethylbenzene). have. As 1,1,1,3,3-pentafluorobutane, Solve 55 (made by Solvex Corporation) etc. are mentioned, for example.

As the fluorine-based solvent, in addition to the above, hydrochlorofluorocarbons such as Asahiclean (registered trademark) AK225 (manufactured by AGC), hydrofluorocarbons such as Asahiclean (registered trademark) AC2000 (manufactured by AGC), etc. can be used. .

As the solvent (D), it is preferable to use at least a fluorinated amine solvent. Moreover, as the solvent (D), it is preferable to use two or more types of fluorine-based solvents, and it is preferable to use a fluorinated amine-based solvent and a fluorinated hydrocarbon-based solvent (especially a fluorinated aliphatic hydrocarbon-based solvent).

In addition, the composition (ca) for forming the water-repellent layer (r) is a silanol condensation catalyst, antioxidant, rust inhibitor, ultraviolet absorber, light stabilizer, mold inhibitor, antibacterial agent, bioadherence within the range that does not impair the effects of the present invention. Various additives, such as an inhibitor, a deodorant, a pigment, a flame retardant, and an antistatic agent, may be mixed.

The water-repellent layer (r) can be formed by apply|coating the composition (ca) for water-repellent layer (r) formation on the layer (c), and drying it. As a method of applying the composition for forming the water-repellent layer (r), for example, a dip coating method, a roll coating method, a bar coating method, a spin coating method, a spray coating method, a die coating method, a gravure coating method, etc. are mentioned. .

After apply|coating the composition for water-repellent layer (r) formation on layer (c), the water-repellent layer (r) can be formed by leaving still for 1 hour or more in normal temperature and air|atmosphere, for example. In this invention, normal temperature is 5-60 degreeC, Preferably, a film can be formed by leaving still in the temperature range of 15-40 degreeC.

The amount of the organosilicon compound (A) in the composition (ca) for forming the water-repellent layer (r) is, for example, 0.01 mass% or more, preferably 0.05 mass%, based on 100 mass% of the entire composition. above, and more preferably 0.5 mass % or less, more preferably 0.3 mass % or less.

When the organosilicon compound (B) is mixed in the composition (ca) for forming the water-repellent layer (r), the amount of the organosilicon compound (B) when the total amount of the composition is 100% by mass is, for example, 0.01 It is mass % or more, Preferably it is 0.03 mass % or more, It is preferable that it is 0.3 mass % or less, More preferably, it is 0.2 mass % or less.

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

Example

Hereinafter, the present invention will be described in more detail by way of Examples. The present invention is not limited by the following examples, and it is, of course, possible to carry out the present invention with appropriate modifications within the range suitable for the purpose of the above and later, and all of them are included in the technical scope of the present invention.

[Example 1]

A solution obtained by mixing 0.125 mass% of KBP90 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) represented by the following formula (c) as the organosilicon compound (C1) and 99.875 mass% of ion-exchanged water as a solvent (E) was stirred at room temperature, A solution for forming a layer (c) was obtained. The obtained solution was placed on a resin base layer (s) (alicyclic urethane acrylate system) having an acrylic hard coat layer to which the surface to be coated was activated using an atmospheric pressure plasma device (manufactured by Fuji Machinery Co., Ltd.), OPTICOAT MS- manufactured by MIKASA Co., Ltd. Using A100 (spin coater), 200 µl of the coating liquid, a rotation speed of 2000 rpm, and the number of rotation seconds were applied under the conditions of 20 seconds to obtain a layer (c).

[Formula 18]

Next, as the organosilicon compound (A), the compound represented by the following formula (1) (hereinafter, the compound a), and as the organosilicon compound (B), FAS13E(C ₆ F ₁₃ -C ₂ H ₄ -Si(OC _{2 )} H ₅ ) ₃ , manufactured by Tokyo Kasei Industrial Co., Ltd.), and FC-3283 (C ₉ F ₂₁ N, Florinut, manufactured by 3M) as a solvent (D) were mixed to prepare a solution, and stirred at room temperature for a predetermined time, A solution for forming a water-repellent layer (r) was obtained. When the whole solution for water-repellent layer (r) formation was 100 mass %, the ratio of the organosilicon compound (A) was 0.085 mass %, and the ratio of the organosilicon compound (B) was 0.05 mass %. A solution for forming the water-repellent layer (r) is applied on the layer (c) using a spray coater manufactured by Apyros Co., Ltd., and left at room temperature for 12 hours, the resin base layer (s), the layer (c), and the water-repellent layer (r) ) was obtained in this order. The spray coating conditions were: scan speed: 600 mm/sec, pitch: 5 mm, liquid amount: 6 cc/min, atomizing air: 350 kPa, and gap: 70 mm.

[Formula 19]

The compound a represented by said Formula (1) is synthesize|combined by the method of synthesis examples 1 and 2 of Unexamined-Japanese-Patent No. 2014-15609, r is 43, s is an integer of 1-6, The average molecular weight is about 8000.

[Examples 2 to 7]

A laminate was obtained in the same manner as in Example 1 except that the amount of KBP90 as the organosilicon compound (C1) and/or the kind of the solvent (E) were as described in Table 2-1.

[Examples 8 to 9]

As the organosilicon compound (C1), KBP64 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) represented by the following formula (c') was used, and the amount and/or the type of solvent (E) were as described in Table 2-1, except that , it carried out similarly to Example 1, and obtained the laminated body.

[Formula 20]

[Comparative Example 1]

The laminate was similar to Example 2 except that KBM903 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., 3-aminopropyltriethoxysilane) was used instead of the organosilicon compound (C1) and methyl ethyl ketone was used as the solvent (E). got

[Comparative Example 2]

Lamination was carried out in the same manner as in Example 2, except that KBM5103 (manufactured by Shin-Etsu Chemical Industries, Ltd., 3-acryloxypropyltrimethoxysilane) was used instead of the organosilicon compound (C1) and methylethyl ketone was used as the solvent (E). got a sieve

The following measurements were performed for the coatings obtained in the above Examples and Comparative Examples.

(1) Measurement of water contact angle (initial contact angle)

3 µL of water droplets were added dropwise to the obtained film, and the contact angle of water was measured by the droplet method (analysis method: θ/2 method) using a contact angle measuring apparatus (manufactured by Kyowa Interface Science, Ltd., DM700). .

(2) Measurement of water contact angle after chemical resistance test

A load of 1000 g was applied to the obtained film using a scratch device equipped with an eraser made by minoan in a state in which the eraser was in contact with the film. About 2.5 ml of ethanol was added dropwise thereto, the eraser was moved at a speed of 40 r/min (a speed of 40 reciprocating per minute) to reciprocate the film phase, and a chemical resistance test was performed. The contact angle of water after the eraser reciprocates the film 3000 times was measured.

The results are shown in Tables 2-1 and 2-2.

[Table 2-1]

[Table 2-2]

According to Tables 2-1 and 2-2, in Examples 1 to 7 in which the layer (c) was formed from the mixed composition of the organosilicon compound (C) specified in the present invention, the water-repellent layer (r) cured at room temperature was Comparative Example 1 using an organosilicon compound different from the organosilicon compound (C) instead of the organosilicon compound (C) of the present invention, whereas the water contact angle after the chemical resistance test was good at 82.0° or more (particularly 90° or more) , 2, the water contact angle after the chemical resistance test was lowered.

Industrial Applicability

The laminate of the present invention is a display device such as a touch panel display, an optical element, a semiconductor element, a building material, a nanoimprint technology, a solar cell, a window glass of an automobile or building, a metal product such as a cooking appliance, a ceramic product such as a tableware, It can be suitably formed into a film for automobile parts made of plastic, etc., and is useful industrially. Moreover, it is used suitably also for a kitchen, a bathroom, a wash basin, a mirror, the article of each member around a toilet, goggles, glasses, etc.

Claims (7)

A water-repellent layer (r) and a resin base layer (s) are laminated through the layer (c), the laminate comprising:
In the layer (c), the organosilicon compound (C1) represented by the following formula (c11) and/or two or more organosilicon compounds (C1) are condensed and bonded to at least one of the ^{following X 1 to X 4 .} formed from a mixed composition (cc) of compound (C2),
The said water-repellent layer (r) is a layer formed from the mixed composition (ca) of the organosilicon compound (A) represented by following formula (a1), The laminated body characterized by the above-mentioned.
[Formula 1]

In the above formula (c11),
Z ¹ , Z ² are each independently a reactive functional group other than a hydrolyzable group and a hydroxy group,
R ^x1, R ^x2, R ^x3, R ^x4 each independently, in the case of a hydrogen atom or 1 to 4 carbon atoms is an alkyl group, R ^x1 is a plurality exist a plurality of R ^x1 is different respectively, R ^x2 is a plurality when there are a plurality of different, each R ^x2, R ^x3 in this case, there is a plurality of the plurality of R ^x3 are respectively different, are a plurality of different R ^x4 each R ^x4 if a plurality is present,
Rf ^{x1, x2} Rf, Rf ^{x3, x4} Rf are, each independently, an alkyl group or a fluorine atom of 1 to 20 carbon atoms substituted with at least one hydrogen atom with a fluorine atom, Rf is a plurality of Rf ^{x1 x1} if there is a plurality each of which is different, Rf if ^x2 plurality existence is different, each a plurality of Rf ^x2, Rf ^x3 this is different each of a plurality of Rf ^x3, are a plurality of Rf ^x4 when Rf ^x4 the plurality, if any plurality presence may be different from each other,
Y is -NH-, -N(CH ₃ )- or -O-, and when there are a plurality of Y, a plurality of Y may be different,
X ¹ , X ² , X ³ , X ⁴ are each independently —OR ^c (R ^c is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an amino C _1-3 alkyldi C _1-3 alkoxysilyl group ), and, X ¹ is the case that a plurality exist a plurality of X ¹ are different each, X ² is the case that a plurality presence are a plurality of X ² different each, X ³ is a plurality of X ³ if a plurality exist each of which is different, and if X ⁴ is present a plurality are a plurality of different X ⁴ respectively,
p11 is an integer from 0 to 20, p12, p13, and p14 are each independently an integer from 0 to 10, p15 is an integer from 0 to 5, p16 is an integer from 1 to 10, p17 is 0 or 1,
The organosilicon compound (C1) has the ends of Z ¹ - and Z ² -, and unless -O- is connected to -O-, p11 -{C(R ^x1 )(R ^x2 )}-, p12 -{C(Rf ^x1 )(Rf ^x2 )}-, p13 -{Si(R ^x3 )(R ^x4 )}-, p14 -{Si(Rf ^x3 )(Rf ^x4 )}-, p15 -Y -, p16 pieces of -{Si(X ¹ )(X ² )-O}-, and p17 pieces of -{Si(X ³ )(X ⁴ )}- are combined side by side in an arbitrary order to constitute.
[Formula 2]

In the above formula (a1),
Rf ^a1 is a divalent perfluoropolyether structure in which both ends are oxygen atoms,
R ^11, R ^12, and R ¹³ is each independently an alkyl group having a carbon number of 1~20, R ¹¹ In this case, a plurality exist a plurality of R ¹¹ are different, respectively, R ¹² is a plurality of R ¹² when a plurality of presence each being different, are each a different plurality of R ¹³ to R ^13, if a plurality is present,
E if ^{1, E 2, E 3,} E 4, and E ⁵ are each independently a hydrogen atom or a fluorine atom, E ¹ is the case that a plurality presence of a plurality of E ¹ are different respectively, E ² has a plurality presence are different, each a plurality of E ^2, E ³ if there is a plurality a plurality of different E ^3, respectively, in the case where E ⁴ is present a plurality a plurality of different E ^4, respectively,
G ¹ and G ² are each independently a 2- to 10-valent organosiloxane group having a siloxane bond,
J ¹ , J ² , and J ³ are each independently a hydrolysable 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 J when the ^first plurality present are different, each with a plurality of J ^1, when J ² is a plurality presence are a plurality of J ² different, respectively, when J ³ a plurality presence are a plurality of J ³ different respectively,
L ¹ and L ² are, each independently, an oxygen atom, a nitrogen atom, or carbon atoms and a divalent linking group of 1 to 12 which may contain a fluorine atom, if L ¹ is a multiple presence or different, each a plurality of L ¹ and, a plurality of L ² are different each case a plurality of L ² is present,
d11 is 1 to 9,
d12 is 0 to 9,
a10 and a14 are each independently 0-10,
a11 and a15 are each independently 0 or 1,
a12 and a16 are each independently 0-9,
a13 is 0 or 1,
a21, a22, and a23 are each independently 0-2,
e1, e2, and e3 are each independently 1 to 3. The method of claim 1,
The organosilicon compound (C2) is
A compound having two or more structures (c21-1) represented by the following formula (c21-1), wherein the structures (c21-1) are chained or cyclically bonded by the following *3 or *4, the following *3 Or the bond by *4 is due to the condensation of ^{X 1} or X ^{2 of two or more of the organosilicon compounds (C1),}
In *1 and *2 of the following formula (c21-1), at least one type of unit bound by p11, p12, p13, p14, p15, (p16)-1, and p17 of the following formula (c21-2), respectively A group bonded in any order and having a terminal Z- is bonded, and in each of the plurality of structures (c21-1), the groups bonding to *1 and *2 may be different,
When a plurality of the structures (c21-1) are chained together, *3 at the end is a hydrogen atom, and *4 is a hydroxyl group.
[Formula 3]

[Formula 4]

In the above formula (c21-2),
Z is a reactive functional group other than a hydrolyzable group and a hydroxy group,
R ^x1 , R ^x2 , R ^x3 , R ^x4 , Rf ^x1 , Rf ^x2 , Rf ^x3 , Rf ^x4 , Y, X ¹ , X ² , X ³ , X ⁴ , p11 to p17 are those in the formula (c11) sign and agreement. 3. The method according to claim 1 or 2,
The said composition (ca) is a laminated body in which the organosilicon compound (B) represented by a following formula (b1) is mixed.
[Formula 5]

In the above formula (b1),
Rf ^b10 is an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom or a fluorine atom,
R ^b11, R ^b12, R ^b13 and R ^b14 each independently is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, a plurality of R if R ^{b11 b11} there are multiple different respectively, R ^b12 is a plurality when there are a plurality of R ^b12 are each different, R ^b13 is if there is a plurality a plurality of R ^b13 are different, respectively, when R ^b14 there is a plurality or different, each a plurality of R ^b14,
Rf ^{b11, b12} Rf, Rf ^b13 and ^b14 Rf are, each independently, an alkyl group or a fluorine atom of 1 to 20 carbon atoms substituted with at least one hydrogen atom with a fluorine atom, Rf is a plurality of Rf ^{b11 b11} if there is a plurality each of which is different, Rf if ^b12 multiple presence are a plurality of Rf ^b12 different, respectively, Rf ^b13 if this plurality there is a plurality of Rf ^b13 are different, respectively, Rf if ^b14 plurality exist a plurality of Rf ^b14 may be different from each other,
R ^b15 is an alkyl group, R ^b15 if there are a plurality of a plurality of different R ^b15 are each from 1 to 20 carbon atoms,
A ¹ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, wherein R is a fluorinated alkyl group of the alkyl group having 1 to 4 carbon atoms or a hydrogen atom, a group having 1 to 4 carbon atoms, a ¹ is the case that there is a plurality a plurality of a ¹ or different, respectively,
A ² is a hydrolyzable group, and when ^two or more A 2 are present, a plurality of A ² may be different from each other,
b11, b12, b13, b14 and b15 are each independently an integer from 0 to 100;
c is an integer of 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 -, Rf ^b10 -, -Si(A ^{2 )} ) _c (R ^b15 ) _3-c is terminated, does not form a perfluoropolyether structure, and bonds side by side in any order, unless -O- is connected with -O- to -F. 4. The method according to any one of claims 1 to 3,
The composition (cc) is a laminate in which at least the organosilicon compound (C1) is mixed. 5. The method according to any one of claims 1 to 4,
The resin base layer (s) is a hard coating layer laminate. A method for producing the laminate according to any one of claims 1 to 5, comprising:
A step of forming a layer (c) by applying the composition (cc) to the resin base layer (s);
A method for producing a laminate comprising a step of applying the composition (ca) to the layer (c) and curing at room temperature to form the water-repellent layer (r). 7. The method of claim 6,
In the step of forming the layer (c), the resin base layer (s) is plasma-treated, and the composition (cc) is applied to the plasma-treated surface.