TW201922497A - Laminate - Google Patents

Abstract

The purpose of the present invention is to provide a laminate that has excellent chemical resistance, while being obtained by laminating a layer, which is formed from a composition that contains a compound having a perfluoropolyether structure, on a substrate with another layer being interposed therebetween. A laminate wherein a water repellent layer (r) and a resin substrate layer (s) are laminated with a layer (c) being interposed therebetween, said layer (c) being formed from a composition that contains an organosilicon compound (C) which has a silicon atom that is bonded with a hydrolyzable group, and which has an amino group or an amine skeleton. This laminate is configured such that the water repellent layer (r) is formed from a composition that contains an organosilicon compound (A) which is represented by formula (a1).

Description

Laminated body

The present invention relates to a laminated body.

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.

When a composition containing a compound having a perfluoropolyether structure is applied to a substrate, the composition may be coated to form an antifouling coating after the substrate is previously formed with another layer such as an undercoat layer. Layer or water and oil repellent coating layer.

For example, Patent Document 1 discloses a hard coating film (hard coating layer) in which a hard coat layer (X), an undercoat layer (Y), and a surface layer (Z) are sequentially laminated on at least one surface of a substrate. coat film), wherein the surface layer (Z) has a water contact angle of 110 ° or more. It is also described that in order to form the surface layer (Z), a fluorine-based compound having a polyperfluoropolyether chain is preferably used, and in order to form the undercoat layer (Y), 3-propenyloxypropane is more preferable. Silyl compounds such as trimethoxysilane.
[Prior Art Literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-120253

[Problems to be Solved by the Invention]

When a film formed of a composition containing a compound having a perfluoropolyether structure is laminated with a substrate through another layer, it may be exposed to chemicals such as alcohol depending on the application. In such a case, it is required to Good performance (water repellency, etc.) can also be maintained after exposure to chemicals (hereinafter referred to as chemical resistance).

Therefore, an object of the present invention is to provide a laminated body in which a layer formed of a composition containing a compound having a perfluoropolyether structure is laminated with a base material through another layer, and the laminated body is excellent in chemical resistance.
[Means for solving problems]

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

[1] A laminated body comprising a water-repellent layer (r) and a resin substrate layer (s) via an organic silicon compound (C) containing a silicon atom having a hydrolyzable group and having an amine group or an amine skeleton. The layer (c) formed by the composition is laminated, and the laminated body is characterized in that:
The water-repellent layer (r) is a layer formed of a composition containing an organosilicon compound (A) represented by the following formula (a1):
[Chemical 1]



In the formula (a1),
Rf ^a1 is a divalent perfluoropolyether structure with oxygen atoms at both ends,
R ^11, R ¹² and R ¹³ are each independently alkyl having 1 to 20, in a case where a plurality of R ^11, R ¹¹ may be respectively different plurality of, in a case where a plurality of R ^12, multiple R ¹² s may be different from each other, 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 ¹ and G ² are each independently a divalent to 10-valent organosiloxy group having a siloxane bond,
J ¹ , J ² and J ³ are each 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. case ^{1, a} plurality of J may be different from each other, in the case where there is a plurality of J ^2, J ² may be different from each other plurality, in the 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 carbon number of fluorine atoms, a divalent linking group having 1 to 12, in the presence of a plurality of L ^1, a plurality of L ¹ may be different from each other, in When there are multiple L ² , the multiple L ² may be different,
d11 is 1-9,
d12 is 0-9,
a10 and a14 are independently 0 to 10,
a11 and a15 are independently 0 or 1,
a12 and a16 are independently 0-9,
a13 is 0 or 1,
a21, a22, and a23 are independently 0 to 2,
e1, e2, and e3 are each independently 1 to 3.

[2] The laminated body according to the above [1], wherein the organosilicon compound (C) is an organosilicon compound represented by the following formula (c1) or an organosilicon compound represented by the following formula (c10) :
[Chemical 2]



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 there are multiple R ^x1s , multiple R ^x1s may be different from each other. ^x2 case, a plurality of R & lt ^x2 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 the case where there is a plurality of R ^x4, R ^x4 may be different from each plurality,
Rf ^x1 , Rf ^x2 , Rf ^x3 , and Rf ^x4 are each independently an alkyl or fluorine atom having 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced with fluorine atoms. When there are multiple Rf ^x1s , multiple Rf ^x1 may be different from each other, 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 the presence of a plurality of Rf ^x4 In the following, multiple Rf ^x4 can be different,
R ^x5 is an alkyl group having 1 to 20 carbon atoms. When multiple R ^x5 are present, multiple R ^x5 may be different,
X is a hydrolyzable group. In the case where there are multiple Xs, the multiple Xs may be different, respectively.
Y is -NH- or -S-. In the case where there are multiple Ys, the multiple Ys may be different, respectively.
Z is a vinyl group, an α-methyl vinyl group, a styryl group, a methacryl group, an acryl group, an amine group, an isocyanate group, an isocyanurate group, an epoxy group, a sulfonylurea group, or a mercapto group
p1 is an integer from 1 to 20, p2, p3, and p4 are each independently an integer from 0 to 10, and p5 is an integer from 1 to 10,
p6 is an integer from 1 to 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 is a terminal and -O- and -O- are not connected, the bonds can be arranged in any order and contain at least one of amine group and -NH-;
[Chemical 3]



In the formula (c10),
R ^x10 and R ^x11 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When a plurality of R ^x10 are present, a plurality of R ^x10 may be different from each other. In a case where a plurality of R ^x11 are present, many R ^x11 can be different,
Rf ^x10 and Rf ^x11 are each independently an alkyl or fluorine atom having 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced with fluorine atoms. In the case where there are multiple Rf ^x10 , the multiple Rf ^x10 may be different, respectively. In the case where there are multiple Rf ^x11 , the multiple Rf ^x11 may be different,
R ^x50 and R ^{x5 1} are each independently an alkyl group having 1 to 20 carbon atoms. When multiple R ^x50 and R ^{x5 1} are present, multiple R ^x50 and R ^{x5 1} may be different, respectively.
X ²⁰ and X ²¹ are independently hydrolyzable groups, and in the case where there are multiple X ²⁰ and X ²¹ , the multiple X ²⁰ and X ²¹ may be different, respectively.
p10 is independently an integer from 1 to 30, p20 is each independently an integer from 0 to 30, and at least one of the repeating units enclosed by parentheses with p10 or p20 is substituted with an amine skeleton -NR ^100- , so R ¹⁰⁰ in the amine skeleton is a hydrogen atom or an alkyl group,
p60 and p60 'are each independently an integer of 1 to 3,
Regarding p10-{C (R ^x10 ) (R ^x11 )}-, p20--(C (Rf ^x10 ) (Rf ^x11 )}-), there is no need to make p10 or p20 consecutive, but to arrange the keys in an arbitrary order And both ends are -Si (X ²⁰ ) _p60 (R ^x50 ) _3-p60 and -Si (X ²¹ ) _{p60 '} (R ^{x5 1} ) _3-p60' .

[3] The layered product according to the above [1] or [2], wherein the water-repellent layer (r) comprises an organosilicon compound (A) represented by the above formula (a1) and the following formula The layer formed by the composition of the organosilicon compound (B) represented by (b1):
[Chemical 4]



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,
R ^b11, R ^B12, R ^B13 and R ^B14 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and in the case where there are plural R ^b11 and R ^b11 may be respectively a plurality of different, in the presence of a plurality of R ^b12 case, a plurality of R ^b12 may be different from each other, in a case where there are plural R ^b13 and R ^b13 may be respectively a plurality of different, in the presence of a case where a plurality of R ^b14 and R ^b14 may be different from each plurality,
Rf ^b11 , Rf ^b12 , Rf ^b13, and Rf ^b14 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. When a plurality of Rf ^b11 are present, a plurality of Rf ^b11 respectively at different, in a case where there are a plurality of Rf ^b12, respectively different plurality Rf ^b12, in the case where there are a plurality Rf ^b13, a plurality of different Rf ^b13 respectively, in the presence of a plurality of Rf ^b14 In the following, multiple Rf ^b14 can be different,
R ^b15 is an alkyl group having 1 to 20 carbon atoms. In the case where there is a plurality of R ^b15 , the plurality of R ^b15 may be different, respectively.
A ¹ is -O-, -C (= O) -O-, -OC (= O)-, -NR-, -NRC (= O)-, or -C (= O) NR-, and R is a hydrogen atom, alkyl 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 a ^1, a plurality of a ¹ may be different from each other,
A ² is a hydrolyzable group. In the case where there is a plurality of A ² , the 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 from 1 to 3,
About Rf ^b10- , -Si (A ² ) _c (R ^b15 ) _3-c , b11 pieces-(C (R ^b11 ) (R ^b12 ))-, b12 pieces-(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 a terminal, does not form a perfluoropolyether structure, and -O- is not connected to -O- or -F, and the bonds can be arranged in any order.

[4] The laminated body according to the above [2], wherein the organosilicon compound (C) represented by the formula (c1) is represented by the following formula (c2):
[Chemical 5]



In the formula (c2),
X ¹ is a methoxy group or an ethoxy group. In the case where there is a plurality of X ¹ , the plurality of X ¹ may be different, respectively.
Y ¹ is -NH-,
Z ¹ is amine or thiol,
R ^x51 is an alkyl group having 1 to 20 carbon atoms. When a plurality of R ^x51 are present, the plurality of R ^x51 may be different, respectively.
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.

[5] The laminated body according to the above [2], wherein the organosilicon compound (C) represented by the formula (c10) is represented by the following formula (c20):
[Chemical 6]



In the formula (c20),
X ³⁰ and X ³¹ are independently hydrolyzable groups, and in the case where there is a plurality of X ³⁰ and X ³¹ , the plurality of X ³⁰ and X ³¹ may be different, respectively.
R ^x55 and R ^x56 are each independently an alkyl group having 1 to 20 carbon atoms, in the presence of a case where a plurality of R ^x55 and R ^x56, a plurality of R ^x55 and R ^x56 may be different from each other,
Regarding -C _w H _2w- , at least one part of the methylene group is substituted with an amine skeleton -NR ^100- , and R ¹⁰⁰ is a hydrogen atom or an alkyl group,
w is an integer from 1 to 30 (except for the number of methylene groups substituted with an amine skeleton),
p65 and p66 are each independently an integer of 1 to 3.

[6] The laminated body according to any one of [1] to [5], wherein the resin substrate layer (s) is an acrylic resin-based hard coat layer.

[7] A method for producing a laminated body, which is the method for producing a laminated body according to any one of [1] to [6], wherein the method for producing a laminated body includes:
A step of coating the resin substrate layer (s) with a composition containing the organic silicon compound (C) to form a layer (c); and coating the layer (c) with the organic silicon compound ( A) a step of hardening the composition at room temperature to form a water-repellent layer (r).

[8] The method for producing a laminated body according to the above [7], wherein in the step of forming the water-repellent layer (r), the composition containing the organic silicon compound (A) further includes the organic Silicon compound (B).

[9] The method for producing a laminated body according to the above [7] or [8], wherein the resin substrate layer (s) is subjected to a plasma treatment, and the plasma-treated surface is coated with A composition of the organosilicon compound (C).
[Effect of the invention]

In the laminated body of the present invention, a water-repellent layer formed of a composition containing a predetermined organosilicon compound (A) having a perfluoropolyether structure is a layer formed of a composition containing a predetermined organosilicon compound (C) Laminated with the base material, so good chemical resistance can be achieved.

In the laminated body of the present invention, a water-repellent layer (r) and a resin substrate layer (s) are laminated via a layer (c) formed of a composition containing a predetermined organosilicon compound (C). Hereinafter, the water-repellent layer (r), the layer (c), and the resin base material layer (s) will be described in order.

1. Water repellent layer (r)
The water-repellent layer (r) is a layer formed of a composition including an organosilicon compound (A) represented by the following formula (a1), and has a structure derived from the organosilicon compound (A). As will be described later, the organosilicon compound (A) has a hydrolyzable group, and the -SiOH groups of the organosilicon compound (A) generated by hydrolysis undergo dehydration condensation with each other. Therefore, the water-repellent layer (r) usually has an organosilicon source. Compound (A) condensation structure.

[Chemical 7]

In the formula (a1),
Rf ^a1 is a divalent perfluoropolyether structure with oxygen atoms at both ends,
R ¹¹ , R ^12, and R ¹³ are each independently (that is, R ¹¹ and R ¹² and R ¹³ may be the same or different from each other) are alkyl groups having 1 to 20 carbon atoms. In the case where multiple R ¹¹ are present, 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 the 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 ¹ and G ² are each independently a divalent to 10-valent organosiloxy group having a siloxane bond,
J ¹ , J ² and J ³ are each 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. case ^{1, a} plurality of J may be different from each other, in the case where there is a plurality of J ^2, J ² may be different from each other plurality, in the 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 carbon number of fluorine atoms, a divalent linking group having 1 to 12, in the presence of a plurality of L ^1, a plurality of L ¹ may be different from each other, in When there are multiple L ² , the multiple L ² may be different,
d11 is 1-9,
d12 is 0-9,
a10 and a14 are independently 0 to 10,
a11 and a15 are independently 0 or 1,
a12 and a16 are independently 0-9,
a13 is 0 or 1,
a21, a22, and a23 are independently 0 to 2,
e1, e2, and e3 are each 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 the polycondensation reaction (polycondensation reaction)) with each other 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 8]

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,
Rf ^a22 , Rf ^a23 , Rf ^a24, and Rf ^a25 are each independently one or more carbon atoms of 1 to 20 carbon atoms or fluorine atoms in which a hydrogen atom is replaced with a fluorine atom. When there are multiple Rf ^a22 , multiple Rf ^a22 may be different from each other, in a case where there are a plurality of Rf ^a23, a plurality of different Rf ^a23 respectively, in the presence of a plurality of Rf ^a24, a plurality of different Rf ^a24 respectively, in the presence of a plurality of Rf ^a25 In the following, multiple Rf ^a25 can 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, and in the case where there is a plurality of R ^20, R ²⁰ may be each a plurality of different, in the presence of a plurality of R the case ^21, a plurality of R ²¹ may be different from each other, in the presence of 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 different from each plurality,
R ²⁴ is an alkyl group having 1 to 20 carbon atoms, and in a case where 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. When a plurality of M ¹ are present, the plurality of M ¹ may be different from each other.
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 a hydrogen atom , An alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms), when there are multiple M ^3s , the multiple M ^3s may be different,
M ⁴ is a hydrolyzable group. In the case where there is a plurality of M ⁴ , the plurality of M ⁴ may be different, respectively.
f11, f12, f13, f14, and f15 are each independently an integer of 0 to 600, and 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,
About 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- and -O- or -F are not Links, 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, even more preferably 50 to 200 (more preferably 30 to 150, especially 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 ^a1 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 9]

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 a fluorine atom, an alkyl group having 1 to 20, in the case where there are a plurality of Rf ^a26, a plurality of Rf ^a26 may be different from each other, in the 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, a plurality of different Rf ^a28 respectively, in the presence of a plurality of Rf ^a29 In the following, multiple Rf ^a29 can be different,
The case where 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, and in the presence of a plurality of R ^25, R ²⁵ may be each a plurality of different, in the presence of a plurality of R the case ^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 respectively a plurality of different, in a case where a plurality of R ^28, R ²⁸ may be different from each plurality,
R ²⁹ and R ³⁰ are each independently an alkyl group having 1 to 20 carbon atoms. When multiple R ²⁹ are present, multiple R ²⁹ may be different from each other. When multiple R ³⁰ are present, multiple R ³⁰ Can be different,
M ⁷ is -O-, -C (= O) -O-, -OC (= O)-, -NR-, -NRC (= O)-, or -C (= O) NR-, and R is In the case where there are a plurality of M ^{7 of} a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluorine-containing alkyl group having 1 to 4 carbon atoms, the plurality of M ⁷ may be different, respectively.
M ^5, M ⁹ 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 different plurality of, in the case where there is a plurality of M ^9, multiple Each M ⁹ can be different,
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, in the presence of a plurality of M ⁸ and M ⁸ may be different from each other plurality, in the case where there is 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, and the total value of f21, f22, f23, f24, and f25 is 13 or more.
f26 and f28 are each independently an integer of 1-20,
f27 and f29 are each independently an integer of 0 to 2,
g2 and g3 are each independently an integer of 1 to 3,
About ^{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-(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 }], as long as M ¹⁰ -and M ⁶ -are terminals, and at least a part of them is arranged in the order of forming a perfluoropolyether structure, and -O- and -O- are discontinuous, and the bonds can be arranged in any 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 10]

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 carbon number 2 R 6 is a trivalent saturated hydrocarbon group, 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 11]

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.

The water-repellent layer (r) is preferably a layer formed of a composition containing the organosilicon compound (A) and further containing an organosilicon compound (B) represented by the following formula (b1). As described later, the organosilicon compound (B) has a hydrolyzable group, and the -SiOH group of the organosilicon compound (B) usually generated by hydrolysis and the -SiOH group of the organosilicon compound (A) generated by hydrolysis and / Or, the -SiOH group of the organosilicon compound (B) produced by hydrolysis undergoes dehydration condensation, so in a preferred form, the water-repellent layer (r) has a condensation structure derived from the organosilicon compound (A) and Condensed structure of organosilicon compound (B).

[Chemical 12]

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,
R ^b11 , R ^b12 , R ^b13 , and R ^b14 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In the case where there is a plurality of R ^b11 , the plurality of R ^b11 may be different from each other. ^b12 case, a plurality of R ^b12 may be different from each other, in a case where there are plural R ^b13 and R ^b13 may be respectively a plurality of different, in the presence of a case where a plurality of R ^b14 and R ^b14 may be different from each plurality,
Rf ^b11 , Rf ^b12 , Rf ^b13 , and Rf ^b14 are each independently an alkyl or fluorine atom having 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced with fluorine atoms. When there are multiple Rf ^b11 , multiple Rf ^b11 respectively at different, in a case where there are a plurality of Rf ^b12, respectively different plurality Rf ^b12, in the case where there are a plurality Rf ^b13, a plurality of different Rf ^b13 respectively, in the presence of a plurality of Rf ^b14 In the following, multiple Rf ^b14 can be different,
R ^b15 is an alkyl group having 1 to 20 carbon atoms. In the case where there is a plurality of R ^b15 , the plurality of R ^b15 may be different, respectively.
A ¹ is -O-, -C (= O) -O-, -OC (= O)-, -NR-, -NRC (= O)-, or -C (= O) NR-, and R is a hydrogen atom, alkyl 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 a ^1, a plurality of a ¹ may be different from each other,
A ² is a hydrolyzable group. In the case where there is a plurality of A ² , the 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 from 1 to 3,
About Rf ^b10- , -Si (A ² ) c (R ^b15 ) _3-c , b11 pieces-(C (R ^b11 ) (R ^b12 ))-, b12 pieces-{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 a terminal, does not form a perfluoropolyether structure, and -O- is not connected to -O- or -F, and 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 13]

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.

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

2. Layer (c)
The layer (c) is formed of a composition containing an organosilicon compound (C) having a silicon atom bonded to a hydrolyzable group and having an amine group or an amine skeleton. The organosilicon compound (C) is preferably one having one or more amine skeletons. In this specification, the organic silicon compound (C) having an amine group or an amine skeleton may be simply referred to as an organic silicon compound (C). The layer (c) can function as an undercoat layer of the water-repellent layer (r). As described above, the organosilicon compound (C) has hydrolyzable groups bonded to silicon, and the -SiOH groups of the organosilicon compound (C) generated by hydrolysis undergo dehydration condensation, so the layer (c) usually has Condensed structure of organosilicon compound (C).

Examples of the organic silicon compound (C) having an amine group or an amine skeleton include one or more organic silicon compounds represented by the following formula (c1) and an amine skeleton represented by the following formula (c10), More than one hydrolyzable organosilicon compound. Hereinafter, these organic silicon compounds will be described. The amine skeleton is represented by -NR ^10- , and R ¹⁰ is hydrogen or an alkyl group. R ^{10 is} preferably hydrogen or an alkyl group having 1 to 5 carbon atoms. When the organosilicon compound (C) contains a plurality of amine skeletons, the plurality of amine skeletons may be the same or different.

The layer (c) can be formed of a composition containing an organosilicon compound (C) represented by the following formula (c1).

[Chemical 14]

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. In the case where there are multiple R ^x1s , multiple R ^x1s may be different from each other. ^x2 case, a plurality of R & lt ^x2 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 the case where there is a plurality of R ^x4, R ^x4 may be different from each plurality,
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 one or more hydrogen atoms are replaced with fluorine atoms. When there are multiple Rf ^x1s , multiple Rf ^x1 may be different from each other, 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 the presence of a plurality of Rf ^x4 In the following, multiple Rf ^x4 can be different,
R ^x5 is an alkyl group having 1 to 20 carbon atoms. When multiple R ^x5 are present, multiple R ^x5 may be different,
X is a hydrolyzable group. In the case where there are multiple Xs, the multiple Xs may be different, respectively.
Y is -NH- or -S-. In the case where there are multiple Ys, the multiple Ys may be different, respectively.
Z is a vinyl group, an α-methylvinyl group, a styryl group, a methacryl group, an acryl group, an amine group, an isocyanate group, an isocyanurate group, an epoxy group, a sulfonylurea group, or a mercapto group,
p1 is an integer from 1 to 20, p2, p3, and p4 are each independently an integer from 0 to 10, and p5 is an integer from 1 to 10,
p6 is an integer from 1 to 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 is a terminal and -O- and -O- are not linked, the bonds can be arranged in any order, and they have at least one amine group and -NH-.

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, p1 is 1 to 10, p2, p3, and p4 are all 0, p5 is 1 to 5 (especially 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 15]

In the formula (c2),
X ¹ is a hydrolyzable group, and when a plurality of X ¹ are present, the plurality of X ¹ may be different from each other,
Y ¹ is -NH-,
Z ¹ is amine or thiol,
R ^x51 is an alkyl group having 1 to 20 carbon atoms. When a plurality of R ^x51 are present, the plurality of R ^x51 may be different, respectively.
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.

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

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 layer (c) may be formed of a composition containing an organosilicon compound (C) represented by the following formula (c10), having one or more amine skeletons, and having two or more hydrolyzable groups.

[Chemical 16]

In the formula (c10),
R ^x10 and R ^x11 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When a plurality of R ^x10 are present, a plurality of R ^x10 may be different from each other. In a case where a plurality of R ^x11 are present, many R ^x11 can be different,
Rf ^x10 and Rf ^x11 are each independently an alkyl or fluorine atom having 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced with fluorine atoms. In the case where there are multiple Rf ^x10 , the multiple Rf ^x10 may be different, respectively. In the case where there are multiple Rf ^x11 , the multiple Rf ^x11 may be different,
The case where R ^x50 and R ^x50 'are each independently an alkyl group having 1 to 20 carbon atoms, and in the presence of a plurality of R ^x50 and R ^x50', a plurality of R ^x50 and R ^x50 'may be different from each other,
X ²⁰ and X ²¹ are independently hydrolyzable groups, and in the case where there are multiple X ²⁰ and X ²¹ , the multiple X ²⁰ and X ²¹ may be different, respectively.
p10 is independently an integer from 1 to 30, p20 is each independently an integer from 0 to 30, and at least one of the repeating units enclosed by parentheses with p10 or p20 is substituted with an amine skeleton -NR ^100- , so R ¹⁰⁰ in the amine skeleton is a hydrogen atom or an alkyl group,
p60 and p60 'are each independently an integer of 1 to 3,
Regarding p10-{C (R ^x10 ) (R ^x11 )}-, p20--(C (Rf ^x10 ) (Rf ^x11 )}-), there is no need to make p10 or p20 consecutive, but to arrange the keys in an arbitrary order And both ends are -Si (X ²⁰ ) _p60 (R ^x50 ) _3-p60 and -Si (X ²¹ ) _{p60 '} (R ^x50 ') _{3-p60 '} .

R ^x10 and R ^{x11 are} preferably a hydrogen atom.

Rf ^x10 and Rf ^x11 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 ^x50 and R ^{x50 'are} preferably an alkyl group having 1 to 5 carbon atoms.

X ²⁰ and X ^{21 are} preferably an alkoxy group, a halogen group, a cyano group, or an isocyanate group, more preferably an alkoxy group, and even more preferably a methoxy group or an ethoxy group.

Amine skeleton -NR ¹⁰⁰ -As mentioned above, as long as there is at least one in the molecule, any of the repeating units enclosed with parentheses p10 or p20 may be substituted with the amine skeleton, but it is preferred It is part of a repeating unit enclosed in parentheses with p10. There may be a plurality of the amine skeleton, and in this case, the number of the amine skeleton is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 5. In this case, it is preferable to have an alkylene group between adjacent amine skeletons. The carbon number of the alkylene group is preferably 1 to 10, and more preferably 1 to 5. The number of carbons of the alkylene group between adjacent amine backbones is included in the total of p10 or p20.

In the amine skeleton -NR ^100- , when R ¹⁰⁰ is an alkyl group, the number of carbons is preferably 5 or less, and more preferably 3 or less. The amine skeleton -NR ¹⁰⁰ -is preferably -NH- (R ¹⁰⁰ is a hydrogen atom).

p10 is preferably from 1 to 15, and more preferably from 1 to 10, excluding the number of repeating units substituted with an amine skeleton.

p20 is preferably 0 to 5 except for the number of repeating units substituted with an amine skeleton, and more preferably 0 to 2 in all.

p60 and p60 'are preferably 2 to 3, and more preferably 3.

As the organosilicon compound (C), preferably used in the formula (c10), R ^x10 and R ^x11 are both hydrogen atoms, X ²⁰ and X ²¹ are alkoxy groups (especially methoxy or ethoxy groups) ), The repeating unit enclosed by p10 is substituted with at least one amine skeleton -NR ^100- , R ¹⁰⁰ is a hydrogen atom, and p10 is 1 to 10 (wherein the Except for the number), compounds with p20 of 0 and p60 and p60 'of 3.

Furthermore, if the formula (c10) is used as a compound (C) in the examples described later, N-2- (aminoethyl)-described in Japanese Patent Laid-Open No. 2012-197330- Reactant of 3-aminopropyltrimethoxysilane and chloropropyltrimethoxysilane (trade name; X-12-5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.), then R ^x10 and R ^x11 are hydrogen atoms , P10 is 8, p20 is 0, two amine skeletons (R ¹⁰⁰ are hydrogen atoms), both ends are the same, p60 and p60 'are 3, and X ²⁰ and X ²¹ are methoxy groups.

The organosilicon compound (C) is preferably a compound represented by the following formula (c20).

[Chemical 17]

In the formula (c20),
X ³⁰ and X ³¹ are independently hydrolyzable groups, and in the case where there is a plurality of X ³⁰ and X ³¹ , the plurality of X ³⁰ and X ³¹ may be different, respectively.
R ^x55 and R ^x56 are each independently an alkyl group having 1 to 20 carbon atoms, in the presence of a case where a plurality of R ^x55 and R ^x56, a plurality of R ^x55 and R ^x56 may be different from each other,
Regarding -C _w H _2w- , at least one part of the methylene group is substituted with an amine skeleton -NR ^100- , and R ¹⁰⁰ is a hydrogen atom or an alkyl group,
w is an integer from 1 to 30 (except for the number of methylene groups substituted with an amine skeleton),
p65 and p66 are each independently an integer of 1 to 3.

X ³⁰ and X ^{31 are} preferably an alkoxy group, a halogen group, a cyano group, or an isocyanate group, and more preferably an alkoxy group.

There may be a plurality of amine skeletons -NR ^100- . In this case, the number of amine skeletons is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 5. In this case, it is preferable to have an alkylene group between adjacent amine skeletons. The carbon number of the alkylene group is preferably 1 to 10, and more preferably 1 to 5. The number of carbons of the alkylene group between adjacent amine backbones is included in the total number of w.

In the amine skeleton -NR ^100- , when R ¹⁰⁰ is an alkyl group, the number of carbons is preferably 5 or less, and more preferably 3 or less. The amine skeleton -NR ¹⁰⁰ -is preferably -NH- (R ¹⁰⁰ is a hydrogen atom).

R ^x55 and R ^x56 is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably is alkyl of 1 to 5.

p65 and p66 are preferably an integer of 2 to 3, and more preferably 3.

w is preferably 1 or more, more preferably 2 or more, more preferably 20 or less, and even more preferably 10 or less.

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

3. Resin base material layer (s)
The material of the resin base material layer (s) of the present invention is not particularly limited, and may be any one of an organic material and an inorganic material, and the shape of the base material may be any of a flat surface and a curved surface, or may be 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, organic materials are particularly preferred. 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 resin base material layer (s) of the present invention is preferably a protective layer (hereinafter, sometimes referred to as a hard coat layer) for protecting an article from damage in applications requiring abrasion resistance such as a display of an electronic device. Preferably, the protective layer is an acrylic resin.

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 said water-repellent layer (r) which passed through the said layer (c) 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 inorganic filler, the adhesion with the water-repellent layer (r) passing through the layer (c) can be improved. The thickness of the hard coat layer is, for example, 1 μm to 100 μm.

As for the laminated body of the present invention, as long as the water-repellent layer (r), the layer (c), and the resin base material layer (s) are arranged in this order, the water-repellent layer (r) and the layer (c) Between the layer (c) and the resin substrate layer (s), and the surface layer of the layer (s) includes other layers, but it is preferable that there is no other layer between the layer (r) and the layer (c) . In addition, when the resin base material layer (s) is a hard coat layer, it is preferable that there is no other layer between the resin base material layer (s) and the layer (c). The laminated body of the present invention preferably further includes a resin layer (s2) different from the resin substrate layer (s), and it is assumed that the water-repellent layer (r), the layer (c), and the resin base are sequentially from the surface of the laminated body. The order of the material layer (s) and the resin layer (s2) is sufficient. The resin component of the resin layer (s2) is not particularly limited, but when the resin substrate layer (s) is a hard coat layer, especially a polyacrylate resin, a polyamide resin, and a polyimide resin Polyamine resin, Polyurethane resin, Polyester resin, Polycarbonate resin, Polyether resin, Ethyl cellulose resin, Cycloolefin resin, Polyethylene Alcohol-based resins and the like are preferred because they can easily improve the adhesion to the hard coat layer, and among them, polyimide-based resins and polyamido-imide-based resins are preferred. The thickness of the resin layer (s2) is, for example, 10 μm to 500 μm.

An undercoat layer may also be provided between the resin layer (s2) and the resin substrate layer (s) (especially a 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. It is preferable that the compound contained in the undercoat layer is chemically bonded to the resin component contained in the resin layer (s2) or the silicon material contained as required. In addition, as the primer, polyamic acid can be used, which can improve the adhesion between the resin layer (s2) and the resin substrate layer (s) (especially 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.

Regarding the multilayer body of the present invention, the water contact angle (initial contact angle) measured by the liquid droplet method (analysis method: θ / 2 method) at a liquid volume: 3 μL is, for example, 105 ° or more, and more preferably 110 ° or more. 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 85 ° or more, and more preferably 90 ° or more. 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 for manufacturing the laminated body of the present invention includes (i) forming a layer (c) having a structure derived from an organic silicon compound (C) on the resin substrate layer (s), and (ii) forming a water-repellent layer. step.

In the step of forming the layer (c), a resin substrate layer (s) is coated with a composition containing the organic silicon compound (C). The composition preferably contains an organosilicon compound (C) and a solvent (E). The solvent (E) is not particularly limited. For example, an alcohol-based solvent, a ketone-based solvent, an ether-based solvent, a hydrocarbon-based solvent, and the like can be used, and an alcohol-based solvent and a ketone-based solvent are particularly preferred.

Examples of the alcohol-based solvent include methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol.
Examples of the ketone-based solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
Examples of the ether-based solvent include diethyl ether, dipropyl ether, tetrahydrofuran, 1,4-dioxane, and the like.
Examples of the hydrocarbon-based solvent include aliphatic hydrocarbon-based solvents such as pentane and hexane, alicyclic hydrocarbon-based solvents such as cyclohexane, and aromatic hydrocarbon-based solvents such as benzene, toluene, and xylene.

The organosilicon compound (C) is preferably 100% by mass or more of the composition containing the organosilicon compound (C), preferably 0.05% by mass or more, more preferably 0.08% by mass or more, still more preferably 0.1% by mass or more, and more preferably 2% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1.2% by mass or less.

Examples of the method for forming the coating layer (c) 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 cloth method and the like are particularly preferably a spin coating method.

Before applying the composition containing the organosilicon compound (C), it is preferable to perform easy adhesion treatment on the resin substrate layer (s). 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 layer (c) and the resin substrate layer (s) can be further improved.

After the composition containing the organosilicon compound (C) is applied to form a layer (c), the composition containing the organosilicon compound (A) is coated, and the composition is hardened at normal temperature, thereby making it possible to A water-repellent layer (r) is formed.

The composition containing the organosilicon compound (A) preferably further contains the organosilicon compound (B), and usually also contains a solvent (D). 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 a tertiary amine in which all hydrogen atoms of ammonia are substituted with a fluoroalkyl group (particularly a perfluoroalkyl group) is preferred. 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).

In addition, the composition for forming the water-repellent layer (r) may contain a silanol condensation catalyst, an antioxidant, a rust inhibitor, an ultraviolet absorber, a light stabilizer, and an antifungal agent within a range not hindering the effects of the present invention. , Antibacterial agents, biological adhesion preventive agents, deodorants, pigments, flame retardants, antistatic agents and other additives.

The water-repellent layer (r) can be formed by applying the composition for forming the water-repellent layer (r) to the layer (c) and drying it. Examples of the method for applying the composition for forming the water-repellent layer (r) include a dip coating method, a roll coating method, a bar coating method, a spin coating method, a spray coating method, a mold coating method, and a gravure plate. Printing coating method and the like.

The conditions after applying the composition for forming the water-repellent layer (r) on the layer (c) are not particularly limited, as long as it is left to stand at room temperature and in the atmosphere, 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 (calcined) at a temperature of 50 ° C to 300 ° C, preferably 100 ° C to 200 ° C, for about 10 minutes to 60 minutes.

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

When the composition for forming the water-repellent layer (r) contains an organic silicon compound (B), the content of the organic silicon compound (B) in the composition is, for example, 0.01% by mass or more, and preferably 0.03% by mass or more. In addition, it is preferably 0.3% by mass or less, and more preferably 0.2% 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.
[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]
Contain KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd., N-2- (aminoethyl) -3-aminopropyltrimethoxysilane) as an organosilicon compound (C) at room temperature, 0.25 mass % And containing a 99.75 mass% solution of methyl ethyl ketone as a solvent (E) to obtain a solution for forming a layer (c). The obtained solution was applied to the surface to be coated using an atmospheric piezoelectric slurry device (manufactured by Fuji Machinery Manufacturing Co., Ltd.) using OPTICOAT MS-A100 (spin coater) manufactured by MIKASA Co., Ltd. On the base material subjected to the activation treatment, the substrate was coated with a coating liquid amount of 200 μl, a rotation speed of 2000 rpm, and a rotation time of 20 seconds to obtain a layer (c).

Next, FC-3283 (C ₉ F ₂₁ N, Fluorinert) represented by the following formula (1) as the organosilicon compound (A) (solvent (D)) was used as a solvent (D). (Manufactured by 3M), and stirred at room temperature for a predetermined time to obtain a solution for forming a water-repellent layer (r). The proportion of the organic silicon compound (A) in the solution for forming the water-repellent layer (r) was 0.085% by mass. The solution for forming the water-repellent layer (r) was applied onto the layer (c) using a spray coater manufactured by Apeiros Co., Ltd. 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. Then, it baked at 120 degreeC for 20 minutes, and obtained the laminated body which consists of a resin base material layer (s), a layer (c), and a water-repellent layer (r) in this order.

[Chemical 18]

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]
In addition to the solution for forming the water-repellent layer (r), 0.05% by mass of FAS13E (C ₆ F ₁₃ -C ₂ H ₄ -Si (OC ₂ H ₅ ) ₃ ) as the organosilicon compound (B) in the solution is further included. Except for Tokyo Chemical Industry Co., Ltd.), a laminated body was obtained in the same manner as in Example 1.

[Comparative Example 1]
A laminated layer was obtained in the same manner as in Example 1 except that KBM-5103 (3-propenyloxypropyltrimethoxysilane produced by Shin-Etsu Chemical Co., Ltd.) was used in the solution for forming the layer (c) instead of KBM-603. body.

[Comparative Example 2]
A laminate was obtained in the same manner as in Example 2 except that KBM-5103 (3-propenyloxypropyltrimethoxysilane produced by Shin-Etsu Chemical Co., Ltd.) was used in the solution for forming the layer (c) instead of KBM-603. body.

[Example 3]
As the organosilicon compound (C), N-2- (aminoethyl) -3-aminopropyltrimethoxysilane described in Japanese Patent Application Laid-Open No. 2012-197330, which is represented by the following formula, is used. A reaction product (trade name; X-12-5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.) with chloropropyltrimethoxysilane was included in a layered product in the same manner as in Example 2 except that it contained 0.50% by mass.

[Chemical 19]

[Comparative Example 3 and Comparative Example 4]
Used in KBM3086 (1,8-bis (trimethylsilyl) octane, manufactured by Shin-Etsu Chemical Co., Ltd.) without an amine group in the molecule, and contains 0.25% by mass or 0.50% by mass, instead of silicone A laminated body was obtained in the same manner as in Example 2 except for the compound (C).

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 added dropwise to the obtained film, and the contact angle of water was measured by a droplet method (analysis method: θ / 2 method) using a contact angle measuring device (produced by Kyowa Interface Science Co., DM700).

(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]

In Examples 1 to 3 where the layer (c) was formed using the specific organosilicon compound (C) of the present invention, the water contact angle after the chemical resistance test was 82.0 ° or more (especially 90 ° or more) and Good. In contrast, in Comparative Examples 1 to 4, where an organosilicon compound different from the organosilicon compound (C) was used instead of the organosilicon compound (C) of the present invention, water contact after the chemical resistance test The angle produced a drop.
[Industrial availability]

The laminated body of the present invention can be used in display devices such as touch panel displays, optical elements, semiconductor elements, building 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 (9)

A laminated body comprising a water-repellent layer (r) and a resin substrate layer (s) formed of a composition containing an organosilicon compound (C) having a silicon atom having a hydrolyzable group and having an amine group or an amine skeleton. The layer (c) is formed by laminating, and the laminated body is characterized in that the water-repellent layer (r) is a layer formed of a composition containing an organic silicon compound (A) represented by the following formula (a1) : 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. The laminated body according to item 1 of the scope of the patent application, wherein the organosilicon compound (C) is an organosilicon compound represented by the following formula (c1) or an organosilicon compound represented by the following formula (c10): 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 X, multiple X may be different, Y is -NH-, or -S-, in the case of multiple Y, multiple Y may be different, and Z is B Group, α-methylvinyl group, styryl group, methacryl group, acryl group, amine group, isocyanate group, isocyanurate group, epoxy group, fluorenyl group or mercapto group, p1 is 1 ～ An integer of 20, p2, p3, and p4 are each independently an integer of 0 to 10, p5 is an integer of 1 to 10, and p6 is an integer of 1 to 3. About Z-, -Si (X) _p6 (R ^x5 ) _{3 -p6,} p1 th ^{- {C (R x1) (} R x2)} -, p2 a ^{- {C (Rf x1) (} Rf x2)} -, p3 a ^{- {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 and contain at least one of amine group and -NH-; In the formula (c10), R ^x10 and R ^x11 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When a plurality of R ^x10 are present, a plurality of R ^x10 may be different from each other. In the case of a single R ^x11 , a plurality of R ^x11 may be different, and Rf ^x10 and Rf ^x11 are each independently one or more hydrogen atoms substituted with fluorine atoms of 1 to 20 carbon or fluorine atoms. Rf ^x10 a case, a plurality of different Rf ^x10 respectively, in the case where there are a plurality of Rf ^x11, Rf ^x11 plurality of respectively different, R ^x50 and R ^{x5 0} 'are each independently 1 to 20 carbon atoms, alkyl, in the presence of 'case, a plurality of R ^x50 and R ^{x5 0'} and a plurality of R ^x50 R ^{x5 0} may be different from each other, X ²⁰ and X ²¹ are each independently a hydrolyzable group, in the presence of a plurality of X ²⁰ In the case of X ²¹ and X ²¹ , multiple X ²⁰ and X ²¹ may be different. P10 is an integer of 1 to 30, p20 is an integer of 0 to 30, and p10 or p20 is attached and enclosed in parentheses. At least one of the repeating units is substituted with an amine skeleton -NR ^100- , wherein R ¹⁰⁰ in the amine skeleton is a hydrogen atom or an alkyl group, and p60 and p60 ′ are each independently 1 to 3 Integer, about p10-{C (R ^x10 ) (R ^x11 )}-, p20-{C (Rf ^x10 ) (Rf ^x11 )}-, there is no need to make p10 or p20 consecutive, but in any order The bonds are arranged with -Si (X ²⁰ ) _p60 (R ^x50 ) _3-p60 and -Si (X ²¹ ) _{p60 '} (R ^x50 ') _{3-p60 '} at both ends. The laminated body according to item 1 or item 2 of the scope of patent application, wherein the water-repellent layer (r) is composed of an organosilicon compound (A) represented by the above formula (a1) and represented by the following formula (b1) The layer formed by the composition of the organosilicon compound (B) represented by): 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. The laminated body according to item 2 of the scope of patent application, wherein the organosilicon compound (C) represented by the formula (c1) is represented by the following formula (c2): In the formula (c2), X ¹ is a methoxy group or an ethoxy group, and when a plurality of X ¹ are present, the plurality of X ¹ may be different, Y ¹ is -NH-, and Z ¹ is an amine group or mercapto, R ^x51 is an alkyl group having 1 to 20 carbon atoms, and in a case where 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, r is An integer from 0 to 5. The laminated body according to item 2 of the scope of patent application, wherein the organosilicon compound (C) represented by the formula (c10) is represented by the following formula (c20): In the formula (C20), X ³⁰ and X ³¹ are each independently a hydrolyzable group, in the presence of a plurality of X ³⁰ and X ^31, X ³⁰ and X ³¹ plurality may be different from each other, R ^x55 and R ^x56 are each independently an alkyl group having 1 to 20 carbon atoms, in the presence of a case where a plurality of R ^x55 and R ^x56, a plurality of R ^x55 and R ^x56 respectively different, about _2w -C _w H -, methylene portion thereof At least one of the groups is substituted with an amine skeleton -NR ^100- , R ¹⁰⁰ is a hydrogen atom or an alkyl group, and w is an integer of 1 to 30 (except for the number of methylene groups substituted with an amine skeleton), p65 and p66 They are each independently an integer of 1 to 3. The laminated body according to any one of claims 1 to 5, in which the resin substrate layer (s) is an acrylic resin-based hard coat layer. A method for manufacturing a laminated body, which is the method for manufacturing a laminated body according to any one of claims 1 to 6 of the scope of patent application, which is characterized by comprising: A step of coating the resin substrate layer (s) with a composition containing the organosilicon compound (C) to form a layer (c); and The step of coating the layer (c) with a composition containing the organosilicon compound (A) and hardening the composition at normal temperature to form a water-repellent layer (r). The method for manufacturing a laminated body according to item 7 of the scope of patent application, wherein in the step of forming the water-repellent layer (r), the composition containing the organic silicon compound (A) further includes the organic silicon compound (B). The method for manufacturing a laminated body according to item 7 or item 8 of the scope of the patent application, wherein the resin substrate layer (s) is subjected to a plasma treatment, and the plasma-treated surface coating includes the Composition of organosilicon compound (C).