WO2019093259A1

WO2019093259A1 - Laminate

Info

Publication number: WO2019093259A1
Application number: PCT/JP2018/040944
Authority: WO
Inventors: 友宏伊藤; 泰治島崎; みちる上原
Original assignee: 住友化学株式会社
Priority date: 2017-11-07
Filing date: 2018-11-05
Publication date: 2019-05-16
Also published as: JP6934002B2; TWI760576B; CN111247001A; JP2019084827A; KR20200085310A; KR102570512B1; TW201922497A

Abstract

In some cases where a coating film, which is formed from a composition that contains a compound having a perfluoropolyether structure, is laminated on a substrate with another layer being interposed therebetween, the thus-obtained laminate is exposed to a chemical such as an alcohol depending on the intended use thereof; and in these cases, the laminate is required to maintain good properties even after the exposure to the chemical. Consequently, 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

Laminate

The present invention relates to a laminate.

A film formed from a composition containing a compound having a perfluoropolyether structure has a very small surface free energy, and thus, a display device such as a touch panel display, an optical element, a semiconductor element, a building material, a window of a car or a building It is used as an antifouling coating or a water and oil repellent coating in various fields such as glass.

When a composition containing a compound having a perfluoropolyether structure is applied to a substrate, the above-described composition is applied to the substrate after forming another layer such as a primer layer on the substrate in advance, and the antifouling coating or water repellency It may form an oil repellent coating.

For example, Patent Document 1 discloses 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, A hardcoat film is disclosed, wherein Z) has a water contact angle of 110 ° or more. In order to form the surface layer (Z), it is preferable to use a fluorine-based compound having a polyperfluoropolyether chain, and to form a primer layer (Y), 3-acryloxypropyltrilyl. It is stated that silane compounds such as methoxysilane are preferred.

JP, 2015-120253, A

When a film formed from a composition containing a compound having a perfluoropolyether structure is laminated to a substrate through another layer, it may be exposed to chemicals such as alcohol depending on the application, and such In such a case, it is required to be able to maintain good performance (such as water repellency) even after exposure to chemicals (hereinafter referred to as chemical resistance).

Therefore, the present invention is a laminate in which a layer formed from a composition containing a compound having a perfluoropolyether structure is laminated to a substrate via another layer, and the laminate is excellent in chemical resistance. Intended to provide.

The present invention which achieved the above-mentioned subject is as follows.

[1] A water repellent layer (r) and a resin base layer (s) are organosilicon compounds having a silicon atom to which a hydrolyzable group is bonded, and an organosilicon compound (C) having an amino group or an amine skeleton A laminate formed via a layer (c) formed of a composition containing
The water repellent layer (r) is a layer formed from a composition containing an organosilicon compound (A) represented by the following formula (a1):

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 1 to 20 carbon atoms, if R ¹¹ there are a plurality may be different plural R ¹¹ are each, R ¹² is more if present may be different plurality of R ¹² each may be the case where R ¹³ there are a plurality of different plural R ¹³ are each,
^{^{^{E 1, E 2, E 3}}} , E 4, and E ⁵ is, independently represents a hydrogen atom or a fluorine atom, if E ¹ there are a plurality may be different plurality of E ^1, respectively, E ² may be the case where there are plural different multiple E ² respectively, when the E ³ there are a plurality may be different plurality of E ³ respectively, the plurality of E if E ⁴ there are a plurality of ⁴ may be different from each other,
G ¹ and G ² are each independently a di- to 10-valent organosiloxane group having a siloxane bond,
J ¹ , J ² and J ³ are each independently a hydrolyzable group _or- (CH ₂ ) _{e 6} -Si (OR ¹⁴ ) ₃ , e 6 is 1 to 5 and R ¹⁴ is a methyl group or an ethyl group, if J ¹ there are a plurality may be different plurality of J ^1, respectively, when J ² there are a plurality may be different plurality of J ^2, respectively, J ³ is more If present, multiple J ³ may be different from each other,
L ¹ and L ² each independently represent an oxygen atom, a nitrogen atom, or a divalent C 1-12 linking group which may contain a fluorine atom, and when a plurality of L ¹ are present, plural L ^{1 s} and L 2 s L ¹ is may be different from each, when L ² there are a plurality may be different plurality of L ^2, respectively,
d11 is 1 to 9,
d12 is 0 to 9,
a10 and a14 are each independently 0 to 10,
a11 and a15 are each independently 0 or 1, and
a12 and a16 are each independently 0 to 9,
a13 is 0 or 1;
and a21, a22 and a23 are each independently 0 to 2;
e1, e2 and e3 are each independently 1 to 3.

[2] The lamination 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) body.

In the above formula (c1),
^{^{^{R x1, R x2, R x3}}} , R x4 are each independently a hydrogen atom or a carbon atoms is an alkyl group of 1 to 4, if R ^x1 there exist a plurality differ plurality of R ^x1, respectively may, if R ^x2 there are a plurality may be different plural R ^x2 are each, it may be the case where R ^x3 there are a plurality of different plural R ^x3 are each if R ^x4 there are multiple And each R ^{x 4} may be different from each other,
Each of Rf ^x1 , Rf ^x2 , Rf ^x3 , and Rf ^x4 independently represents an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms have been substituted with a fluorine atom, or a fluorine atom, and a plurality of Rf ^x1 are present If you want may be different multiple of Rf ^x1, respectively, different from the case where Rf ^x2 there is more than one may be different from each of the plurality of Rf ^x2, a plurality of Rf ^x3 If Rf ^x3 there is more than one, respectively even if well, if Rf ^x4 there are a plurality may be different plurality of Rf ^x4, respectively,
R ^x5 is an alkyl group having 1 to 20 carbon atoms, may be the case where R ^x5 there are a plurality of different plural R ^x5 are each,
X is a hydrolyzable group, and when a plurality of X are present, the plurality of X may be different from each other,
Y is -NH- or -S-, and when there are a plurality of Y, a plurality of Y may be different from each other,
Z is a vinyl group, α-methyl vinyl group, styryl group, methacryloyl group, acryloyl group, amino group, isocyanate group, isocyanurate group, epoxy group, ureido group, or mercapto group,
p1 is an integer of 1 to 20, p2, p3 and p4 are each independently an integer of 0 to 10, and p5 is an integer of 1 to 10,
p6 is an integer of 1 to 3 and
_{Z -, - Si (X)} p6 (R x5) 3-p6, p1 amino ^{- {C (R x1) (} R x2)} -, p2 amino ^{- {C (Rf x1) (} Rf x2)} - , P3-{Si (R ^x3 ) (R ^x4 )}-, p4-{Si (Rf ^x3 ) (Rf ^x4 )}-, p5 -Y- are Z- and -Si (X ) _P6 (R ^{x 5} ) _3-p6 is terminated, and so long as -O- is not linked to -O-, they are linked in any order and contain at least one of amino group and -NH-.

In the above formula (c10),
R ^x10 and R ^x11 are each independently a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, if R ^x10 there are a plurality may be different plural R ^x10 are each, R ^x11 is When there are two or more R ^{x 11} may be different from each other,
Rf ^x10 and Rf ^x11 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted by a fluorine atom or a fluorine atom, and when there are a plurality of Rf ^{x10, a} plurality of Rf ^x10 well be different from each other, when the Rf ^x11 there is more than one may be different multiple of Rf ^x11, respectively,
And each R ^x50 and R ^x51 is independently an alkyl group having 1 to 20 carbon atoms, may be the case where R ^x50 and R ^x51 there are a plurality of different plural R ^x50 and R ^x51 are each,
X ²⁰ and X ²¹ are each independently a hydrolysable group, if X ²⁰ and X ²¹ there are a plurality may be different plurality of X ²⁰ and X ²¹ are each,
p10 is each independently an integer of 1 to 30, p20 is each independently an integer of 0 to 30, and at least one of the parenthesized repeating units with p10 or p20 attached is R ¹⁰⁰ in the amine skeleton is a hydrogen atom or an alkyl group, which is substituted for the amine skeleton -NR ^100-
p60 and p60 'are each independently an integer of 1 to 3,
The p10-{C (R ^x10 ) (R ^x11 )}-and the p20-{C (Rf ^x10 ) (Rf ^x11 )}-do not have to be p10 or p20 continuous and may be any coupled side by side in this order, both ends is ^{_{-Si (X 20) p60 (R}} x50) 3-p60 and ^{_{-Si (X 21) p60 '(}} R x51) 3-p60'.

[3] The water repellent layer (r) is formed of a composition containing the organosilicon compound (A) represented by the formula (a1) and the organosilicon compound (B) represented by the following formula (b1) The laminated body as described in said [1] or [2] which is a layer.

In the above formula (b1),
Rf ^b10 is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted by a fluorine atom,
R ^b11, R ^b12, R ^b13 and R ^b14 are each independently a hydrogen atom or a carbon atoms is an alkyl group of 1 to 4, if R ^b11 there are a plurality differ plurality of R ^b11 each may, if R ^b12 there are a plurality may be different plural R ^b12 each may be the case where R ^b13 there are a plurality of different plural R ^b13 are each if R ^b14 there are multiple And R ^{b14 's} may be different from each other,
Rf ^b11, Rf ^b12, Rf ^b13 and Rf ^b14 are each independently one or more hydrogen atoms is an alkyl group or a fluorine atom carbon number of 1 to 20 substituted by a fluorine atom, Rf ^b11 multiple presence In the case of multiple Rf ^b11 may be different from each other, when multiple R f ^b12 are present, multiple R f ^b12 may be different from each other, and when multiple R f ^b13 is present, multiple R f ^b13 are different from each other even if well, if Rf ^b14 there are a plurality may be different plurality of Rf ^b14, respectively,
R ^b15 is an alkyl group having 1 to 20 carbon atoms, it may be the case where R ^b15 there are a plurality of different plural R ^b15 are each,
A ¹ is —O—, —C (= O) —O—, —O—C (= O) —, —NR—, —NRC (= O) — or —C (= O) NR— There, wherein R is a hydrogen atom, a fluorine-containing alkyl group of the alkyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms, if a ¹ there are a plurality may be different plurality of a ^1, respectively,
A ² is a hydrolyzable group, if A ² there are a plurality may be different plurality of A ^2, respectively,
b11, b12, b13, b14 and b15 are each independently an integer of 0 to 100,
c is an integer of 1 to 3 and
^{Rf b10 -, - Si (A} 2) c (R b15) 3-c, b11 amino ^{- {C (R b11) (} R b12)} -, b12 amino ^{- {C (Rf b11) (} Rf b12) }-, B13-{Si (R ^b13 ) (R ^b14 )}-, b14-{Si (Rf ^b13 ) (Rf ^b14 )}-, b15 -A ¹ -is Rf ^b10- , As long as -Si (A ² ) _c (R ^b15 ) _3-c is terminated to form no perfluoropolyether structure and -O- is not linked to -O- to -F, they are arranged in any order. Join.

[4] The laminate according to the above [2], wherein the organosilicon compound (C) represented by the formula (c1) is represented by the following formula (c2).

In the above formula (c2),
X ¹ is a methoxy group or an ethoxy group, if X ¹ there are a plurality may be different plurality of X ¹ are each,
Y ¹ is -NH-,
Z ¹ is an amino group or a mercapto group,
R ^x51 is an alkyl group having 1 to 20 carbon atoms, it may be the case where R ^x51 there are a plurality of different plural R ^x51 are each,
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 laminate according to the above [2], wherein the organosilicon compound (C) represented by the formula (c10) is represented by the following formula (c20).

In the above formula (c20),
X ³⁰ and X ³¹ are each independently a hydrolyzable group, when X ³⁰ and X ³¹ there are a plurality may be different plurality of X ³⁰ and X ³¹ are each,
R ^x55 and R ^x56 are each independently, is an alkyl group having 1 to 20 carbons, even if the R ^x55 and R ^x56 there are a plurality of different plural R ^x55 and R ^x56 are each Often,
In -C _w H _2w- , at least one of its partial methylene groups is replaced with an amine skeleton -NR ^100- , and R ¹⁰⁰ is a hydrogen atom or an alkyl group,
w is an integer of 1 to 30 (except the number of methylene groups replacing the amine skeleton),
p65 and p66 are each independently an integer of 1 to 3.

[6] The laminate according to any one of the above [1] to [5], wherein the resin base material layer (s) is an acrylic resin hard coat layer.

[7] A method for producing a laminate according to any one of the above [1] to [6],
Applying a composition containing the organosilicon compound (C) to the resin base material layer (s) to form a layer (c);
Applying a composition containing the organosilicon compound (A) to the layer (c) and curing the composition at normal temperature to form a water repellent layer (r). Method.

[8] In the step of forming the water repellent layer (r), the composition containing the organosilicon compound (A) further contains the organosilicon compound (B). Method.

[9] The laminate according to the above [7] or [8], wherein the resin base material layer (s) is subjected to plasma treatment, and the composition containing the organosilicon compound (C) is applied to the plasma treated surface. Production method.

In the laminate of the present invention, a water repellent layer formed from a composition containing a predetermined organosilicon compound (A) having a perfluoropolyether structure is formed from a composition containing a predetermined organosilicon compound (C) Since it is laminated with the base material via the layer, good chemical resistance can be realized.

In the laminate of the present invention, the water repellent layer (r) and the resin base material layer (s) are laminated via a layer (c) formed of a composition containing a predetermined organosilicon compound (C) . The water repellent layer (r), the layer (c) and the resin base material layer (s) will be sequentially described below.

1. Water repellent layer (r)
The water repellent layer (r) is a layer formed from a composition containing an organosilicon compound (A) represented by the following formula (a1), that is, has a structure derived from the organosilicon compound (A) . As described later, since the organosilicon compound (A) has a hydrolysable group and the -SiOH groups of the organosilicon compound (A) formed by hydrolysis are dehydrated and condensed, the water repellent layer (r) is And usually have a condensed structure derived from the organosilicon compound (A).

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 (that is, R ¹¹ , R ¹² and R ¹³ may be identical or different from each other) an alkyl group having 1 to 20 carbon atoms , and the case where R ¹¹ there are a plurality may be different plurality of R ¹¹ each may be the case where R ¹² there are a plurality of different plural R ¹² are each, if R ¹³ there are a plurality of And each of a plurality of R ¹³ 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, and when a plurality of E ¹ is present, a plurality of R ^{13 s} may be different E ¹ of each may be different plurality of E ² respectively when the E ² there are a plurality, it may be the case where E ³ there are a plurality of different multiple E ³ respectively If the E ⁴ there are a plurality of different multiple E ⁴ each It may be,
G ¹ and G ² are each independently a di- to 10-valent organosiloxane group having a siloxane bond,
J ¹ , J ² and J ³ are each independently a hydrolyzable group _or- (CH ₂ ) _{e 6} -Si (OR ¹⁴ ) ₃ , e 6 is 1 to 5 and R ¹⁴ is a methyl group or an ethyl group, if J ¹ there are a plurality may be different plurality of J ^1, respectively, when J ² there are a plurality may be different plurality of J ^2, respectively, J ³ is more If present, multiple J ³ may be different from each other,
L ¹ and L ² each independently represent an oxygen atom, a nitrogen atom, or a divalent C 1-12 linking group which may contain a fluorine atom, and when a plurality of L ¹ are present, plural L ^{1 s} and L 2 s L ¹ is may be different from each, when L ² there are a plurality may be different plurality of L ^2, respectively,
d11 is 1 to 9,
d12 is 0 to 9,
a10 and a14 are each independently 0 to 10,
a11 and a15 are each independently 0 or 1, and
a12 and a16 are each independently 0 to 9,
a13 is 0 or 1;
and a21, a22 and a23 are each independently 0 to 2;
e1, e2 and e3 are each independently 1 to 3.

The organosilicon compound (A) has a perfluoropolyether structure represented by ^Rfa1 as represented by the above formula (a1), and a hydrolyzable group represented by J ² or-(CH ₂ ) _It has at least one _{e 6} -Si (OR ¹⁴ ) ₃ (wherein R ¹⁴ is a methyl group or an ethyl group). The perfluoropolyether structure is a structure in which all hydrogen atoms of the polyoxyalkylene group are replaced with fluorine atoms, and it can be said that a perfluorooxyalkylene group can impart water repellency to the obtained film. Further, it is a compound which can be a matrix of a film obtained by bonding J ² together with organic silicon compounds (A) or with other monomers through a polymerization reaction (particularly a polycondensation reaction).

Rf ^a1 _{_{is, -O- (CF 2 CF 2 O}} ) e4 -, or _{_{_{-O- (CF 2 CF 2 CF 2}}} O) e5 - is preferred. Each of e4 and e5 is 15 to 80.

Each of R ¹¹ , R ¹² and R ¹³ is preferably independently an alkyl group having 1 to 10 carbon atoms.

Each of L ¹ and L ² is preferably independently a divalent C ¹ -C 5 linking group containing a fluorine atom.

G ¹ and G ² are preferably each independently a divalent 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 ) _{e 6} -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), a14 is preferably 1 to 6 (more preferably 1) A3 is preferably 0, a16 is preferably 0 to 6, and all of a21 to a23 are preferably 0 or 1 (more preferably 0), and d11 is preferably 1 to 5 (more preferably 1) -3) and d12 are preferably 0 to 3 (more preferably 0 or 1), and all of e1 to e3 are preferably 3. In addition, a13 is preferably 1.

As compound (A), the formula (a1) Rf ^a1 is -O- in _{_{_{(CF 2 CF 2 CF 2 O}}} ) e5 - a and, e5 is 35-50, carbon both L ¹ and L ² And each of E ¹ , E ² , and E ³ is a hydrogen atom, and E ⁴ and E ⁵ are a hydrogen atom or a fluorine atom; J ¹ , J ² , and J ³ all also a methoxy group or an ethoxy group (particularly methoxy group), a10 is 1 ~ 3, a11 is 0, a12 is 0 to 5, a13 is 1, a14 is 2 And a15 is 0, a16 is 0 to 6, and a21 to a23 are each independently 0 or 1 (more preferably all of a21 to a23 are 0), and d11 is 1 Using a compound wherein d12 is 0 or 1 and e1 to e3 are all 3 It is preferable.

The compound in Example to be described later Compound a to be used as (A), is represented by the formula (a1), Rf ^a1 is _{_{_{-O- (CF 2 CF 2 CF 2}}} O) 43 - a and, L ¹ and L ² is all-(CF ₂ )-, E ¹ , E ² and E ³ are all hydrogen atoms, E ⁵ is a fluorine atom and J ¹ and J ² are all methoxy groups , A10 is 2, a11 is 0, a12 is 0-5, 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 And e2 are both 3.

The compound (A), the formula (a1) Rf ^a1 is -O- in _{_{_{(CF 2 CF 2 CF 2 O}}} ) e5 - a and, e5 is 25 ~ 40, L ¹ is a fluorine atom and an oxygen atom L ² is a C 1 -C 3 perfluoroalkylene group, E ² and E ³ are both hydrogen atoms, and E ⁵ is a fluorine atom. Yes, J ² is — (CH ₂ ) _{e 6} —Si (OCH ₃ ) ₃ , e 6 is 2 to 4, a 10 is 1 to 3, a 11 is 0, a 12 is 0, a 13 Is 0, a14 is 2 to 5, a15 is 0, a16 is 0, and a21 to a23 are each independently 0 or 1 (more preferably all of a21 to a23 are 0) It is also preferable to use a compound in which 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).

In the above formula (a2-1),
^Rfa21 is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted by a fluorine atom,
^{^{^{Rf a22, Rf a23, Rf a24}}} , and Rf ^a25 are each independently, 1 or more hydrogen atoms is an alkyl group or a fluorine atom carbon number of 1 to 20 substituted by a fluorine atom, Rf ^a22 plurality if present may be different plurality of Rf ^a22 respectively, if Rf ^a23 there are a plurality may be different plurality of Rf ^a23, respectively, a plurality of Rf ^a24 If Rf ^a24 are present in plural It may be different, if Rf ^a25 there are a plurality may be different plurality of Rf ^a25 respectively,
R ^20, R ^21, R ^22, and R ²³ are each independently hydrogen atom or an alkyl group having 1 to 4 carbon atoms, if R ²⁰ there are a plurality differ plurality of R ²⁰ each may, if R ²¹ there are a plurality may be different plurality of R ²¹ each may be the case where R ²² there are a plurality of different plural R ²² are each, if R ²³ there are a plurality of And each R ²³ may be different from each other,
R ²⁴ is an alkyl group having 1 to 20 carbon atoms, it may be the case where R ²⁴ there are a plurality of different plural R ²⁴ are each,
M ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, if M ¹ there are a plurality may be different plurality of M ^1, respectively,
M ² is a hydrogen atom or a halogen atom,
M ³ represents -O-, -C (= O) -O-, -O-C (= 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), and when there are a plurality of M ^{3 's,} Several M ³ may be different from each other,
M ⁴ is a hydrolysable group, if M ⁴ there are a plurality may be different plurality of M ^4, 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 of 1 to 20,
f17 is an integer of 0 to 2;
g1 is an integer of 1 to 3 and
^{^{Rf a21 -, M 2 -,}} f11 amino ^{- {C (R 20) (} R 21)} -, f12 amino ^{- {C (Rf a22) (} Rf a23)} -, f13 amino - {Si (R ^{^{22) (R 23)} -}} , f14 amino ^{- {Si (Rf a24) (} Rf a25)} -, f15 amino -M ³ -, and f16 amino _{^{- [CH 2 C (M 1}} ) {(CH _{_{^{2) f17 -Si (M 4)}}} g1 (R 24) 3-g1}] - is, Rf ^a21 -, M ² - is terminated, the arrangement in order to form a perfluoropolyether structure at least in part, and As long as -O- is not linked to -O- to -F, they are linked in any order. That is, the formula (a2-1) is not necessarily f11 amino ^{- {C (R 20) (} R 21)} - are continuous, f12 amino ^{- {C (Rf a22) (} Rf a23)} - is continuously , F13-{Si (R ²² ) (R ²³ )}-are continuous, f14-{Si (Rf ^a24 ) (Rf ^a25 )}-is continuous, f15 -M ³ -is continuous _{And f16-} [CH ₂ C (M ¹ ) {(CH ₂ ) _{f 17} -Si (M ⁴ ) _{g 1} (R ²⁴ ) _{3-g 1} }]-are not continuously arranged 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) - such as, you can be respectively are arranged in any order is there.

^Rfa21 is preferably an alkyl group of 1 to 10 carbon atoms substituted with one or more fluorine atoms, more preferably a perfluoroalkyl group of 1 to 10 carbon atoms, and still more preferably 1 to 10 carbon atoms 5 is a perfluoroalkyl group.

Rf ^a22 , R f ^a23 , R f ^a24 and R f ^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 by a fluorine atom, Preferably all are fluorine atoms.

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

R ²⁴ is preferably an alkyl group of 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 hydrogen atoms.

M ² is preferably a hydrogen atom.

M ³ is preferably —C (= O) —O—, —O—, —O—C (= O) —, 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.

Preferably, 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 particularly preferably f13 and f14 is 0 It is.

F15 is preferably 1⁄5 or more of the total value of f11, f12, f13 and f14, and is not more than the total value of f11, f12, f13 and f14.

The f12 is preferably 20 to 600, more preferably 20 to 200, and still more preferably 50 to 200 (more preferably 30 to 150, particularly 50 to 150, most preferably 80 to 140). The f 15 is preferably 4 to 600, more preferably 4 to 200, and still 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 still more preferably 50 to 200.

F16 is preferably 1 to 18. More preferably, it is 1-15. More preferably, it is 1 to 10.

F17 is preferably 0 to 1.

G1 is preferably 2 to 3, and more preferably 3.

f11 amino ^{- {C (R 20) (} R 21)} -, f12 amino ^{- {C (Rf a22) (} Rf a23)} -, f13 amino ^{- {Si (R 22) (} R 23)} - , f14 amino ^{- {Si (Rf a24) (} Rf a25)} -, and f15 amino -M ³ - order of as long as arranged in the order of forming the perfluoropolyether structure at least in part, in the formula Although it is optional, preferably the parenthesized repeating unit (ie,-{C ( ^Rfa22 ) ( ^Rfa23 )}-) attached with f12 on the most fixed end side (the side bonded to a silicon atom) is , most free end repeating units in parentheses are given the f11 ^{(i.e., - {C (R 20)} (R 21)} -) located at the free end than, more preferably most fixed end Parenthesized repeat units with f12 and f14 on the side (ie,-{C (Rf ^a22 ) (Rf ^a23 )}- ^and- {Si (Rf ^a24 ) (Rf ^a25 )}-) are the repeating units bracketed with f11 and f13 at the most free end (ie,-{- It is located closer to the free end than C (R ²⁰ ) (R ²¹ )}-and-{Si (R ²² ) (R ²³ )}-).

In the above 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- M ⁴ is all methoxy, ethoxy or chlorine (in particular methoxy or ethoxy), M ¹ and M ² are both hydrogen, f 11 is 0, f 12 is 30 to 150 It is preferable that f15 is 30 to 60, f13 and f14 are 0, f17 is 0 to 1 (particularly 0), g1 is 3 and f16 is 1 to 10.

Incidentally, the compounds a to be used as compound (A) in Example to be described later, is represented by the above formula (a2-1), Rf ^a1 is C ₃ F ₇ - a and, both Rf ^a22 and Rf ^a23 is a fluorine atom There is f11 = f13 = f14 = 0, f12 is 131, f15 is 44, f16 is 1 ~ 6, f17 is 0, M ¹ and M ² is a hydrogen atom, M ³ is -O-, M ⁴ Is a methoxy group, and g1 is 3.

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

In the above formula (a2-2),
^{Each of Rfa26} , ^Rfa27 , ^Rfa28 and ^Rfa29 is independently an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted by a fluorine atom, and ^Rfa26 is plural. if present may be different plurality of Rf ^a26 respectively, if Rf ^a27 there are a plurality may be different plurality of Rf ^a27, respectively, a plurality of Rf ^a28 If Rf ^a28 are present in plural It may be different, if Rf ^a29 there are a plurality may be different plurality of Rf ^a29 respectively,
R ^25, R ^26, R ^27, and R ²⁸ are each independently hydrogen atom or an alkyl group having 1 to 4 carbon atoms, if R ²⁵ there are a plurality differ plurality of R ²⁵ each may, if R ²⁶ there are a plurality may be different plurality of R ²⁶ each may be the case where R ²⁷ there are a plurality of different plural R ²⁷ are each, if R ²⁸ there are a plurality of And each R ²⁸ may be different from each other,
R ^29, and R ³⁰ are each independently an alkyl group having 1 to 20 carbon atoms, if R ²⁹ there are a plurality may be different plural R ²⁹ are each, R ³⁰ there are a plurality of If multiple R ³⁰ may be different,
M ⁷ is —O—, —C (= O) —O—, —O—C (= O) —, —NR—, —NRC (= O) — or —C (= O) NR— There, wherein R is a hydrogen atom, a fluorine-containing alkyl group of the alkyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms, if M ⁷ there are a plurality may be different plurality of M ^7, respectively,
M ^5, M ⁹ are each independently hydrogen atom or an alkyl group having 1 to 4 carbon atoms, if M ⁵ there are a plurality may be different plurality of M ^5, respectively, M ⁹ are multiple If present, multiple Ms ⁹ may be different from each other,
M ⁶ and M ¹⁰ each independently represent a hydrogen atom or a halogen atom,
M ^8, and M ¹¹ are each independently a hydrolysable group, if M ⁸ there are a plurality may be different plurality of M ^8, respectively, of a plurality if M ¹¹ there are a plurality of M ¹¹ may be different from each other,
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 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- , f 21-{C (R ²⁵ ) (R ²⁶ )}-, f ^22- {C (R f a ²⁶ ) (R f a ²⁷ )}-, f ^23- {Si (R ^{^{27) (R 28)} -}} , f24 amino ^{- {Si (Rf a28) (} Rf a29)} -, f25 amino -M ⁷ -, f26 amino _{^{- [CH 2 C (M 5}} ) {(CH 2 _{^{_{) f27 -Si (M 8) g2}}} (R 29) 3-g2}], and f28 amino _{^{- [CH 2 C (M 9}} ) {(CH 2) f29 -Si (M 11) g3 (R 30) 3 _-g3 }] are arranged in the order in which M ¹⁰ -and M ⁶ -are terminated and at least a part of them form a perfluoropolyether structure, and in any order as long as -O- is not continuous with -O- Combine with Bonding in arbitrary order is the same as described in the above formula (a2-1), and each repeating unit is continuously arranged in the order as described in the above formula (a2-2) It is not limited to the meaning.

In the above formula ^{(a2-2), Rf a26, Rf} a27, Rf a28, and Rf ^a29 are all fluorine atoms, M ⁷ are all -O-, all methoxy groups M ⁸ and M ¹¹ are, ethoxy group Or a chlorine atom (especially a methoxy group or an ethoxy group), and M ⁵ , M ⁶ , M ⁹ and M ¹⁰ are all hydrogen atoms, f 21 is 0, f 22 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 (particularly preferably 0), g2 and g3 are 3, and f26 and f28 are preferably 1 to 10.

More specific examples of the compound (A) include compounds of the following formula (a3).

In the above formula (a3), R ³⁰ is a perfluoroalkyl group having 2 to 6 carbon atoms, and R ³¹ and R ³² are each independently a perfluoroalkylene group having 2 to 6 carbon atoms, R ³³ is a trivalent saturated hydrocarbon group having 2 to 6 carbon atoms, and R ³⁴ is an alkyl group having 1 to 3 carbon atoms. The number of carbon atoms of R ³⁰ , R ³¹ , R ³² and R ³³ is 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.

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

In the above 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 2 to 5 carbon atoms 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, each of which is a fluoroalkylene group in which a part of hydrogen atoms of the alkylene group is substituted with fluorine is there. 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, still more preferably 6,000 or more, particularly preferably 7,000 or more, 000 or less is preferable, More preferably, it is 20,000 or less, More preferably, it is 15,000 or less.

The water repellent layer (r) is preferably a layer formed from a composition containing an organosilicon compound (B) represented by the following formula (b1) together with the above-mentioned organosilicon compound (A). As described later, the organosilicon compound (B) has a hydrolysable group, and usually an organosilicon compound (-SiOH group of the organosilicon compound (B) formed by hydrolysis is generated by hydrolysis) In a preferred embodiment, the water repellent layer (r) is a condensation derived from the organosilicon compound (A) in order to dehydrate and condense with the -SiOH group of A) and / or the -SiOH group of the organosilicon compound (B) formed by hydrolysis. Along with the structure, it has a condensed structure derived from the organosilicon compound (B).

In the above formula (b1),
Rf ^b10 is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted by a fluorine atom,
^{^{^{R b11, R b12, R b13}}} , R b14 are each independently a hydrogen atom or a carbon atoms is an alkyl group of 1 to 4, if R ^b11 there are a plurality differ plurality of R ^b11 each may, if R ^b12 there are a plurality may be different plural R ^b12 each may be the case where R ^b13 there are a plurality of different plural R ^b13 are each if R ^b14 there are multiple And R ^{b14 's} may be different from each other,
^{^{^{Rf b11, Rf b12, Rf b13}}} , Rf b14 are each independently one or more hydrogen atoms is an alkyl group or a fluorine atom carbon number of 1 to 20 substituted by a fluorine atom, Rf ^b11 multiple presence In the case of multiple Rf ^b11 may be different from each other, when multiple R f ^b12 are present, multiple R f ^b12 may be different from each other, and when multiple R f ^b13 is present, multiple R f ^b13 are different from each other even if well, if Rf ^b14 there are a plurality may be different plurality of Rf ^b14, respectively,
R ^b15 is an alkyl group having 1 to 20 carbon atoms, it may be the case where R ^b15 there are a plurality of different plural R ^b15 are each,
A ¹ is —O—, —C (= O) —O—, —O—C (= O) —, —NR—, —NRC (= O) — or —C (= O) NR— There, wherein R is a hydrogen atom, a fluorine-containing alkyl group of the alkyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms, if a ¹ there are a plurality may be different plurality of a ^1, respectively,
A ² is a hydrolyzable group, if A ² there are a plurality may be different plurality of A ^2, respectively,
b11, b12, b13, b14 and b15 are each independently an integer of 0 to 100,
c is an integer of 1 to 3 and
^{Rf b10 -, - Si (A} 2) c (R b15) 3-c, b11 amino ^{- {C (R b11) (} R b12)} -, b12 amino ^{- {C (Rf b11) (} Rf b12) }-, B13-{Si (R ^b13 ) (R ^b14 )}-, b14-{Si (Rf ^b13 ) (Rf ^b14 )}-, b15 -A ¹ -is Rf ^b10- , As long as -Si (A ² ) _c (R ^b15 ) _3-c is terminated to form no perfluoropolyether structure and -O- is not linked to -O- to -F, they are arranged in any order. Join.

Each of Rf ^b10 is preferably 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 is preferably a hydrogen atom.

R ^b15 is preferably an alkyl group of 1 to 5 carbon atoms.

A ¹ is preferably —O—, —C (= O) —O—, or —O—C (OO) —.

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.

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 0-15, more preferably 0-10.

B13 is preferably 0 to 5, more preferably 0 to 2.

B14 is preferably 0-4, more preferably 0-2.

B15 is preferably 0-4, more preferably 0-2.

C is preferably 2 to 3, more preferably 3.

The total value of b11, b12, b13, b14 and b15 is preferably 3 or more, preferably 5 or more, and preferably 80 or less, more preferably 50 or less, still more preferably 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 ^{b 11} is 1 to Preferably, 5 and b12 are 0 to 5, and b13, b14 and b15 are all 0 and c is 3.

In the examples described later, when FAS13E used as the compound (B) is represented by the above formula (b1), each of R ^b11 and R ^b12 is a hydrogen atom, b11 is 2, b13, ^b14 and b15 are all 0. , c is 3, a ² is ethoxy ^{group, Rf b10 - {C (Rf} b11) (Rf b12)} b12 - is terminated, C ₆ F ₁₃ - is defined to be.

Specific examples of the compound represented by the above formula (b1) include CF ₃ —Si— (OCH ₃ ) ₃ and C _j F ₂ _j _{+ 1} —Si— (OC ₂ H ₅ ) ₃ (j is 1 to 12). In particular, 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 and C ₈ F ₁₇ -Si- (OC ₂ H ₅ ) ₃ are 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 (CF 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 and the like (k Yes Re is also 5 to 20, preferably 8 to 15). _{_{_{Also, 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 can also be mentioned (m is 1 to 10, preferably 3 to 7 and n is 1 to 5, preferably 2 to 4). ). There may also be mentioned CF ₃ (CF ₂ ) _p- (CH ₂ ) _q -Si- (CH ₂ CH = CH ₂ ) ₃ (p is any of 2 to 10, preferably 2 to 8 and q Are all 1 to 5, 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 can be mentioned (p is any of 2 to 10, preferably 3 to 7 and q is any of 1 to 5, preferably 2 to 4 Is).

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

In the above 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 to 1000 nm.

2. Layer (c)
The layer (c) is an organosilicon compound having a silicon atom to which a hydrolyzable group is bonded, and is formed from a composition containing the organosilicon compound (C) having an amino group or an amine skeleton. The organic silicon compound (C) is preferably one having one or more amine skeletons. In the present specification, the organosilicon compound (C) having an amino group or an amine skeleton may be simply referred to as the organosilicon compound (C). The layer (c) can function as a primer layer of the water repellent layer (r). As described above, the organosilicon compound (C) has a hydrolyzable group bonded to silicon, and the -SiOH groups of the organosilicon compound (C) formed by hydrolysis are dehydrated and condensed, and hence the layer (c) ) Usually have a condensed structure derived from the organosilicon compound (C).

Examples of the organosilicon compound (C) having an amino group or an amine skeleton include an organosilicon compound represented by the following formula (c1) and one or more amine skeletons represented by the following formula (c10); And organosilicon compounds having one or more hydrolyzable groups. Hereinafter, these organosilicon compounds will be described. The above 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 a plurality of amine skeletons are included in the organosilicon compound (C), the plurality of amine skeletons may be the same or different.

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

In the above formula (c1),
^{^{^{R x1, R x2, R x3}}} , and R ^x4 are each independently a hydrogen atom or a carbon atoms is an alkyl group of 1 to 4, if R ^x1 there exist a plurality different plurality of R ^x1, respectively at best, if the R ^x2 there are a plurality may be different plural R ^x2 are each, may be the case where R ^x3 there are a plurality of different plural R ^x3 are each R ^x4 there are a plurality of If multiple ^Rx4s may be different from each other,
Rf ^x1 , R f ^x2 , R f ^x3 and R f ^x4 are each independently an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted by a fluorine atom, and R f ^x1 is plural If there may be different multiple of Rf ^x1, respectively, when the Rf ^x2 there is more than one may be different from each of the plurality of Rf ^x2, a plurality of Rf ^x3 If Rf ^x3 there is more than one, respectively It may be different, if Rf ^x4 there are a plurality may be different plurality of Rf ^x4, respectively,
R ^x5 is an alkyl group having 1 to 20 carbon atoms, may be the case where R ^x5 there are a plurality of different plural R ^x5 are each,
X is a hydrolyzable group, and when a plurality of X are present, the plurality of X may be different from each other,
Y is -NH- or -S-, and when there are a plurality of Y, a plurality of Y may be different from each other,
Z is a vinyl group, α-methyl vinyl group, styryl group, methacryloyl group, acryloyl group, amino group, isocyanate group, isocyanurate group, epoxy group, ureido group, or mercapto group,
p1 is an integer of 1 to 20, p2, p3 and p4 are each independently an integer of 0 to 10, and p5 is an integer of 1 to 10,
p6 is an integer of 1 to 3 and
_{Z -, - Si (X)} p6 (R x5) 3-p6, p1 amino ^{- {C (R x1) (} R x2)} -, p2 amino ^{- {C (Rf x1) (} Rf x2)} - , P3-{Si (R ^x3 ) (R ^x4 )}-, p4-{Si (Rf ^x3 ) (Rf ^x4 )}-, and p5 -Y- are Z- and -Si ( X) _p6 (R ^{x 5} ) _3-p6 is terminated, and so long as -O- is not linked to -O-, they are linked in any order and contain at least one of amino group and -NH- .

Preferably, R ^x1 , R ^x2 , R ^x3 and R ^x4 are hydrogen atoms.

Each of Rf ^x1 , Rf ^x2 , Rf ^x3 and Rf ^x4 is preferably independently an alkyl group having 1 to 10 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted by a fluorine atom.

Preferably, R ^x5 is 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, still more preferably a methoxy group or an ethoxy group.

Y is preferably -NH-.

Z is preferably a methacryloyl group, an acryloyl group, a mercapto group or an amino group, more preferably a mercapto group or an amino group, and still more preferably an amino group.

P1 is preferably 1 to 15, more preferably 2 to 10.

Each of p2, p3 and p4 is preferably independently 0 to 5, more preferably all 0 to 2.

P5 is preferably 1 to 5, more preferably 1 to 3.

P6 is preferably 2 to 3, more preferably 3.

As the organosilicon compound (C), in the above formula (c1), R ^x1 and R ^x2 are both hydrogen atoms, Y is -NH-, and X is an alkoxy group (in particular, a methoxy group or an ethoxy group) And Z is an amino group or mercapto group, p1 is 1 to 10, p2, p3 and p4 are all 0, p5 is 1 to 5 (especially 1 to 3), p6 is 3 It is preferred to use certain compounds.

When N-2- (aminoethyl) -3-aminopropyltrimethoxysilane used as compound (C) in the examples described later is represented by the above formula (c1), Z is an amino group, and R ^x1 and R ^x2 are In any of them, a hydrogen atom, p1 is 5, p2, p3 and p4 are all 0, Y is -NH-, p5 is 1, p6 is 3 and X is a methoxy group.

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

In the above formula (c2),
X ¹ is a hydrolyzable group, when X ¹ there are a plurality may be different plurality of X ¹ are each,
Y ¹ is -NH-,
Z ¹ is an amino group or a mercapto group,
R ^x51 is an alkyl group having 1 to 20 carbon atoms, it may be the case where R ^x51 there are a plurality of different plural R ^x51 are each,
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 halogeno group, a cyano group or an isocyanate group, and more preferably an alkoxy group.

Z ¹ is preferably an amino group.

R ^{x 51} 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, more preferably 3.

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

In addition, the layer (c) is formed of a composition represented by the following formula (c10), which has one or more amine skeletons and an organosilicon compound (C) having two or more hydrolysable groups. be able to.

In the above formula (c10),
R ^x10 and R ^x11 are each independently a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, if R ^x10 there are a plurality may be different plural R ^x10 are each, R ^x11 is When there are two or more R ^{x 11} may be different from each other,
Rf ^x10 and Rf ^x11 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted by a fluorine atom or a fluorine atom, and when there are a plurality of Rf ^{x10, a} plurality of Rf ^x10 well be different from each other, when the Rf ^x11 there is more than one may be different multiple of Rf ^x11, respectively,
R ^x50 and R ^{x50 'is} independently an alkyl group having a carbon number of 1 ~ 20, R ^x50 and R ^x50' even if there are a plurality of different respective plurality of R ^x50 and R ^{x50 '} Often,
X ²⁰ and X ²¹ are each independently a hydrolysable group, if X ²⁰ and X ²¹ there are a plurality may be different plurality of X ²⁰ and X ²¹ are each,
p10 is each independently an integer of 1 to 30, p20 is each independently an integer of 0 to 30, and at least one of the parenthesized repeating units with p10 or p20 attached is R ¹⁰⁰ in the amine skeleton is a hydrogen atom or an alkyl group, which is substituted for the amine skeleton -NR ^100-
p60 and p60 'are each independently an integer of 1 to 3,
The p10-{C (R ^x10 ) (R ^x11 )}-and the p20-{C (Rf ^x10 ) (Rf ^x11 )}-do not have to be p10 or p20 continuous and may be any coupled side by side in this order, both ends is ^{_{-Si (X 20) p60 (R}} x50) 3-p60 and ^{_{-Si (X 21) p60 '(}} R x50') 3-p60 '.

R ^x10 and R ^x11 are preferably hydrogen atoms.

Each of Rf ^x10 and Rf ^x11 is preferably independently an alkyl group having 1 to 10 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted by a fluorine atom.

It is preferable that R ^x50 and R ^{x50 ′ be} an alkyl group having 1 to 5 carbon atoms.

Each of X ²⁰ and X ²¹ is preferably an alkoxy group, a halogeno group, a cyano group or an isocyanate group, more preferably an alkoxy group, still more preferably a methoxy group or an ethoxy group.

The amine skeleton -NR ^100- may be at least one in the molecule as described above, and any of the repeating units in parentheses with p10 or p20 may be substituted for the amine skeleton, , P10 and is preferably part of a repeating unit enclosed in parentheses. A plurality of the amine skeletons may be present, and in this case, the number of the amine skeletons is preferably 1 to 10, more preferably 1 to 5, and still 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 carbon number of the alkylene group between adjacent amine skeletons is included in the total number of p10 or p20.

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

P10 is preferably 1 to 15, more preferably 1 to 10, except for the number of repeating units replaced in the amine skeleton.

P20 is preferably 0 to 5, and more preferably all 0 to 2, except for the number of repeating units replaced in the amine skeleton.

P60 and p60 'are preferably 2 to 3, more preferably 3.

As the organosilicon compound (C), in the above formula (c10), each of R ^x10 and R ^x11 is a hydrogen atom, and X ²⁰ and X ²¹ are an alkoxy group (in particular, a methoxy group or an ethoxy group); And the repeating unit enclosed in parentheses is replaced by at least one amine skeleton -NR ^100- , R ¹⁰⁰ is a hydrogen atom, and p10 is 1 to 10 (provided that the amine skeleton is replaced by an amine skeleton) It is preferable to use a compound in which p20 is 0 and p60 and p60 ′ are 3 except the number of repeating units).

In addition, the reaction product of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and chloropropyltrimethoxysilane described in JP-A-2012-197330, which is used as a compound (C) in Examples described later Name: X-12-5263HP (Shin-Etsu Chemical Co., Ltd. product) is represented by the above formula (c10), R ^x10 and R ^x11 are both hydrogen atoms, p10 is 8, p20 is 0, and two amine skeletons (In both cases, R ¹⁰⁰ is a hydrogen atom), both ends are the same, p60 and p60 ′ are 3 and X ²⁰ and X ²¹ are a methoxy group.

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

In the above formula (c20),
X ³⁰ and X ³¹ are each independently a hydrolyzable group, when X ³⁰ and X ³¹ there are a plurality may be different plurality of X ³⁰ and X ³¹ are each,
R ^x55 and R ^x56 are each independently alkyl groups having 1 to 20 carbons, it may be the case where R ^x55 and R ^x56 there are a plurality of different plural R ^x55 and R ^x56 are each,
In -C _w H _2w- , at least one of its partial methylene groups is replaced with an amine skeleton -NR ^100- , and R ¹⁰⁰ is a hydrogen atom or an alkyl group,
w is an integer of 1 to 30 (except the number of methylene groups replacing the 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 halogeno group, a cyano group or an isocyanate group, and more preferably an alkoxy group.

A plurality of amine skeletons -NR ¹⁰⁰ -may be present, in which case the number of amine skeletons is preferably 1 to 10, more preferably 1 to 5, and 2 to 5 More preferable. 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 carbon number of the alkylene group between adjacent amine skeletons is included in the total number of w.

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

P65 and p66 are preferably an integer of 2 to 3, more preferably 3.

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

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

3. Resin base layer (s)
The material of the resin base material layer (s) of the present invention is not particularly limited, and may be either an organic material or an inorganic material, and the shape of the substrate may be either flat or curved, It may be a combined shape. As organic materials, acrylic resin, polycarbonate resin, polyester resin, styrene resin, acrylic-styrene copolymer resin, cellulose resin, polyolefin resin, vinyl resin (polyethylene, polyvinyl chloride, polystyrene, vinyl benzyl chloride resin, polyvinyl resin Thermoplastic resins such as alcohol, etc .; thermosetting resins such as phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester, silicone resin, urethane resin etc. may be mentioned. Examples of the inorganic material include metals such as iron, silicon, copper, zinc and aluminum, or alloys containing these metals, ceramics, glass and the like. Among these, organic materials are particularly preferable. Among resin substrates, at least one of an acrylic resin, a benzyl chloride resin, an epoxy resin, a silicone resin, and a urethane resin is preferable, and an acrylic resin is particularly preferable.

The resin base material layer (s) in the present invention is a protective layer (hereinafter sometimes referred to as a hard coat layer) provided to protect an article from scratches in applications requiring wear resistance such as displays of electronic devices. The protective layer is more preferably an acrylic resin.

The above-described hard coat layer is a layer having a surface hardness, and the hardness is, for example, 2 H or more in pencil hardness. The hard coat layer may have a single layer structure or a multilayer structure. The hard coat layer contains a hard coat layer resin, and examples of the hard coat layer resin include acrylic resins, epoxy resins, urethane resins, vinyl benzyl chloride resins, vinyl resins or silicone resins, or the like. Examples thereof include ultraviolet curable resins such as mixed resins, electron beam curable resins, and thermosetting resins. In particular, the hard coat layer preferably contains an acrylic resin in order to develop high hardness. It is preferable to contain an epoxy-based resin because a tendency of good adhesion to the water repellent layer (r) through the layer (c) is observed.

The hard coat layer may further contain an ultraviolet absorber, and may contain a metal oxide such as silica or alumina, or an inorganic filler such as polyorganosiloxane. By including such an inorganic filler, the adhesion to the water repellent layer (r) through the layer (c) can be improved. The thickness of the hard coat layer is, for example, 1 to 100 μm.

The laminate of the present invention is a layer between the water repellent layer (r) and the layer (c) as long as the water repellent layer (r), the layer (c) and the resin substrate layer (s) are arranged in this order. Another layer may be included between c) and the resin substrate layer (s) and on the surface side of the layer (s), but another layer is present between the layer (r) and the layer (c). Preferably not. Moreover, when resin base material layer (s) is a hard-coat layer, it is preferable that there is no other layer between resin base material layer (s) and layer (c). The laminate of the present invention preferably further comprises a resin layer (s2) different from the resin base material layer (s), and the water repellent layer (r), the layer (c), The resin base material layer (s) and the resin layer (s2) may be in this order. The resin component of the resin layer (s2) is not particularly limited, but particularly when the resin base layer (s) is a hard coat layer, polyacrylate resins, polyamide resins, polyimide resins, polyamideimide resins, polyurethane resins Resin, polyester resin, polycarbonate resin, polyether sulfone resin, acetyl cellulose resin, cycloolefin resin, polyvinyl alcohol resin and the like are preferable because they can easily improve the adhesion to the hard coat layer, among which polyimide resin Resins and polyamideimide resins are preferred. The thickness of the resin layer (s2) is, for example, 10 to 500 μm.

A primer layer may be provided between the resin layer (s2) and the resin base layer (s) (in particular, the hard coat layer). As a primer agent, there are, for example, a primer agent such as an ultraviolet curing type, a thermosetting type, or a two-component curing type epoxy compound. It is preferable that the compound contained in the primer layer is chemically bonded to the resin component contained in the resin layer (s2) or the silicon material optionally contained. Moreover, a polyamic acid may be used as a primer agent, and the adhesiveness of resin layer (s2) and resin base material layer (s) (especially hard-coat layer) can be improved. Furthermore, a silane coupling agent may be mentioned as a primer agent, and it may be chemically bonded to the silicon material optionally contained in the resin substrate by a condensation reaction. The thickness of the primer layer is, for example, 0.1 to 20 μm.

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

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

The method for producing the laminate of the present invention comprises the steps of (i) forming a layer (c) having a structure derived from an organosilicon compound (C) on a resin substrate layer (s), and (ii) a water repellent layer And (r).

In the step of forming the layer (c), a composition containing the organosilicon compound (C) is applied to the resin substrate layer (s). The composition preferably contains an organosilicon compound (C) and a solvent (E). The solvent (E) is not particularly limited, and for example, alcohol solvents, ketone solvents, ether solvents, hydrocarbon solvents and the like can be used, and alcohol solvents and ketone solvents are particularly preferable.

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

The organosilicon compound (C) is preferably 0.05% by mass or more, more preferably 0.08% by mass or more, and still more preferably 0.1% by mass in 100% by mass of the composition containing the organosilicon compound (C). It is not less than 2% by mass, more preferably not more than 1.5% by mass, and still more preferably not more than 1.2% by mass.

The composition for forming the layer (c) may be coated by, for example, dip coating, roll coating, bar coating, spin coating, spray coating, die coating, gravure coating, etc. The coat method is preferred.

Before applying the composition containing the organosilicon compound (C), the resin base material layer (s) is preferably subjected to an easy adhesion treatment. Examples of the easy adhesion treatment include hydrophilic treatment such as corona treatment, plasma treatment, and ultraviolet treatment. A functional group such as an OH group (especially when the substrate is an epoxy resin) or a COOH group (especially when the substrate is an acrylic resin) is formed on the surface of the substrate by carrying out an easy adhesion treatment such as plasma treatment. When such a functional group is formed on the surface of the substrate, the adhesion between the layer (c) and the resin substrate layer (s) can be further improved.

The composition containing the organosilicon compound (C) is applied to form the layer (c), and then the composition containing the organosilicon compound (A) is applied and cured at normal temperature to obtain a water repellent layer ( r) can be formed.

The composition containing the organosilicon compound (A) preferably further contains the organosilicon compound (B), and usually contains a solvent (D). 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, a fluorinated hydrocarbon-based solvent or the like can be used. Is preferred. The fluorinated ether solvent is preferably a hydrofluoroether such as fluoroalkyl (especially perfluoroalkyl group having 2 to 6 carbon atoms) -alkyl (especially methyl group or ethyl group) ether, such as ethyl nona fluorobutyl ether or ethyl nona ether. Fluoroisobutyl ether is mentioned. Examples of ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether include Novec (registered trademark) 7200 (manufactured by 3M, having a molecular weight of about 264). As the fluorinated amine solvent, an amine in which at least one of hydrogen atoms of ammonia is substituted with a fluoroalkyl group is preferable, and a third of all ammonia hydrogen atoms is substituted with a fluoroalkyl group (particularly, perfluoroalkyl group) Preferred are primary amines, and specific examples thereof include tris (heptafluoropropyl) amine, and Florinert (registered trademark) FC-3283 (manufactured by 3M, having a molecular weight of about 521) corresponds thereto. As the fluorinated hydrocarbon solvents, fluorinated aliphatic hydrocarbon solvents such as 1,1,1,3,3-pentafluorobutane, fluorinated aromatics such as 1,3-bis (trifluoromethylbenzene) and the like Hydrocarbon solvents may be mentioned. As 1,1,1,3,3-pentafluorobutane, for example, Solve 55 (made by Solbex) and the like can be mentioned.

As the fluorine-based solvent, in addition to the above, hydrochlorofluorocarbons such as ASAHIKLIN (registered trademark) AK 225 (manufactured by Asahi Glass Co., Ltd.) and hydrofluorocarbons such as ASAHIKLIN (registered trademark) AC 2000 (manufactured by Asahi Glass Co., Ltd.) Can.

It is preferable to use at least a fluorinated amine solvent as the solvent (D). The solvent (D) preferably contains two or more fluorinated solvents, and contains a fluorinated amine solvent and a fluorinated hydrocarbon solvent (especially a fluorinated aliphatic hydrocarbon solvent). Is preferred.

The composition for forming a water repellent layer (r) is a silanol condensation catalyst, an antioxidant, an antirust agent, an ultraviolet absorber, a light stabilizer, an antifungal agent, an antibacterial agent, as long as the effects of the present invention are not impaired. You may contain various additives, such as an anti-biofouling agent, a deodorizer, a pigment, a flame retardant, and an antistatic agent.

The composition for forming a water repellent layer (r) is applied onto the layer (c) and dried to form a water repellent layer (r). Examples of the method for applying the composition for forming the water repellent layer (r) include dip coating method, roll coating method, bar coating method, spin coating method, spray coating method, die coating method, gravure coating method and the like.

The conditions after applying the composition for forming a water repellent layer (r) on the layer (c) are not particularly limited, and for example, they may be left standing for 1 hour or more in the air at normal temperature. In the present invention, the normal temperature is 5 to 60 ° C., preferably by leaving at a temperature range of 15 to 40 ° C., a film can be formed. Thereafter, heating (baking) may be further performed at a temperature of 50 to 300 ° C., preferably 100 to 200 ° C., for about 10 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% by mass or more, preferably 0.05% by mass or more in 100% by mass of the composition. Also, it is preferably 0.5% by mass or less, more preferably 0.3% by mass or less.

When the composition for forming the water repellent layer (r) contains the organosilicon compound (B), the content of the organosilicon compound (B) in the composition is, for example, 0.01% by mass or more, and preferably It is preferably 0.03% by mass or more and 0.3% by mass or less, and more preferably 0.2% by 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 preferably 3 or less, more preferably 1.5 or less .

Hereinafter, the present invention will be more specifically described by way of examples. The present invention is not limited by the following examples, and it is of course possible to implement with appropriate modifications as long as it can conform to the above-mentioned and the following effects, and all of them can be technical of the present invention. It is included in the scope.

Example 1
0.25% by mass of KBM-603 (N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) as organosilicon compound (C), and methyl ethyl ketone as solvent (E) The solution containing 99.75% by mass was stirred at room temperature to obtain a solution for forming layer (c). On the substrate having an acrylic hard coat layer obtained by activating the surface to be coated of the obtained solution using an atmospheric pressure plasma apparatus (manufactured by Fuji Machine Mfg. Co., Ltd.), OPTICOAT MS-A 100 manufactured by MIKASA Co., Ltd. Using a (spin coater), a layer (c) was obtained by applying a coating solution amount of 200 μl, a rotational speed of 2000 rpm, and a rotational speed of 20 seconds.

Next, as an organosilicon compound (A), a compound represented by the following formula (1) (hereinafter, compound a), and as a solvent (D), FC-3283 (C ₉ F ₂₁ N, Fluorinert, manufactured by 3M Co.) The solution was mixed and stirred at room temperature for a predetermined time to obtain a solution for forming a water repellent layer (r). The proportion of the organosilicon compound (A) in the solution for forming the water repellent layer (r) was 0.085% by mass. The solution for forming a water repellent layer (r) was applied onto the layer (c) using a spray coater manufactured by Apiros Corporation. The spray coating conditions are: scan speed: 600 mm / sec, pitch: 5 mm, liquid volume: 6 cc / min, atomizing air: 350 kPa, gap: 70 mm. Then, it baked at 120 degreeC for 20 minutes, and obtained the laminated body which contains resin base material layer (s), layer (c), and water repellent layer (r) in this order.

The compound a represented by the above formula (1) is one synthesized by the method described in Synthesis Examples 1 and 2 of JP-A-2014-15609, r is 43 and s is an integer of 1 to 6, The number average molecular weight is about 8000.

Example 2
In a solution for forming a water repellent layer (r), FAS ₁₃ E (C ₆ F ₁₃ -C ₂ H ₄ -Si (OC ₂ H ₅ ) ₃ , manufactured by Tokyo Chemical Industry Co., Ltd.) as an organosilicon compound (B) is further added. A laminate was obtained in the same manner as in Example 1 except that the solution contained 0.05% by mass.

Comparative Example 1
In the same manner as in Example 1 except that KBM-5103 (3-acryloyloxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.) was used in place of KBM-603 for the solution for forming layer (c). I got a body.

Comparative Example 2
In the same manner as in Example 2 except that KBM-5103 (3-acryloyloxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.) was used in place of KBM-603 for the solution for forming layer (c). I got a body.

[Example 3]
Reactant of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and chloropropyltrimethoxysilane described in JP-A-2012-197330, represented by the following formula, as an organosilicon compound (C) Name: X-12-5263HP (Shin-Etsu Chemical Co., Ltd. product) was used, and a laminate was obtained in the same manner as Example 2, except that it contained 0.50% by mass.

[Comparative Example 3 and Comparative Example 4]
In place of the organosilicon compound (C), KBM 3086 (1,8-bis (trimethylsilyl) octane, manufactured by Shin-Etsu Chemical Co., Ltd.) having no amino group in the molecule is used, each containing 0.25 mass% or A laminate was obtained in the same manner as Example 2, except that 0.50% by mass was contained.

The following measurement was performed about the film | membrane obtained by the said Example and comparative example.

(1) Measurement of water contact angle (initial contact angle)
A 3 μL water droplet is dropped on the obtained film, and the contact angle of water is measured by a droplet method (analysis method: θ / 2 method) using a contact angle measuring device (DM700 manufactured by Kyowa Interface Science Co., Ltd.) did.

(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 a minoan eraser, with the eraser in contact with the film. About 2.5 ml of ethanol was dropped thereto, and the eraser was reciprocated on the film at a speed of 40 r / min (a speed of 40 reciprocations per minute) to conduct a chemical resistance test. The contact angle of water after the eraser reciprocated the film 3000 times was measured.

The results are shown in Table 1.

In Examples 1 to 3 in which the layer (c) is formed using the organosilicon compound (C) specified in the present invention, the water contact angle after the chemical resistance test is good at 82.0 ° or more (particularly 90 ° or more). 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, the water contact angle after the chemical resistance test was It has fallen.

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 a car or building, a metal product such as a cooker, a ceramic product such as a dish, plastic The film can be suitably formed on manufactured automobile parts and the like, which is industrially useful. Moreover, it is preferably used also for articles of each member around a kitchen, a bathroom, a wash basin, a mirror, a toilet, goggles, glasses and the like.

Claims

Composition in which the water repellent layer (r) and the resin base layer (s) are organosilicon compounds having a silicon atom to which a hydrolysable group is bonded and which comprises an organosilicon compound (C) having an amino group or an amine skeleton A laminate formed via a layer (c) formed of
The water repellent layer (r) is a layer formed from a composition containing an organosilicon compound (A) represented by the following formula (a1):

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 1 to 20 carbon atoms, if R 11 there are a plurality may be different plural R 11 are each, R 12 is more if present may be different plurality of R 12 each may be the case where R 13 there are a plurality of different plural R 13 are each,
E 1, E 2, E 3 , E 4, and E 5 is, independently represents a hydrogen atom or a fluorine atom, if E 1 there are a plurality may be different plurality of E 1, respectively, E 2 may be the case where there are plural different multiple E 2 respectively, when the E 3 there are a plurality may be different plurality of E 3 respectively, the plurality of E if E 4 there are a plurality of 4 may be different from each other,
G 1 and G 2 are each independently a di- to 10-valent organosiloxane group having a siloxane bond,
J 1 , J 2 and J 3 are each independently a hydrolyzable group or- (CH 2 ) e 6 -Si (OR 14 ) 3 , e 6 is 1 to 5 and R 14 is a methyl group or an ethyl group, if J 1 there are a plurality may be different plurality of J 1, respectively, when J 2 there are a plurality may be different plurality of J 2, respectively, J 3 is more If present, multiple J 3 may be different from each other,
L 1 and L 2 each independently represent an oxygen atom, a nitrogen atom, or a divalent C 1-12 linking group which may contain a fluorine atom, and when a plurality of L 1 are present, plural L 1 s and L 2 s L 1 is may be different from each, when L 2 there are a plurality may be different plurality of L 2, respectively,
d11 is 1 to 9,
d12 is 0 to 9,
a10 and a14 are each independently 0 to 10,
a11 and a15 are each independently 0 or 1, and
a12 and a16 are each independently 0 to 9,
a13 is 0 or 1;
and a21, a22 and a23 are each independently 0 to 2;
e1, e2 and e3 are each independently 1 to 3.
The laminate according to claim 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).

In the above formula (c1),
R x1, R x2, R x3 , R x4 are each independently a hydrogen atom or a carbon atoms is an alkyl group of 1 to 4, if R x1 there exist a plurality differ plurality of R x1, respectively may, if R x2 there are a plurality may be different plural R x2 are each, it may be the case where R x3 there are a plurality of different plural R x3 are each if R x4 there are multiple And each R x 4 may be different from each other,
Each of Rf x1 , Rf x2 , Rf x3 , and Rf x4 independently represents an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms have been substituted with a fluorine atom, or a fluorine atom, and a plurality of Rf x1 are present If you want may be different multiple of Rf x1, respectively, different from the case where Rf x2 there is more than one may be different from each of the plurality of Rf x2, a plurality of Rf x3 If Rf x3 there is more than one, respectively even if well, if Rf x4 there are a plurality may be different plurality of Rf x4, respectively,
R x5 is an alkyl group having 1 to 20 carbon atoms, may be the case where R x5 there are a plurality of different plural R x5 are each,
X is a hydrolyzable group, and when a plurality of X are present, the plurality of X may be different from each other,
Y is -NH- or -S-, and when there are a plurality of Y, a plurality of Y may be different from each other,
Z is a vinyl group, α-methyl vinyl group, styryl group, methacryloyl group, acryloyl group, amino group, isocyanate group, isocyanurate group, epoxy group, ureido group, or mercapto group,
p1 is an integer of 1 to 20, p2, p3 and p4 are each independently an integer of 0 to 10, and p5 is an integer of 1 to 10,
p6 is an integer of 1 to 3 and
Z -, - Si (X) p6 (R x5) 3-p6, p1 amino - {C (R x1) ( R x2)} -, p2 amino - {C (Rf x1) ( Rf x2)} - , P3-{Si (R x3 ) (R x4 )}-, p4-{Si (Rf x3 ) (Rf x4 )}-, p5 -Y- are Z- and -Si (X ) P6 (R x 5 ) 3-p6 is terminated, and so long as -O- is not linked to -O-, they are linked in any order and contain at least one of amino group and -NH-.

In the above formula (c10),
R x10 and R x11 are each independently a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, if R x10 there are a plurality may be different plural R x10 are each, R x11 is When there are two or more R x 11 may be different from each other,
Rf x10 and Rf x11 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted by a fluorine atom or a fluorine atom, and when there are a plurality of Rf x10, a plurality of Rf x10 well be different from each other, when the Rf x11 there is more than one may be different multiple of Rf x11, respectively,
R x50 and R x50 'is independently an alkyl group having a carbon number of 1 ~ 20, R x50 and R x50' even if there are a plurality of different respective plurality of R x50 and R x50 ' Often,
X 20 and X 21 are each independently a hydrolysable group, if X 20 and X 21 there are a plurality may be different plurality of X 20 and X 21 are each,
p10 is each independently an integer of 1 to 30, p20 is each independently an integer of 0 to 30, and at least one of the parenthesized repeating units with p10 or p20 attached is R 100 in the amine skeleton is a hydrogen atom or an alkyl group, which is substituted for the amine skeleton -NR 100-
p60 and p60 'are each independently an integer of 1 to 3,
The p10-{C (R x10 ) (R x11 )}-and the p20-{C (Rf x10 ) (Rf x11 )}-do not have to be p10 or p20 continuous and may be any coupled side by side in this order, both ends is -Si (X 20) p60 (R x50) 3-p60 and -Si (X 21) p60 '( R x50') 3-p60 '.
The water repellent layer (r) is a layer formed from a composition containing the organosilicon compound (A) represented by the above formula (a1) and the organosilicon compound (B) represented by the following formula (b1) The laminated body according to claim 1 or 2.

In the above formula (b1),
Rf b10 is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted by a fluorine atom,
R b11, R b12, R b13 and R b14 are each independently a hydrogen atom or a carbon atoms is an alkyl group of 1 to 4, if R b11 there are a plurality differ plurality of R b11 each may, if R b12 there are a plurality may be different plural R b12 each may be the case where R b13 there are a plurality of different plural R b13 are each if R b14 there are multiple And R b14 's may be different from each other,
Rf b11, Rf b12, Rf b13 and Rf b14 are each independently one or more hydrogen atoms is an alkyl group or a fluorine atom carbon number of 1 to 20 substituted by a fluorine atom, Rf b11 multiple presence In the case of multiple Rf b11 may be different from each other, when multiple R f b12 are present, multiple R f b12 may be different from each other, and when multiple R f b13 is present, multiple R f b13 are different from each other even if well, if Rf b14 there are a plurality may be different plurality of Rf b14, respectively,
R b15 is an alkyl group having 1 to 20 carbon atoms, it may be the case where R b15 there are a plurality of different plural R b15 are each,
A 1 is —O—, —C (= O) —O—, —O—C (= O) —, —NR—, —NRC (= O) — or —C (= O) NR— There, wherein R is a hydrogen atom, a fluorine-containing alkyl group of the alkyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms, if a 1 there are a plurality may be different plurality of a 1, respectively,
A 2 is a hydrolyzable group, if A 2 there are a plurality may be different plurality of A 2, respectively,
b11, b12, b13, b14 and b15 are each independently an integer of 0 to 100,
c is an integer of 1 to 3 and
Rf b10 -, - Si (A 2) c (R b15) 3-c, b11 amino - {C (R b11) ( R b12)} -, b12 amino - {C (Rf b11) ( Rf b12) }-, B13-{Si (R b13 ) (R b14 )}-, b14-{Si (Rf b13 ) (Rf b14 )}-, b15 -A 1 -is Rf b10- , As long as -Si (A 2 ) c (R b15 ) 3-c is terminated to form no perfluoropolyether structure and -O- is not linked to -O- to -F, they are arranged in any order. Join.
The laminate according to claim 2, wherein the organosilicon compound (C) represented by the formula (c1) is represented by the following formula (c2).

In the above formula (c2),
X 1 is a methoxy group or an ethoxy group, if X 1 there are a plurality may be different plurality of X 1 are each,
Y 1 is -NH-,
Z 1 is an amino group or a mercapto group,
R x51 is an alkyl group having 1 to 20 carbon atoms, it may be the case where R x51 there are a plurality of different plural R x51 are each,
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.
The laminate according to claim 2, wherein the organosilicon compound (C) represented by the formula (c10) is represented by the following formula (c20).

In the above formula (c20),
X 30 and X 31 are each independently a hydrolyzable group, when X 30 and X 31 there are a plurality may be different plurality of X 30 and X 31 are each,
R x55 and R x56 are each independently, is an alkyl group having 1 to 20 carbons, even if the R x55 and R x56 there are a plurality of different plural R x55 and R x56 are each Often,
In -C w H 2w- , at least one of its partial methylene groups is replaced with an amine skeleton -NR 100- , and R 100 is a hydrogen atom or an alkyl group,
w is an integer of 1 to 30 (except the number of methylene groups replacing the amine skeleton),
p65 and p66 are each independently an integer of 1 to 3.
The laminate according to any one of claims 1 to 5, wherein the resin base material layer (s) is an acrylic resin hard coat layer.
A method of manufacturing a laminate according to any one of claims 1 to 6, wherein
Applying a composition containing the organosilicon compound (C) to the resin base material layer (s) to form a layer (c);
Applying a composition containing the organosilicon compound (A) to the layer (c) and curing the composition at normal temperature to form a water repellent layer (r). Method.
The method for producing a laminate according to claim 7, wherein, in the step of forming the water repellent layer (r), the composition containing the organosilicon compound (A) further contains the organosilicon compound (B).
The method for producing a laminate according to claim 7 or 8, wherein the resin base material layer (s) is subjected to plasma treatment, and the composition containing the organosilicon compound (C) is applied to the plasma treated surface.