CN114868045A - Laminate and flexible display device - Google Patents

Abstract

A laminate comprising a substrate(s), an intermediate layer (c), and a water-repellent layer (r) in this order, wherein the following requirements (1) and (2) are satisfied. (1) The reflectance obtained by subtracting the surface reflection loss and the back reflection loss from the reflectance obtained by calculating the spectral reflectance at a wavelength of 530nm at an incident angle of 12 DEG and a reflection angle of 12 DEG measured on the side surface of the water-repellent layer (r) by using a 2-degree field of view (C light source) according to JIS Z8701 is 4.5% or less. (2) The thickness of the laminate is 500 μm or less.

Description

Laminate and flexible display device

technical field

The present invention relates to a laminate and a flexible display device.

Background technique

Since the surface free energy of fluorine-based water-repellent films, typified by films formed from compositions containing compounds having a perfluoropolyether structure, is very small, they are used in display devices such as touch panel displays, optical elements, and semiconductors. It is used as an antifouling coating or a water- and oil-repellent coating in various fields such as components, building materials, automobiles, and building window glass.

A water-repellent film is usually used by being formed on a substrate. When the composition for forming a water-repellent film is applied to a substrate, other layers such as a primer layer may be formed on the substrate in advance and then the composition may be applied to form a waterproof film. Stain coating or water and oil repellent coating.

For example, Patent Document 1 discloses a hard coat film obtained by laminating a hard coat layer (X), a primer layer (Y), and a surface layer (Z) in this order on at least one surface of a substrate The film, the aforementioned surface layer (Z) has a water contact angle of 110° or more. It is described that in order to form the aforementioned surface layer (Z), a fluorine-based compound having a polyperfluoropolyether chain is preferably used, and in order to form the primer layer (Y), 3-acryloyloxypropyltrimethyl is preferably used. Silane compounds such as oxysilane are preferred.

prior art literature

Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2015-120253

SUMMARY OF THE INVENTION

The problem to be solved by the invention

In order to maintain favorable water repellency in a laminate having a water-repellent layer on a base material, abrasion resistance when evaluated from the water-repellent layer side exposed on the surface side is required. Therefore, an object of the present invention is to provide a laminate in which a base material, an intermediate layer, and a water-repellent layer are laminated in this order, which laminate is excellent in abrasion resistance even if it is a thin film.

means of solving problems

The inventors of the present application found that, by adjusting the reflection characteristics of the surface of the laminate, good abrasion resistance can be achieved despite being a thin film. Specifically, this invention which achieved the above subject is as follows.

[1] A laminate comprising a substrate (s), an intermediate layer (c), and a water-repellent layer (r) in this order, and satisfying the following requirements (1) and (2).

(1) Reflectance obtained by calculating the spectral reflectance at a wavelength of 530 nm at an incident angle of 12° and a reflection angle of 12° measured on the water repellent layer (r) side surface from a 2-degree field of view (C light source) using JIS Z8701 The reflectance after subtracting the surface reflection loss and the back reflection loss is 4.5% or less.

(2) The thickness of the said laminated body is 500 micrometers or less.

[2] The laminate according to [1], which further satisfies the requirements of the following (3).

(3) The surface fluorine element ratio on the water-repellent layer (r) side is 30 atomic % or more.

[3] The laminate according to [1] or [2], which further satisfies at least one of the following requirements (4) and (5).

(4) The arithmetic mean height Sa on the side of the water repellent layer (r) is 0.03 to 1.00 μm.

(5) The slip angle of water on the water repellent layer (r) side is 25° or less.

[4] The laminate according to any one of [1] to [3], wherein the surface Si ratio of the outermost layer on the side of the intermediate layer (c) of the base material (s) is 1 atomic % or more .

[5] The laminate according to any one of [1] to [4], wherein the water repellent layer (r) is an organosilicon compound (A) represented by the following formula (a1) and the following formula The cured layer of the mixed composition (ca) of the organosilicon compound (B) shown in (b1).

[Chemical formula 1]

In the above formula (a1),

Rf ^a1 is a bivalent perfluoropolyether structure with oxygen atoms at both ends,

R ¹¹ , R ¹² and R ¹³ are each independently an alkyl group having 1 to 20 carbon atoms, and when there are multiple R ¹¹ s, the multiple R ¹¹ may be different from each other, and when there are multiple R ¹² s, A plurality of R ¹² may be different from each other, and when there are a plurality of R ¹³ , 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,

If there are multiple ^E1s , the multiple ^E1s may be different from each other, if there are multiple ^E2s , the multiple ^E2s may be different from each other, and if there are multiple ^E3s , the multiple ^E3 They can be different from each other. When there are multiple ^E4s , the multiple ^E4s can be different from each other. When there are multiple ^E5s , the multiple ^E5s can be different from each other.

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

J ¹ , J ² and J ³ are each independently a hydrolyzable group or -(CH ₂ ) _e6 -Si(OR ¹⁴ ) ₃ , e6 is 1 to 5, R ¹⁴ is methyl or ethyl, and J ¹ is present In the case of multiple, multiple J ^1s may be different from each other, when multiple J ² exist, multiple J ² may be different from each other, and when multiple J ³ exists, multiple J ³ may be different from each other,

L ¹ and L ² are each independently a divalent linking group having 1 to 12 carbon atoms that may contain an oxygen atom, a nitrogen atom, or a fluorine atom, and when there are multiple L ^1s , the multiple L ^1s may be different from each other. , when there are multiple L ² , the multiple L ² can be different from each other,

d11 is 1 to 9,

d12 is 0～9,

a10 and a14 are independently 0 to 10,

a11 and a15 are each independently 0 or 1,

a12 and a16 are independently 0 to 9,

a13 is 0 or 1,

a21, a22, and a23 are independently 0 to 2,

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

[Chemical formula 2]

In the above formula (b1),

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

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 when there is a plurality of R ^b11 , the plurality of R ^b11 may be different from each other, and R ^b12 is present When there are multiple R ^b12s , they may be different from each other, when there are multiple R ^b13s , multiple R ^b13s may be different from each other, and when there are multiple R ^b14s , multiple R ^b14s may be different from each other. ,

Rf ^b11 , Rf ^b12 , Rf ^b13 and Rf ^b14 are each independently an alkyl group ^having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom, or a fluorine atom. The Rf ^b11s may be different from each other, and if there are multiple Rf ^b12s , the multiple Rf ^b12s may be different from each other, and if there are multiple Rf ^b13s , the multiple Rf ^b13s may be different from each other, and there are multiple Rf ^b14s . case, multiple Rf ^b14 can be different from each other,

R ^b15 is an alkyl group having 1 to 20 carbon atoms, and when there are a plurality of R ^b15 , the plurality of R ^b15 may be different from each other,

A ¹ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, and the aforementioned R is When there are a plurality of hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, or fluorine-containing alkyl groups having ^{1 to 4 carbon atoms, the plurality of A 1s may} be different from each other.

A ² is a hydrolyzable group, and when there are multiple A ² s, the multiple A ² s 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,

For Rf ^b10 -, -Si(A ² ) _c (R ^b15 ) _3-c , b11 -{C(R ^b11 )(R ^b12 )}-, b12 -{C(Rf ^b11 )(Rf ^b12 )} -, b13 -{Si(R ^b13 )(R ^b14 )}-, b14 -{Si(Rf ^b13 )(Rf ^b14 )}-, b15 -A ¹ -, as long as Rf ^b10 -, -Si (A ² ) _c (R ^b15 ) _3-c becomes a terminal, does not form a perfluoropolyether structure, and -O- is not connected to -O- or -F, and is arranged and bonded in an arbitrary order.

[6] The laminate according to any one of [1] to [5], wherein the intermediate layer (c) is an organosilicon compound represented by any one of the following formulae (c1) to (c3) The cured layer of the mixed composition (cc) of (C) or the vapor-deposited layer of the aforementioned organosilicon compound (C).

[Chemical formula 3]

In the above formula (c1),

R ^x11 , R ^x12 , R ^x13 , and R ^x14 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when there is a plurality of R ^x11 , the plurality of R ^x11 may be different from each other, and R ^x12 is present When there are multiple Rx12s, the multiple ^Rx12s may be different from each other, when there are multiple ^Rx13s , the multiple ^Rx13s may be different from each other, and when there are multiple ^Rx14s , the multiple ^Rx14s may be different from each other. ,

Rf ^x11 , Rf ^x12 , Rf ^x13 , and Rf ^x14 are each independently an alkyl group ^having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom, or a fluorine atom. The Rf ^x11s may be different from each other. If there are multiple Rf ^x12s , the multiple Rf ^x12s may be different from each other. If there are multiple Rf ^x13s , the multiple Rf ^x13s may be different from each other. There are multiple Rf ^x14s . case, multiple Rf ^x14 can be different from each other,

R ^x15 is an alkyl group having 1 to 20 carbon atoms, and when there are a plurality of R ^x15 , the plurality of R ^x15 may be different from each other,

X ¹¹ is a hydrolyzable group, and when there are a plurality of X ¹¹ , the plurality of X ¹¹ may be different from each other,

Y ¹¹ is -NH- or -S-, and when there are a plurality of Y ¹¹ , the plurality of Y ¹¹ may be different from each other,

Z ¹¹ is vinyl, α-methyl vinyl, styryl, methacryloyl, acryloyl, amino, isocyanate, isocyanurate, epoxy, urea or mercapto,

p1 is an integer from 1 to 20, p2, p3, and p4 are each independently an integer from 0 to 10, p5 is an integer from 1 to 10,

p6 is an integer from 1 to 3,

When Z ¹¹ is not an amino group, at least one of Y ¹¹ is -NH-, and when all Y ¹¹ are -S-, Z ¹¹ is an amino group,

For Z ¹¹ -, -Si(X ¹¹ ) _p6 (R ^x15 ) _3-p6 , p1 -{C(R ^x11 )(R ^x12 )}-, p2 -{C(Rf ^x11 )(Rf ^x12 )} -, p3 -{Si(R ^x13 )(R ^x14 )}-, p4 -{Si(Rf ^x13 )(Rf ^x14 )}-, p5 -Y ¹¹ -, as long as Z ¹¹ - and -Si (X ¹¹ ) _p6 (R ^x15 ) _3-p6 serves as a terminal, and -O- is not linked to -O-, and they are arranged and bonded in an arbitrary order.

[Chemical formula 4]

In the above formula (c2),

R ^x20 and R ^x21 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when there are plural R ^x20s , the plural R ^x20s may be different from each other, and when there are plural R ^x21s , multiple R ^x21 can be different from each other,

Rf ^x20 and Rf ^x21 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms, or a fluorine atom, and when there are multiple Rf ^x20s , the multiple Rf ^x20s may be different from each other. , if there are multiple Rf ^x21s , the multiple Rf ^x21s can be different from each other,

^Rx22 and ^Rx23 are each independently an alkyl group having 1 to 20 carbon atoms, and when there are a plurality of ^Rx22 and ^Rx23 , the plurality of ^Rx22 and ^Rx23 may be different from each other,

X ²⁰ and X ²¹ are each independently a hydrolyzable group, and when there are a plurality of X ²⁰ and X ²¹ , the plurality of X ²⁰ and X ²¹ may be different from each other,

p20 is each independently an integer of 1 to 30, p21 is each independently an integer of 0 to 30, and at least one of the repeating units marked with p20 or p21 and enclosed in parentheses is replaced with an amine skeleton -NR ¹⁰⁰ -, the aforementioned R ¹⁰⁰ in the amine skeleton is a hydrogen atom or an alkyl group,

p22 and p23 are each independently an integer of 1 to 3,

For p20 -{C(R ^x20 )(R ^x21 )}-, p21 -{C(Rf ^x20 )(Rf ^x21 )}-, it is not necessary that p20 or p21 be consecutive, but to any are arranged and bonded in order, and both ends become -Si(X ²⁰ ) _p22 (R ^x22 ) _3-p22 and -Si(X ²¹ ) _p23 (R ^x23 ) _3-p23 .

[Chemical formula 5]

In the above formula (c3),

Z ³¹ and Z ³² are each independently a reactive functional group other than a hydrolyzable group and a hydroxyl group,

R ^x31 , R ^x32 , R ^x33 , and R ^x34 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when there is a plurality of R ^x31 , the plurality of R ^x31 may be different from each other, and R ^x32 is present When there are multiple Rx32s, they may be different from each other. ^When there are multiple ^Rx33s , multiple ^Rx33s may be different from each other. When there are multiple ^{Rx34s, multiple Rx34s may} be different from each other. ,

Rf ^x31 , Rf ^x32 , Rf ^x33 , and Rf ^x34 are each independently an alkyl group ^having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom, or a fluorine atom. The Rf ^x31s may be different from each other. If there are multiple Rf ^x32s , the multiple Rf ^x32s may be different from each other. If there are multiple Rf ^x33s , the multiple Rf ^x33s may be different from each other. There are multiple Rf ^x34s . case, multiple Rf ^x34 can be different from each other,

Y ³¹ is -NH-, -N(CH ₃ )- or -O-, and when there are a plurality of Y ³¹ , the plurality of Y ³¹ may be different from each other,

X ³¹ , X ³² , X ³³ and X ³⁴ are each independently -OR ^c (R ^c is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an amino C _1-3 alkyl _{diC 1-3} alkoxy group silyl group), when there are multiple X ³¹ , the multiple X ³¹ may be different from each other, when there are multiple X ³² , the multiple X ³² may be different from each other, and there are multiple X ³³ . Below, a plurality of X ³³ can be different from each other, and when there are multiple X ³⁴ , the plurality of X ³⁴ can be different from each other,

p31 is an integer from 0 to 20, p32, p33, and p34 are each independently an integer from 0 to 10, p35 is an integer from 0 to 5, p36 is an integer from 1 to 10, and p37 is 0 or 1.

As long as at least one of Z ³¹ and Z ³² is an amino group, or at least one of Y ³¹ is -NH- or -N(CH ₃ )-, and the terminal is Z ³¹ - and Z ³² -, -O -Not connected with -O-, then p31-{C( ^Rx31 )( ^Rx32 )}-, p32-{C( ^Rfx31 )( ^Rfx32 )}-, p33-{Si( ^Rx33 ) (R ^x34 )}-, p34 -{Si(Rf ^x33 )(Rf ^x34 )}-, p35 -Y ³¹ -, p36 -{Si(X ³¹ )(X ³² )-O}-, p37 -{Si(X ³³ )(X ³⁴ )}- is arranged and bonded in an arbitrary order.

[7] A flexible display device comprising the laminate according to any one of [1] to [6], a polarizing plate, a touch sensor, and a display panel.

Invention effect

The laminate of the present invention including the base material (s), the intermediate layer (c), and the water repellent layer (r) in this order has the above water repellency calculated from the 2-degree field of view (C light source) using JIS Z8701. The reflectance obtained from the spectral reflectance at a wavelength of 530 nm at an incident angle of 12° and a reflection angle of 12° measured on the surface of the layer side is a requirement that the reflectance after subtracting the surface reflection loss and the back reflection loss is 4.5% or less, so it is resistant to It is excellent in abrasion resistance, and further has the requirement of a thickness of 500 μm or less, so that both abrasion resistance and thin film can be realized.

Detailed ways

The laminate of the present invention is a laminate including a base material (s), an intermediate layer (c), and a water repellent layer (r) in this order, and satisfies the following requirements (1) and (2).

(1) Subtract the reflectance obtained by calculating the spectral reflectance at a wavelength of 530 nm at an incident angle of 12° and a reflection angle of 12° measured on the surface of the water repellent layer using a 2-degree field of view (C light source) using JIS Z8701 The reflectance after surface reflection loss and back reflection loss is 4.5% or less.

(2) The thickness of the said laminated body is 500 micrometers or less.

By satisfying the aforementioned requirement (1), good wear resistance can be achieved. In the requirement (1), the reflectance is preferably 4.3% or less, more preferably 3.5% or less, still more preferably 2.5% or less, and may be 0.5% or more.

In the requirement (2), the thickness of the laminate of the present invention is preferably 400 μm or less, more preferably 300 μm or less, still more preferably 200 μm or less, most preferably 100 μm or less, and may be 10 μm or more. By making the thickness of the said laminated body into a predetermined value or less, when the laminated body of this invention is used for a touch panel application, the sensitivity can be improved, and visibility can be improved.

Further, the laminate of the present invention preferably satisfies at least one of the following requirements (3) to (5) while satisfying the aforementioned requirements (1) and (2). In particular, it is more preferable to satisfy the following requirements (3) while satisfying the aforementioned requirements (1) and (2), and it is still more preferable to satisfy all of the requirements (1) to (5).

(3) The surface fluorine element ratio on the water-repellent layer (r) side is 30 atomic % or more.

By having the above-mentioned requirement (3), more favorable water repellency can be realized. The surface fluorine element ratio is more preferably 40 atomic % or more, and further preferably 50 atomic % or more. The upper limit of the surface fluorine element ratio is not particularly limited, but is, for example, 80 atomic %. The said surface fluorine element ratio can be measured by the method described in the Example mentioned later.

(4) The arithmetic mean height Sa on the side of the water repellent layer (r) is 0.03 to 1.00 μm.

The wear resistance can be further improved by having the requirement of (4) above. In addition, the requirement of the above-mentioned (4) is also effective in realizing more favorable water repellency and/or sliding property. The surface height Sa on the side of the water repellent layer (r) is more preferably 0.70 μm or less, still more preferably 0.50 μm or less, and even more preferably 0.30 μm or less. Moreover, the said surface height Sa may be 0.04 micrometer or more, and 0.05 micrometer or more may be sufficient as it. It should be noted that the arithmetic mean height Sa is calculated in accordance with ISO 25178.

(5) The slip angle of water on the water repellent layer (r) side is 25° or less.

In the above-mentioned requirement (5), the sliding angle of water is more preferably 20° or less, still more preferably 15° or less, and still more preferably 10° or less. The lower limit of the said slip angle of water is not specifically limited, For example, it is 1 degree.

It is preferable that the said water repellent layer (r) is a cured layer of the mixed composition (ca) of an organosilicon compound (A) and an organosilicon compound (B).

I. Organosilicon compound (A)

The aforementioned organosilicon compound (A) is a monovalent group having a perfluoropolyether structure bonded to a silicon atom, and a hydrolysis bond is bonded to the silicon atom through a linking group or not through a linking group compounds with sexual groups. It is preferable that the said water repellent layer (r) is obtained by apply|coating and hardening the said composition (ca), and has the structure derived from the said organosilicon compound (A). As described above, the organosilicon compound (A) has a hydrolyzable group bound to a silicon atom (may be bound via a linking group), and the -SiOH group ( Si and OH may be bonded through a linking group) and dehydrate each other and condense each other, so the water-repellent layer (r) usually has a condensed structure derived from the organosilicon compound (A). As said hydrolyzable group, an alkoxy group, a halogen atom, a cyano group, an acetoxy group, an isocyanate group, etc. are mentioned.

The aforementioned perfluoropolyether structure may also be referred to as a perfluorooxyalkylene group. The perfluoropolyether structure has liquid repellency such as water repellency or oil repellency. The number of carbon atoms contained in the longest linear portion of the perfluoropolyether structure is preferably 5 or more, more preferably 10 or more, and still more preferably 20 or more, for example. The upper limit of the number of carbon atoms is not particularly limited, but may be, for example, about 200. It is preferable that the monovalent group which has a perfluoropolyether structure of the said organosilicon compound (A) further has a perfluoroalkyl group at a free terminal.

The above-mentioned water repellent layer (r) can also be expressed as a layer having a perfluoropolyether structure and a polysiloxane skeleton, and preferably further has a perfluoroalkyl group. The water repellent layer (r) preferably has a structure in which a monovalent group having a perfluoropolyether structure and having a perfluoroalkyl group at its free terminal is bonded to a part of silicon atoms of the polysiloxane skeleton. Water repellency is improved by making a perfluoroalkyl group exist on the free terminal side.

The number of carbon atoms in the perfluoroalkyl group (in particular, the number of carbon atoms in the longest linear portion) is, for example, preferably 3 or more, more preferably 5 or more, and still more preferably 7 or more. In addition, the upper limit of the said carbon number is not specifically limited, For example, even if it is about 20, excellent water repellency is exhibited.

The above-mentioned perfluoroalkyl group may form a fluorine-containing group such as a fluoroalkyl group by bonding to a hydrocarbon group and/or a group obtained by substituting at least a part of hydrogen atoms of the hydrocarbon group with a fluorine atom, for example, CF ₃ (CF ₂ ) _m -(CH ₂ ) _n -, CF ₃ (CF ₂ ) _m -C ₆ H ₄ - (m is 1-10, preferably 3-7, n is 1-5, preferably 2-4), Preferably, it is CF ₃ (CF ₂ ) _m -(CH ₂ ) _n - (m is all 1 to 10, preferably 3 to 7, and n is all 1 to 5, preferably 2 to 4). The aforementioned perfluoroalkyl group is more preferably directly bonded to the perfluoropolyether structure.

In the aforementioned organosilicon compound (A), a monovalent group having a perfluoropolyether structure and a silicon atom may be bonded through an appropriate linking group, or the linking group may not exist and the above-mentioned perfluoropolyether The monovalent group of the ether is directly bonded to the silicon atom. Examples of the linking group include alkylene groups, hydrocarbon groups such as aromatic hydrocarbon groups, (poly)alkylene glycol groups, or groups obtained by substituting a part of their hydrogen atoms with fluorine atoms or substituents, and their appropriately linked groups, etc. The number of carbon atoms of the linking group is, for example, 1 or more and 20 or less, and preferably 2 or more and 15 or less.

The said hydrolyzable group has a function of bonding the organosilicon compounds (A) to each other or to the active hydrogen (hydroxyl group etc.) on the surface of the base material by a hydrolysis/dehydration condensation reaction. As such a hydrolyzable group, an alkoxy group (especially C1-C4 alkoxy group), a hydroxyl group, an acetoxy group, a halogen atom (especially a chlorine atom) etc. are mentioned, for example. Preferred hydrolyzable groups are alkoxy groups and halogen atoms, and particularly preferred are methoxy groups, ethoxy groups, and chlorine atoms.

The aforementioned hydrolyzable group may be bonded to a silicon atom via a linking group, or may be directly bonded to a silicon atom without a linking group. The number of hydrolyzable groups bonded to the silicon atom may be one or more, and may be 2 or 3, but preferably 2 or 3, particularly preferably 3. Two or more hydrolyzable groups are bonded to silicon In the case of atoms, different hydrolyzable groups may be bonded to silicon atoms, but the same hydrolyzable groups are preferably bonded to silicon atoms. The total number of the fluorine-containing group and the hydrolyzable group bonded to the silicon atom is usually 4, but may be 2 or 3 (especially 3). In the case of 3 or less, a monovalent group other than a hydrolyzable group may be bonded to the remaining chemical bonds, for example, an alkyl group (especially an alkyl group having 1 to 4 carbon atoms) may be bonded. , H, NCO, etc.

The monovalent group which has a perfluoropolyether structure of the said organosilicon compound (A) may be linear or may have a side chain, and a linear is preferable.

The aforementioned organosilicon compound (A) can be represented by, for example, the following formula (a).

[Chemical formula 6]

In the above formula (a), D ¹ is a monovalent group having a perfluoropolyether structure, and the terminal on the side of D ¹ that is bonded to D ² is -CF ₂ -O-*, -CFD ⁹ -* (* is a chemical bond ^on the D2 side ⁾ , D2 is a single bond or a divalent hydrocarbon group not substituted by a fluorine atom, ^D3 is a trivalent hydrocarbon group not substituted by a fluorine atom, and a part of the methylene group of the hydrocarbon group may be substituted is an oxygen atom, D ⁴ is a hydrogen atom or a fluorine atom, D ⁵ is a single bond or a divalent hydrocarbon group, D ⁶ is a monovalent group other than a hydrolyzable group, D ⁷ is a divalent group or a single bond, D ⁸ is a hydrolyzable group, D ⁹ is a hydrogen atom, a fluorine atom or a hydrocarbon group, n1 is 1-30, and n2 is 1-3. As a hydrolyzable group of ^D8 , the above-mentioned hydrolyzable group is mentioned.

The aforementioned organosilicon compound (A) is preferably represented by the following formula (a1).

[Chemical formula 7]

In the above formula (a1),

Rf ^a1 is a bivalent perfluoropolyether structure with oxygen atoms at both ends,

R ¹¹ , R ¹² and R ¹³ are each independently (that is, R ¹¹ , R ¹² and R ¹³ may be the same or different from each other) are alkyl groups having 1 to 20 carbon atoms, and when there are multiple R ¹¹ s , a plurality of R ¹¹ may be different from each other, if there are multiple R ¹² , a plurality of R ¹² may be different from each other, and if there are multiple R ¹³ , 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. When there are plural E ¹ s, the plural E ^1s may be different from each other, and there are plural E ² s. In the following cases, multiple E ^2s may be different from each other, if there are multiple E ^3s , multiple E ^3s may be different from each other, if there are multiple E ^4s , multiple E ^4s may be different from each other, and E ⁵ exists. In the case of multiple, multiple ^E5 can be different from each other,

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

J ¹ , J ² and J ³ are each independently a hydrolyzable group or -(CH ₂ ) _e6 -Si(OR ¹⁴ ) ₃ , e6 is 1 to 5, R ¹⁴ is methyl or ethyl, and J ¹ is present In the case of multiple, multiple J ^1s may be different from each other, when multiple J ² exist, multiple J ² may be different from each other, and when multiple J ³ exists, multiple J ³ may be different from each other,

L ¹ and L ² are each independently a divalent linking group having 1 to 12 carbon atoms that may contain an oxygen atom, a nitrogen atom, or a fluorine atom, and when there are multiple L ^1s , the multiple L ^1s may be different from each other. , when there are multiple L ² , the multiple L ² can be different from each other,

d11 is 1 to 9,

d12 is 0～9,

a10 and a14 are independently 0 to 10,

a11 and a15 are each independently 0 or 1,

a12 and a16 are independently 0 to 9,

a13 is 0 or 1,

a21, a22, and a23 are independently 0 to 2,

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

As represented by the above formula (a1), the aforementioned organosilicon compound (A) has a perfluoropolyether structure represented by Rf ^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 the polyoxyalkylene group are replaced by fluorine atoms, and can also be referred to as a perfluorooxyalkylene group, and can impart water repellency to the obtained coating film. Moreover, it is a compound which can bond the said organosilicon compound ( ^A ) by a polymerization reaction (especially a polycondensation reaction) with other monomers or by J2, and can become a matrix of the obtained coating film.

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 independently preferably an alkyl group having 1 to 10 carbon atoms.

L ¹ and L ² are each independently preferably a C1-C5 divalent linking group containing a fluorine atom.

G ¹ and G ² are each independently preferably a 2- to 5-valent organosiloxane group having a siloxane bond.

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

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

As the aforementioned organosilicon compound (A), it is preferable to use a compound in which Rf ^a1 of the above formula (a1) is -O-(CF ₂ CF ₂ CF ₂ O) _e5 -, e5 is 35 to 50, L ¹ and L ² All are perfluoroalkylene groups having 1 to 3 carbon atoms, E ¹ , E ² and E ³ are all hydrogen atoms, E ⁴ and E ⁵ are hydrogen atoms or fluorine atoms, and J ¹ , J ² and J ³ are all Methoxy or ethoxy (especially methoxy), a10 is 1-3, a11 is 0, a12 is 0-5, a13 is 1, a14 is 2-5, a15 is 0, a16 is 0-6 , a21 to a23 are each independently 0 or 1 (more preferably, all of a21 to a23 are 0), d11 is 1, d12 is 0 or 1, and e1 to e3 are all 3 compounds.

As the aforementioned organosilicon compound (A), it is also preferable to use a compound in which Rf ^a1 of the above formula (a1) is -O-(CF ₂ CF ₂ CF ₂ O) _e5 -, e5 is 25 to 40, and L ¹ is a A divalent linking group with 3 to 6 carbon atoms of fluorine atom and oxygen atom, L ² is a perfluoroalkylene group with 1 to 3 carbon atoms, E ² and E ³ are both hydrogen atoms, and E ⁵ is a fluorine atom , J ² is -(CH ₂ ) _e6 -Si(OCH ₃ ) ₃ , e6 is 2～4, a10 is 1～3, a11 is 0, a12 is 0, a13 is 0, a14 is 2～5, a15 is 0, 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 a compound of 3.

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

[Chemical formula 8]

In the above formula (a2-1),

Rf ^a21 is 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,

Rf ^a22 , Rf ^a23 , Rf ^a24 , and Rf ^a25 are each independently an alkyl group ^having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom, or a fluorine atom. The Rf ^a22s may be different from each other. When there are multiple Rf ^a23s , the multiple Rf ^a23s may be different from each other. When there are multiple Rf ^a24s , the multiple Rf ^a24s may be different from each other. There are multiple Rf ^a25s . case, multiple Rf ^a25 can be different from each other,

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 when there are multiple R ²⁰ , the multiple R ²⁰ may be different from each other, and R ²¹ may exist In the case of a plurality of R 21s, the plurality of R ^21s may be different from each other, when there are a plurality of R ^22s , the plurality of R ^22s may be different from each other, and when there are a plurality of R ²³ s, the plurality of R ²³ s may be different from each other,

R ²⁴ is an alkyl group having 1 to 20 carbon atoms, and when there are a plurality of R ²⁴ , the plurality of R ²⁴ may be different from each other,

M ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when there are multiple M ^1s , the multiple M ^1s 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 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 ³ s, the multiple M ³ s may be different from each other,

M ⁴ is a hydrolyzable group, and when there are a plurality of M ⁴ , the plurality of M ⁴ may be different from each other,

f11, f12, f13, f14, and f15 are each independently an integer from 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,

For 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 - become terminals, they are arranged in the order of forming a perfluoropolyether structure in at least a part, and -O- is not associated with -O- or -F connection is arranged and bonded in any order. That is, the formula (a2-1) is not necessarily f11-{C(R ²⁰ )(R ²¹ )}-continuous, f12-{C(Rf ^a22 )(Rf ^a23 )}-continuous, f13-{ Si(R ²² )(R ²³ )}-continuous, f14-{Si(Rf ^a24 )(Rf ^a25 )}-continuous, f15-M ³ -continuous, f16-[CH ₂ C(M ¹ ){ (CH ₂ ) _f17 -Si(M ⁴ ) _g1 (R ²⁴ ) _3-g1 }]-consecutive, and in this order, and can be like -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 )- and the like, each of which is arranged in an arbitrary order.

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

Rf ^a22 , Rf ^a23 , Rf ^a24 and Rf ^a25 are each independently preferably 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, and more preferably all of them 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 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)-, more preferably all of them are -O-.

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

Each of f11, f13 and f14 is preferably 1/2 or less of f12, more preferably 1/4 or less, further preferably f13 or f14 is 0, and particularly preferably f13 and f14 are 0.

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

f12 is preferably 20 to 600, more preferably 20 to 200, further preferably 50 to 200 (more preferably 30 to 150, particularly preferably 50 to 150, and most preferably 80 to 140). f15 is preferably 4 to 600, more preferably 4 to 200, 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 even more preferably 50 to 200.

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

f17 is preferably 0-1.

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

For 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 - may be arranged in an order in which a perfluoropolyether structure is formed in at least a part, and is arbitrary in the formula , but preferably the repeating unit marked f12 and enclosed in parentheses (i.e., -{C(Rf ^a22 )(Rf ^a23 )}-) on the most fixed end side (the side bonded to the silicon atom) is located at the most The repeating unit (ie, -{C(R ²⁰ )(R ²¹ )}-) marked with f11 on the free end side and enclosed in parentheses (ie, -{C(R 20 )(R 21 )}-) is located closer to the free end side, and more preferably, the most fixed end side is marked with The repeating units in which f12 and f14 are enclosed in parentheses (ie, -{C(Rf ^a22 )(Rf ^a23 )}-, and -{Si(Rf ^a24 )(Rf ^a25 )}-) are located on the most free end side than Repeating units marked with f11 and f13 and enclosed in parentheses (ie, -{C(R ²⁰ )(R ²¹ )}-, and -{Si(R ²² )(R ²³ )}-) are more on the free end side Location.

In the above formula (a2-1), preferably 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, M ³ is all -O-, M ⁴ are all methoxy, ethoxy or chlorine atoms (especially methoxy or ethoxy), M ¹ and M ² are both hydrogen atoms, f11 is 0, and f12 is 30-150 (more preferably 80- 140), f15 is 30-60, f13 and f14 are 0, f17 is 0-1 (especially 0), g1 is 3, and f16 is 1-10.

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

[Chemical formula 9]

In the above formula (a2-2),

Rf ^a26 , Rf ^a27 , Rf ^a28 , and Rf ^a29 are each independently an alkyl group ^having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom, or a fluorine atom. The Rf ^a26s may be different from each other, and if there are multiple Rf ^a27s , the multiple Rf ^a27s may be different from each other, and if there are multiple Rf ^a28s , the multiple Rf ^a28s may be different from each other, and there are multiple Rf ^a29s . case, multiple Rf ^a29 can be different from each other,

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 when there are multiple R ²⁵ , the multiple R ²⁵ may be different from each other, and R ²⁶ may exist In the case of a plurality of R 26s, the plurality of R ²⁶ may be different from each other, when there are a plurality of R ²⁷ , the plurality of R ²⁷ may be different from each other, and when there are a plurality of R ²⁸ , the plurality of 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, and when there are plural R ^29s , the plural R ^29s may be different from each other, and when there are plural R ^30s , the plural R ³⁰ can be different from each other,

M ⁷ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, and the aforementioned R is When there are a plurality of hydrogen atoms, 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 from each other.

M ⁵ and M ⁹ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when there are multiple M ⁵ , the multiple M ⁵ may be different from each other, and when there are multiple M ⁹ , Multiple M ^9s can be different from each other,

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

M ⁸ and M ¹¹ are each independently a hydrolyzable group, and when there are multiple M ⁸ , the multiple M ⁸ may be different from each other, and when there are multiple M ¹¹ , the multiple M ¹¹ may be different from each other,

f21, f22, f23, f24, and f25 are each independently an integer from 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 from 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,

For M ¹⁰ -, M ⁶ -, f21 -{C(R ²⁵ )(R ²⁶ )}-, f22 -{C(Rf ^a26 )(Rf ^a27 )}-, f23 -{Si(R ²⁷ ) (R ²⁸ )}-, f24-{Si(Rf ^a28 )(Rf ^a29 )}-, f25-M ⁷ -, f26-[CH ₂ C(M ⁵ ){(CH ₂ ) _f27 -Si( For 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 - become terminals, they are arranged in an order in which a perfluoropolyether structure is formed in at least a part, and -O- and -O- are discontinuous, they are arranged and bonded in any order. Arrangement and bonding in an arbitrary order are not limited to the meaning that each repeating unit is continuous and arranged in the order described in the above-mentioned formula (a2-2), as described in the above-mentioned formula (a2-1).

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

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

[Chemical formula 10]

In the above 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 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 each independently preferably 2-4, and more preferably 2-3. h1 is 5 to 70, h2 is 1 to 5, and h3 is 1 to 10. h1 is preferably 10-60, more preferably 20-50, h2 is preferably 1-4, more preferably 1-3, h3 is preferably 1-8, more preferably 1-6.

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

[Chemical formula 11]

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 a perfluoroalkyl group having 2 to 5 carbon atoms. In the fluoroalkylene group obtained by substituting a part of hydrogen atoms of an alkylene group with fluorine, R ⁴³ and R ⁴⁴ are each independently an alkylene group having 2 to 5 carbon atoms, and R ⁴⁵ is a methyl group or an ethyl group. k1, k2, and k3 are each independently an integer of 1-5.

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

As said organosilicon compound (A), for example, a compound represented by the following formula (1) or a compound having a similar structure to this compound can be mentioned, and OPTOOL (registered trademark) UF503 manufactured by Daikin Industries, Ltd. can be mentioned. Wait.

[Chemical formula 12]

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

Examples of the above-mentioned similar structures include structures in which the number of carbon atoms of the hydrocarbon group of the above formula (1) or the number of carbon atoms of the hydrocarbon group substituted by a fluorine atom is different, and the structure in which the perfluoropolyether structure and the silicon atom do not interpose a linking group. Structures bonded in a manner, structures in which other hydrocarbon groups (including hydrocarbon groups in which at least a part of hydrogen atoms are substituted with fluorine atoms) are sandwiched between the perfluoropolyether structure and the linking group between the silicon atom, silicon atoms and hydrolyzability A structure in which a group is bonded via a linking group, a structure in which the values of r and s are different, and the like are not limited to these structures.

II. Organosilicon compound (B)

As will be described later, the organosilicon compound (B) represented by the following formula (b1) has a hydrolyzable group represented by A ² . Usually, the -SiOH group of the organosilicon compound (B) produced by hydrolysis and the hydrolysis The -SiOH group of the resulting organosilicon compound (A) and/or the -SiOH group of the organosilicon compound (B) produced by hydrolysis undergo dehydration condensation, and therefore, in a preferred embodiment, as the aforementioned mixed composition (ca) The water repellent layer (r) of the cured layer has a condensation structure derived from the organosilicon compound (A) and a condensation structure derived from the organosilicon compound (B). As said hydrolyzable group, an alkoxy group, a halogen atom, a cyano group, an acetoxy group, an isocyanate group, etc. are mentioned.

[Chemical formula 13]

In the above formula (b1),

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

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 when there is a plurality of R ^b11 , the plurality of R ^b11 may be different from each other, and R ^b12 may be present. When there are multiple R ^b12s , they may be different from each other, when there are multiple R ^b13s , multiple R ^b13s may be different from each other, and when there are multiple R ^b14s , multiple R ^b14s may be different from each other. ,

Rf ^b11 , Rf ^b12 , Rf ^b13 , and Rf ^b14 are each independently an alkyl group ^having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom, or a fluorine atom. The Rf ^b11s may be different from each other, and if there are multiple Rf ^b12s , the multiple Rf ^b12s may be different from each other, and if there are multiple Rf ^b13s , the multiple Rf ^b13s may be different from each other, and there are multiple Rf ^b14s . case, multiple Rf ^b14 can be different from each other,

R ^b15 is an alkyl group having 1 to 20 carbon atoms, and when there are a plurality of R ^b15 , the plurality of R ^b15 may be different from each other,

A ¹ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, and the aforementioned R is When there are a plurality of hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, or fluorine-containing alkyl groups having ^{1 to 4 carbon atoms, the plurality of A 1s may} be different from each other.

A ² is a hydrolyzable group, and when there are multiple A ² s, the multiple A ² s 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,

For Rf ^b10 -, -Si(A ² ) _c (R ^b15 ) _3-c , b11 -{C(R ^b11 )(R ^b12 )}-, b12 -{C(Rf ^b11 )(Rf ^b12 )} -, b13 -{Si(R ^b13 )(R ^b14 )}-, b14 -{Si(Rf ^b13 )(Rf ^b14 )}-, b15 -A ¹ -, as long as Rf ^b10 -, -Si (A ² ) _c (R ^b15 ) _3-c becomes a terminal, does not form a perfluoropolyether structure, and -O- is not connected to -O- or -F, and is arranged and bonded in an arbitrary order.

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

R ^b11 , R ^b12 , R ^b13 and R ^b14 are preferably hydrogen atoms.

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

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

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

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

b12 is preferably 0-15, more preferably 0-10.

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

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

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

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

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

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

It should be noted that when FAS13E used as compound (B) in the examples to be described later is represented by the above formula (b1), it can be determined that both R ^b11 and R ^b12 are hydrogen atoms, b11 is 2, b13, Both b14 and b15 are 0, c is 3, A ² is an ethoxy group, Rf ^b10 -{C(Rf ^b11 )(Rf ^b12 )} _b12 - is a terminal, and it becomes C ₆ F ₁₃ -.

Specific examples of the compound represented by the above formula (b1) include CF ₃ -Si-(OCH ₃ ) ₃ , C _j F _2j+1 -Si-(OC ₂ H ₅ ) ₃ (j is an integer of 1 to 12) ), of which C ₄ F ₉ -Si-(OC ₂ H ₅ ) ₃ , C ₆ F ₁₃ -Si-(OC ₂ H ₅ ) ₃ , and C ₇ F ₁₅ -Si-(OC ₂ H ₅ ) are particularly preferred _3. C ₈ F ₁₇ -Si-(OC ₂ H ₅ ) ₃ . In addition, 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 all 5 to 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 all 2 to 10, preferably 2 to 8, q is all 1 to 5, It is preferably 2 to 4). In addition, 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 (all p are 2 to 10, preferably 3 to 7, and q are all 1 to 5, preferably 2 to 4).

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

[Chemical formula 14]

R ⁶⁰ --R ⁶¹ --Si(OR ⁶² ) ₃ ···(b2)

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.

In addition, the said mixed composition (ca) is a composition in which the said organosilicon compound (A) and the said organosilicon compound (B) are mixed, and can be obtained by mixing the said organosilicon compound (A) and the said organosilicon compound (B) is obtained by mixing, and when components other than the organosilicon compound (A) and the organosilicon compound (B) are mixed, the organosilicon compound (A), the organosilicon compound (B) is obtained by mixing with other components. The said mixed composition (ca) also includes the composition which reacted after mixing, for example, during storage.

III. Solvent (D)

The solvent (D) is usually mixed in the above-mentioned mixed composition (ca). 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, or the like can be used, and the boiling point is particularly preferably 100°C or higher. As the fluorinated ether-based solvent, hydrofluoroethers such as fluoroalkyl (especially perfluoroalkyl having 2 to 6 carbon atoms)-alkyl (especially methyl or ethyl) ethers are preferable, and for example, ethyl acetate is exemplified. nonafluorobutyl ether or ethyl nonafluoroisobutyl ether. As ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether, Novec (registered trademark) 7200 (manufactured by 3M Corporation, molecular weight is about 264) is mentioned, for example. The fluorinated amine-based solvent is preferably an amine obtained by substituting at least one hydrogen atom of ammonia with a fluoroalkyl group, and more preferably an amine obtained by substituting all of the hydrogen atoms of ammonia with a fluoroalkyl group (especially a perfluoroalkyl group). Specific examples of the tertiary amine include tris(heptafluoropropyl)amine, and Fluorinert (registered trademark) FC-3283 (manufactured by 3M Co., Ltd., molecular weight of about 521) belongs to this. Examples of the fluorinated hydrocarbon-based solvent include fluorinated aliphatic hydrocarbon-based solvents such as 1,1,1,3,3-pentafluorobutane, and fluorinated aromatic solvents such as 1,3-bis(trifluoromethylbenzene). Hydrocarbon solvents. As 1,1,1,3,3-pentafluorobutane, Sorb 55 (made by SOLVEX) etc. are mentioned, for example.

As the fluorine-based solvent, hydrochlorofluorocarbons such as Asahiklin (registered trademark) AK225 (manufactured by AGC Corporation) and the like, and hydrofluorocarbons such as Asahiklin (registered trademark) AC2000 (manufactured by Asahi Glass Co. Ltd.) can be used in addition to the above-mentioned solvents. Wait.

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

The amount of the aforementioned organosilicon compound (A) in the aforementioned mixed composition (ca) is, for example, 0.01 mass % or more, preferably 0.03 mass % or more, more preferably 0.01 mass % or more with respect to 100 mass % of the entire composition. 0.05 mass % or more, and preferably 1.0 mass % or less, more preferably 0.5 mass % or less, still more preferably 0.3 mass % or less, and particularly preferably 0.1 mass % or less.

The amount of the aforementioned organosilicon compound (B) in the aforementioned mixed composition (ca) is, for example, 0.01 mass % or more, preferably 0.03 mass % or more, preferably 0.03 mass % or more with respect to 100 mass % of the entire composition. It is 0.3 mass % or less, More preferably, it is 0.2 mass % or less.

The mass ratio of the organosilicon compound (B) to the organosilicon compound (A) is preferably 0.01 or more, more preferably 0.1 or more, still more preferably 0.3 or more, and preferably 2.0 or less, more preferably 1.5 or less, and further Preferably it is 1.0 or less.

The amounts of the above-mentioned organosilicon compounds (A) and (B) can be adjusted when preparing the composition. The amounts of the aforementioned organosilicon compounds (A) and (B) can also be calculated from the results of analysis of the composition.

In addition, in the aforementioned mixed composition (ca) for forming the water repellent layer (r), a silanol condensation catalyst, an antioxidant, a rust inhibitor, an ultraviolet absorber, a silanol condensation catalyst, an antioxidant, a rust inhibitor, an ultraviolet absorber, Various additives such as light stabilizer, antifungal agent, antibacterial agent, bioadhesion inhibitor, deodorant, pigment, flame retardant, antistatic agent, etc.

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

The aforementioned intermediate layer (c) is a cured layer of a mixed composition (cc) of an organosilicon compound (C) having a silicon atom and having an amino group or an amine skeleton (being -NR ¹⁰⁰ -, R ¹⁰⁰ being a hydrogen atom or an alkyl group) or In the vapor-deposited layer of the aforementioned organosilicon compound (C), the intermediate layer (c) has an amino group or an amine skeleton. In a preferred embodiment, a hydrolyzable group or a hydroxyl group is bonded to the silicon atom of the organosilicon compound (C), and the Si—OH group of the organosilicon compound (C) or the hydrolyzability due to the bond to the silicon atom is Since the -SiOH groups of the organosilicon compound (C) generated by the hydrolysis of the groups undergo dehydration condensation, the intermediate layer (c) preferably has a condensed structure derived from the organosilicon compound (C). The intermediate layer (c) can function as a primer layer for the water repellent layer (r). As a hydrolyzable group couple|bonded with the silicon atom of an organosilicon compound (C), an alkoxy group, a halogen atom, a cyano group, an acetoxy group, an isocyanate group, etc. are mentioned. Preferably, an alkoxy group or a hydroxyl group having 1 to 4 carbon atoms is bonded to the silicon atom of the organosilicon compound (C).

The organosilicon compound (C) is preferably a compound represented by any one of the following formulae (c1) to (c3).

IV-1. Organosilicon compound (C) represented by the following formula (c1) (hereinafter, organosilicon compound (C1))

[Chemical formula 15]

In the above formula (c1),

R ^x11 , R ^x12 , R ^x13 , and R ^x14 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when there is a plurality of R ^x11 , the plurality of R ^x11 may be different from each other, and R ^x12 is present When there are multiple Rx12s, the multiple ^Rx12s may be different from each other, when there are multiple ^Rx13s , the multiple ^Rx13s may be different from each other, and when there are multiple ^Rx14s , the multiple ^Rx14s may be different from each other. ,

Rf ^x11 , Rf ^x12 , Rf ^x13 , and Rf ^x14 are each independently an alkyl group ^having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom, or a fluorine atom. The Rf ^x11s may be different from each other. If there are multiple Rf ^x12s , the multiple Rf ^x12s may be different from each other. If there are multiple Rf ^x13s , the multiple Rf ^x13s may be different from each other. There are multiple Rf ^x14s . case, multiple Rf ^x14 can be different from each other,

R ^x15 is an alkyl group having 1 to 20 carbon atoms, and when there are a plurality of R ^x15 , the plurality of R ^x15 may be different from each other,

X ¹¹ is a hydrolyzable group, and when there are a plurality of X ¹¹ , the plurality of X ¹¹ may be different from each other,

Y ¹¹ is -NH- or -S-, and when there are a plurality of Y ¹¹ , the plurality of Y ¹¹ may be different from each other,

Z ¹¹ is vinyl, α-methyl vinyl, styryl, methacryloyl, acryloyl, amino, isocyanate, isocyanurate, epoxy, urea or mercapto,

p1 is an integer from 1 to 20, p2, p3, and p4 are each independently an integer from 0 to 10, p5 is an integer from 1 to 10,

p6 is an integer from 1 to 3,

When Z ¹¹ is not an amino group, at least one of Y ¹¹ is -NH-, and when all Y ¹¹ are -S-, Z ¹¹ is an amino group,

For Z ¹¹ -, -Si(X ¹¹ ) _p6 (R ^x15 ) _3-p6 , p1 -{C(R ^x11 )(R ^x12 )}-, p2 -{C(Rf ^x11 )(Rf ^x12 )} -, p3 -{Si(R ^x13 )(R ^x14 )}-, p4 -{Si(Rf ^x13 )(Rf ^x14 )}-, p5 -Y ¹¹ -, as long as Z ¹¹ - and -Si (X ¹¹ ) _p6 (R ^x15 ) _3-p6 serves as a terminal, and -O- is not linked to -O-, and they are arranged and bonded in an arbitrary order.

R ^x11 , R ^x12 , R ^x13 and R ^x14 are preferably hydrogen atoms.

Rf ^x11 , Rf ^x12 , Rf ^x13 and Rf ^x14 are each independently preferably an alkyl group having 1 to 10 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom, or a fluorine atom.

R ^x15 is preferably an alkyl group having 1 to 5 carbon atoms.

X ¹¹ is preferably an alkoxy group, a halogen atom, a cyano group or an isocyanate group, more preferably an alkoxy group, still more preferably a methoxy group or an ethoxy group.

Y ¹¹ is preferably -NH-.

Z ¹¹ 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.

It is preferable that p1 is 1-15, and it is more preferable that it is 2-10. p2, p3 and p4 are each independently preferably 0 to 5, and more preferably all of 0 to 2. It is preferable that p5 is 1-5, and it is more preferable that it is 1-3. p6 is preferably 2 to 3, and more preferably 3.

As the organosilicon compound (C), the following compounds are preferably used: In the above formula (c1), R ^x11 and R ^x12 are both hydrogen atoms, Y ¹¹ is -NH-, and X ¹¹ is an alkoxy group (especially a methoxy group). or ethoxy), Z ¹¹ is an amino group or a mercapto group, p1 is 1-10, p2, p3 and p4 are all 0, p5 is 1-5 (especially 1-3), and p6 is a compound of 3.

The organosilicon compound (C1) is preferably represented by the following formula (c1-2).

[Chemical formula 16]

Z ¹² -C _q H2 _q -Y ¹² -C _r H _2r -Si(X ¹² ) _p (R ^x16 ) _3-p …(c1-2)

In the above formula (c1-2),

X ¹² is a hydrolyzable group, and when there are a plurality of X ¹² , the plurality of X ¹² may be different from each other,

Y ¹² is -NH-,

Z ¹² is an amino group or a thiol group,

R ^x16 is an alkyl group having 1 to 20 carbon atoms, and when there are a plurality of R ^x16 , the plurality of R ^x16 may be different from each other,

p is an integer of 1-3, q is an integer of 2-5, and r is an integer of 0-5.

X ¹² is preferably an alkoxy group, a halogen atom, a cyano group, or an isocyanate group, more preferably an alkoxy group, and still more preferably an alkoxy group having 1 to 4 carbon atoms.

Z ¹² is preferably an amino group.

R ^x16 is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

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

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

IV-2. Organosilicon compound (C) represented by the following formula (c2) (hereinafter, organosilicon compound (C2))

[Chemical formula 17]

In the above formula (c2),

R ^x20 and R ^x21 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when there are plural R ^x20s , the plural R ^x20s may be different from each other, and when there are plural R ^x21s , multiple R ^x21 can be different from each other,

Rf ^x20 and Rf ^x21 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms, or a fluorine atom, and when there are multiple Rf ^x20s , the multiple Rf ^x20s may be different from each other. , if there are multiple Rf ^x21s , the multiple Rf ^x21s can be different from each other,

^Rx22 and ^Rx23 are each independently an alkyl group having 1 to 20 carbon atoms, and when there are a plurality of ^Rx22 and ^Rx23 , the plurality of ^Rx22 and ^Rx23 may be different from each other,

X ²⁰ and X ²¹ are each independently a hydrolyzable group, and when there are a plurality of X ²⁰ and X ²¹ , the plurality of X ²⁰ and X ²¹ may be different from each other,

p20 is an integer of 1 to 30, p21 is an integer of 0 to 30, and at least one of the repeating units marked with p20 or p21 and enclosed in parentheses is replaced with an amine skeleton -NR ¹⁰⁰ -, R ¹⁰⁰ in the aforementioned amine skeleton is a hydrogen atom or an alkyl group,

p22 and p23 are each independently an integer of 1 to 3,

For p20-{C( ^Rx20 )( ^Rx21 )}-, p21-{C( ^Rfx20 )( ^Rfx21 )}-, it is not necessary for p20 or p21 to be consecutive, in any order The two ends are bonded together to form -Si(X ²⁰ ) _p22 (R ^x22 ) _3-p22 and -Si(X ²¹ ) _p23 (R ^x23 ) _3-p23 .

R ^x20 and R ^x21 are preferably hydrogen atoms.

Rf ^x20 and Rf ^x21 are each independently preferably an alkyl group having 1 to 10 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom, or a fluorine atom.

R ^x22 and R ^x23 are preferably an alkyl group having 1 to 5 carbon atoms.

X ²⁰ and X ²¹ are preferably an alkoxy group, a halogen atom, a cyano group, or an isocyanate group, more preferably an alkoxy group, and still more preferably a methoxy group or an ethoxy group.

Amine skeleton -NR ¹⁰⁰ - As described above, at least one of the repeating units in the parentheses marked with p20 or p21 may be replaced with the aforementioned amine skeleton, but preferably Part of a repeating unit marked p20 and enclosed in parentheses. A plurality of the amine skeletons may exist. In this case, the number of the 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, and the number of carbon atoms of the alkylene group is preferably 1-10, and more preferably 1-5. The number of carbon atoms of the alkylene group between adjacent amine skeletons is included in the total number of p20 or p21.

In the amine skeleton -NR ¹⁰⁰ -, when R ¹⁰⁰ is an alkyl group, the number of carbon atoms 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).

As for p20, 1-15 are preferable, and 1-10 are more preferable, excluding the number of repeating units substituted by the amine skeleton.

It is preferable that p21 is 0-5 when the number of repeating units substituted by the amine skeleton is not included, and it is more preferable that it is all 0-2.

p22 and p23 are preferably 2 to 3, and more preferably 3.

As the organosilicon compound (C2), the following compounds are preferably used: in the above formula (c2), both R ^x20 and R ^x21 are hydrogen atoms, and X ²⁰ and X ²¹ are alkoxy groups (especially methoxy or ethoxy groups). ), at least one of the repeating units marked with p20 and enclosed in parentheses is replaced with an amine skeleton -NR ¹⁰⁰ -, R ¹⁰⁰ is a hydrogen atom, and p20 is 1 to 10 (wherein, repeats replaced with an amine skeleton are not included The number of units), p21 is 0, p22 and p23 are 3 compounds.

In addition, N-2-(aminoethyl)-3-aminopropyltrimethoxy group described in JP-A No. 2012-197330 was used as compound (C) in the examples described later. When the reaction product of silane and chloropropyltrimethoxysilane (trade name; X-12-5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.) is represented by the above formula (c2), both R ^x20 and R ^x21 are hydrogen atoms, and p20 is 8, p21 is 0, the amine skeleton is 2 (R ¹⁰⁰ is both a hydrogen atom), both ends are the same, p22 and p23 are 3, and X ²⁰ and X ²¹ are methoxy groups.

The organosilicon compound (C2) is preferably a compound represented by the following formula (c2-2).

[Chemical formula 18]

(R ^x25 ) _3-p25 (X ²³ ) _p25 Si--C _w H _2w -Si(X ²² ) _p24 (R ^x24 ) _3-p24 (c2-2)

In the above formula (c2-2),

X ²² and X ²³ are each independently a hydrolyzable group, and when there are a plurality of X ²² and X ²³ , the plurality of X ²² and X ²³ may be different from each other,

^Rx24 and ^Rx25 are each independently an alkyl group having 1 to 20 carbon atoms, and when there are a plurality of ^Rx24 and ^Rx25 , the plurality of ^Rx24 and ^Rx25 may be different from each other,

For -C _w H _2w -, at least one of a part of its methylene groups is replaced by an amine skeleton -NR ¹⁰⁰ -, R ¹⁰⁰ is a hydrogen atom or an alkyl group,

w is an integer of 1 to 30 (wherein, the number of methylene groups replaced by the amine skeleton is not included),

p24 and p25 are each independently an integer of 1-3.

X ²² and X ²³ are preferably an alkoxy group, a halogen atom, a cyano group or an isocyanate group, more preferably an alkoxy group, and still more preferably an alkoxy group having 1 to 4 carbon atoms (especially a methoxy group or an ethoxy group). ).

A plurality of amine skeletons -NR ¹⁰⁰ - may exist, and the number of amine skeletons in this case is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 5. Moreover, in this case, it is preferable to have an alkylene group between adjacent amine skeletons. 1-10 are preferable and, as for carbon number of the said alkylene group, 1-5 are more preferable. The number of carbon atoms of the alkylene group between adjacent amine skeletons is included in the total number of w.

In the amine skeleton -NR ¹⁰⁰ -, when R ¹⁰⁰ is an alkyl group, the number of carbon atoms 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 ^x24 and R ^x25 are preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

p24 and p25 are preferably an integer of 2 to 3, and more preferably 3.

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

IV-3. Organosilicon compound (C) represented by the following formula (c3) (hereinafter, organosilicon compound (C3))

[Chemical formula 19]

In the above formula (c3),

Z ³¹ and Z ³² are each independently a reactive functional group other than a hydrolyzable group and a hydroxyl group. Examples of the reactive functional group include vinyl groups, α-methyl vinyl groups, styryl groups, methacryloyl groups, acryloyl groups, amino groups, epoxy groups, urea groups, or mercapto groups. As Z ³¹ and Z ³² , an amino group, a mercapto group, or a methacryloyl group is preferable, and an amino group is particularly preferable.

R ^x31 , R ^x32 , R ^x33 , and R ^x34 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when there is a plurality of R ^x31 , the plurality of R ^x31 may be different from each other, and R ^x32 is present When there are multiple Rx32s, they may be different from each other. ^When there are multiple ^Rx33s , multiple ^Rx33s may be different from each other. When there are multiple ^{Rx34s, multiple Rx34s may} be different from each other. . R ^x31 , R ^x32 , R ^x33 , and R ^x34 are preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably a hydrogen atom.

Rf ^x31 , Rf ^x32 , Rf ^x33 , and Rf ^x34 are each independently an alkyl group ^having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom, or a fluorine atom. The Rf ^x31s may be different from each other. If there are multiple Rf ^x32s , the multiple Rf ^x32s may be different from each other. If there are multiple Rf ^x33s , the multiple Rf ^x33s may be different from each other. There are multiple Rf ^x34s . In this case, the plurality of Rf ^x34 may be different from each other. Rf ^x31 , Rf ^x32 , Rf ^x33 , and Rf ^x34 are preferably an alkyl group having 1 to 10 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted with a fluorine atom.

Y ³¹ is -NH-, -N(CH ₃ )- or -O-, and when there are plural Y ^31s , the plural Y ^31s may be different from each other. Y ³¹ is preferably -NH-.

X ³¹ , X ³² , X ³³ and X ³⁴ are each independently -OR ^c (R ^c is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an amino C _1-3 alkyl _{diC 1-3} alkoxy group silyl group), when there are multiple X ³¹ , the multiple X ³¹ may be different from each other, when there are multiple X ³² , the multiple X ³² may be different from each other, and there are multiple X ³³ . In the following, a plurality of X ³³ may be different from each other, and when there are a plurality of X ³⁴ , a plurality of X ³⁴ may be different from each other. X ³¹ , X ³² , X ³³ and X ³⁴ are preferably —OR ^c in which R ^c is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R ^c is more preferably a hydrogen atom.

p31 is an integer of 0 to 20, p32, p33, and p34 are each independently an integer of 0 to 10, p35 is an integer of 0 to 5, p36 is an integer of 1 to 10, and p37 is 0 or 1. It is preferable that p31 is 1-15, It is more preferable that it is 3-13, It is still more preferable that it is 5-10. p32, p33, and p34 are each independently preferably 0 to 5, and more preferably all of 0 to 2. It is preferable that p35 is 1-5, and it is more preferable that it is 1-3. It is preferable that p36 is 1-5, and it is more preferable that it is 1-3. p37 is preferably 1.

For the organosilicon compound (C3), as long as at least one of Z ³¹ and Z ³² is an amino group, or at least one of Y ³¹ is -NH- or -N(CH ₃ )-, and the terminal is Z ³¹ - and Z ³² -, -O- is not connected to -O-, then p31 -{C(R ^x31 )(R ^x32 )}-, p32 -{C(Rf ^x31 )(Rf ^x32 )}- , p33-{Si( ^Rx33 )( ^Rx34 )}-, p34-{Si( ^Rfx33 )( ^Rfx34 )}-, p35- ^Y31- , ^p36- {Si(X31)( X ³² )-O}- and p37 pieces -{Si(X ³³ )(X ³⁴ )}- are arranged in an arbitrary order and bonded together. p31 units -{C(R ^x31 )(R ^x32 )}- do not need to be -{C(R ^x31 )(R ^x32 )}- consecutively bonded, but may be bonded through other units in the middle, and the total is p31 one is enough. The same applies to the units enclosed by p32 to p37.

The organosilicon compound (C3) is preferably a compound in which Z ³¹ and Z ³² are amino groups, R ^x31 and R ^x32 are hydrogen atoms, p31 is 3 to 13 (preferably 5 to 10), and both R ^x33 and R ^x34 are is a hydrogen atom, Rf ^x31 to Rf ^x34 are all alkyl groups with 1 to 10 carbon atoms or fluorine atoms in which one or more hydrogen atoms are replaced by fluorine atoms, p32 to p34 are all 0 to 5, and Y ³¹ is -NH- , p35 is 0 to 5 (preferably 0 to 3), X ³¹ to X ³⁴ are all -OH, p36 is 1 to 5 (preferably 1 to 3), and p37 is a compound of 1.

The organosilicon compound (C3) is preferably represented by the following formula (c3-2).

[Chemical formula 20]

In the aforementioned formula (c3-2), Z ³¹ , Z ³² , X ³¹ , X ³² , X ³³ , X ³⁴ , and Y ³¹ have the same meanings as those in the formula (c3), and p41 to p44 are each independently 1 to An integer of 6, and p45 and 46 are each independently 0 or 1.

In formula (c3-2), Z ³¹ and Z ³² are preferably an amino group, a mercapto group or a methacryloyl group, and particularly preferably an amino group. X ³¹ , X ³² , X ³³ and X ³⁴ are preferably —OR ^c in which R ^c is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R ^c is more preferably a hydrogen atom. Y ³¹ is preferably -NH-. It is preferable that p41-p44 is 2 or more, and it is preferable that it is 5 or less, and it is more preferable that it is 4 or less. Both p45 and p46 are preferably 0.

The aforementioned mixed composition (cc) is a composition in which the aforementioned organosilicon compound (C) is mixed, and the aforementioned organosilicon compound (C) may be one type or two or more types. The mixed composition (cc) can be obtained by mixing the organosilicon compound (C), and when mixing components other than the organosilicon compound (C), it can be obtained by mixing the organosilicon compound (C) with other components . The said mixed composition (cc) also includes the composition which reacted after mixing, for example, during storage.

As an example in which the reaction proceeds during storage of the mixed composition (cc), the case where the mixed composition (cc) contains the condensate of the above-mentioned organosilicon compound (C) can be mentioned, and more specifically, there can be mentioned The said mixed composition (cc) contains the organosilicon compound (C3') which the said organosilicon compound (C3) was condensed and couple|bonded by at least any one of said ^X31 - ^X34 .

The aforementioned organosilicon compound (C3') has two or more structures (c31-1) represented by the following formula (c31-1), and the aforementioned structures (c31-1) are bonded to each other by the following *3 or *4 To synthesize a chain or cyclic compound, the following bond at *3 or *4 is formed by condensation of the aforementioned X ³¹ or X ³² of two or more of the aforementioned organosilicon compounds (C3),

Units enclosed by p31, p32, p33, p34, p35, (p36)-1, and p37 of the following formula (c31-2) are bonded to *1 and *2 of the following formula (c31-1), respectively. At least one of the groups is bonded in an arbitrary order and has a Z- terminal, and the groups bonded to *1 and *2 may be different for each of the plurality of aforementioned structures (c31-1) ,

When a plurality of the above-mentioned structures (c31-1) are bonded into a chain, *3 which becomes the terminal is a hydrogen atom, and *4 is a hydroxyl group.

[Chemical formula 21]

[Chemical formula 22]

In the aforementioned formula (c31-2),

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

The meanings of R ^x31 , R ^x32 , R ^x33 , R ^x34 , Rf ^x31 , Rf ^x32 , Rf ^x33 , Rf ³⁴ , Y ³¹ , X ³¹ , X ³² , X ³³ , X ³⁴ , p31 to p37 are the same as those of the aforementioned formula (c3) These symbols in are the same.

When the organosilicon compound (C3) is a compound represented by the aforementioned formula (c3-2), the organosilicon compound (C3') includes, for example, a structure represented by the following formula (c31-3), and the following *3 or *4 is a compound obtained by synthesizing a chain or a cyclic bond. When the structure represented by the following formula (c31-3) is bonded to a chain, *3 at the terminal is a hydrogen atom, and *4 at the terminal is a hydroxyl group.

[Chemical formula 23]

The meanings of the symbols in the aforementioned formula (c31-3) are all the same as those in the aforementioned formula (c3-2).

The organosilicon compound (C3') is preferably a compound in which 2 to 10 (preferably 3 to 8) structures represented by the aforementioned formula (c31-3) are bonded.

V. Solvent (E)

It is preferable that the solvent (E) is mixed with the said mixed composition (cc). The solvent (E) is not particularly limited, and for example, water, alcohol-based solvents, ketone-based solvents, ether-based solvents, hydrocarbon-based solvents, ester-based solvents, and the like can be used, and water, alcohol-based solvents, ketone-based solvents, and hydrocarbon-based solvents are particularly preferred. .

Examples of the alcohol-based solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and the like.

As a ketone solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. are mentioned.

As an ether-based solvent, diethyl ether, dipropyl ether, tetrahydrofuran, 1,4-dioxane, etc. are mentioned.

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.

As an ester solvent, ethyl acetate, propyl acetate, butyl acetate, etc. are mentioned.

The total amount of the organosilicon compound (C) is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.02% by mass or more, when the entire composition (cc) is taken as 100% by mass, still more preferably 0.02% by mass or more. 0.1 mass % or more is preferable, and 5 mass % or less is preferable, 3 mass % or less is more preferable, and 2 mass % or less is further more preferable. The amount of the above-mentioned organosilicon compound (C) can be adjusted at the time of preparing the composition. The amount of the aforementioned organosilicon compound (C) can also be calculated from the analysis result of the composition. In addition, when the range of the quantity, mass ratio, or molar ratio of each component is described in this specification, the range can be adjusted when preparing a composition similarly to the above.

The substrate (s) is preferably a layer having a function of preventing reflection of incident light on the surface on the side of the intermediate layer (c). The layer on the side showing the reflective properties in which the reflectance is reduced to about 5.0% or less is more preferably 4.80% or less, and still more preferably 4.5% or less. This reflectance can be evaluated using the spectral reflectance at a wavelength of 530 nm.

The substrate (s) preferably has a surface Si ratio of 1 atomic % or more in at least the outermost layer on the side of the intermediate layer (c), and the substrate (s) is preferably an organic material or an inorganic material. When the surface Si ratio is a predetermined value or more, the surface of the substrate (s) and the components constituting the intermediate layer (c) or the water-repellent layer (r) are easily bonded, and the laminate of the present invention is on the water-repellent layer (r) side. The wear resistance of the surface is further improved. The surface Si ratio is more preferably 5 atomic % or more, still more preferably 10 atomic % or more, still more preferably 20 atomic % or more, and may be 40 atomic % or less.

The said base material (s) may consist of 1 type of material, and may consist of 2 or more types of materials. Examples of the material constituting the base material (s) include acrylic resins, polycarbonate resins, polyester resins (polyethylene terephthalate, etc.), styrene resins, and acrylic-styrene copolymer resins. , cellulose resin, polyolefin resin, vinyl resin (polyethylene, polyvinyl chloride, polystyrene, vinylbenzyl chloride resin, polyvinyl alcohol, etc.) thermoplastic resin; or phenolic resin, urea resin, melamine Thermosetting resins such as resins, epoxy resins, unsaturated polyesters, silicone resins, and polyurethane resins; or resin materials such as engineering plastics such as polyamide-based resins, polyimide-based resins, and polyamide-imide-based resins; or titanium , oxides of metals such as zirconium, aluminium, niobium, tantalum, lanthanum or silicon.

When the said base material (s) consists of one type of material, it may be a resin layer whose surface Si ratio is 1 atomic % or more, or may be a metal oxide layer such as silica.

When the aforementioned base material (s) is composed of two or more kinds of materials, it is preferable to provide a protective layer on the resin layer (which is used to protect articles from damage in applications that require abrasion resistance, such as displays of electronic equipment). provided, hereinafter sometimes referred to as a hard coat layer.) to obtain a base material. As the material constituting the resin layer, the above-mentioned thermosetting resins, thermoplastic resins, or engineering plastics can be used, and polyester resins are particularly preferred. The above-mentioned hard coat layer is a layer having surface hardness, and the hardness thereof is, for example, 2H or more in terms of pencil hardness. The hard coat layer may have a single-layer structure or a multi-layer structure. The hard coat layer contains a hard coat resin, and examples of the hard coat resin include acrylic resins, epoxy resins, urethane resins, vinylbenzyl chloride resins, vinyl resins UV-curable, electron beam-curable, or thermosetting resins such as resins, silicone-based resins, or mixed resins thereof, and further, as described above, in the resins forming these hard coat layers, it is preferable that the surface Si ratio is 1 atomic % or more. In particular, in order to exhibit high hardness, it is preferable that the hard coat layer contains an acrylic resin, and the surface Si ratio is 1 atomic % or more. It is also preferable to contain an epoxy-type resin from the viewpoint that the tendency for the adhesiveness with the said water repellent layer (r) to interpose the said intermediate layer (c) becomes favorable is seen.

The hard coat layer may further contain an ultraviolet absorber, and may contain metal oxides such as silica and alumina, and inorganic fillers such as polyorganosiloxane. By containing such an inorganic filler, the adhesiveness with the said water repellent layer (r) with the said intermediate layer (c) interposed therebetween can be improved.

When the base material (s) is composed of two or more kinds of materials, it may be a base material obtained by providing an antireflection layer on a resin layer, and it is also preferable to further have a hard coat layer provided on the resin layer. The base material of the antireflection layer, in this case, is laminated in the order of a resin layer, a hard coat layer, an antireflection layer, an intermediate layer (c), and a water repellent layer (r). As the material constituting the resin layer, the above-mentioned thermosetting resin, thermoplastic resin, or engineering plastic can be used. The antireflection layer is a layer having a function of preventing reflection of incident light, and is a layer showing a reflection characteristic in which the reflectance is reduced to about 5% or less in the visible light region of 380 to 780 nm. The structure of the antireflection layer is not particularly limited, and may be a single-layer structure or a multilayer structure. In the case of a multilayer structure, a structure in which low-refractive-index layers and high-refractive-index layers are alternately laminated is preferable, and the number of laminations is preferably 2 to 20 in total. Examples of the material constituting the high refractive index layer include oxides of titanium, zirconium, aluminum, niobium, tantalum, or lanthanum, and examples of the material constituting the low refractive index layer include oxides of silicon (ie, silicon dioxide). Wait. The antireflection layer of the multilayer structure is preferably a structure in which SiO ₂ and ZrO ₂ , or SiO ₂ and Nb ₂ O ₅ are alternately stacked, and the outermost layer on the opposite side to the substrate (s) is SiO ₂ . The antireflection layer can be formed by, for example, a vapor deposition method.

In the above-mentioned base material (s), the above-mentioned reflection characteristics and/or the above-mentioned material may be satisfied in at least the outermost layer on the side of the intermediate layer (c) of the above-mentioned base material (s), and preferably in the above-mentioned base material (s) The thickness of the intermediate layer (c) side is 10% or more from the outermost layer (the thickness of the base material (s)), more preferably 40% or more of the thickness, even more preferably The material(s) is satisfied in the whole.

The thickness of the substrate (s) is, for example, 1 to 498 μm, preferably 1 to 300 μm, more preferably 1 to 100 μm, still more preferably 10 to 95 μm, and particularly preferably 30 to 90 μm.

The water contact angle (initial contact angle) when the laminate of the present invention is evaluated by the method described in the examples below is, for example, 105° or more, more preferably 110° or more, and, for example, 125° or less.

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

The first method for producing the laminate of the present invention includes (i) a step of applying the mixed composition (cc) to the substrate (s), and (ii) applying the mixed composition (cc) to the coated surface of the substrate (s). The step of distributing the mixed composition (ca), and (iii) the step of curing the mixed composition (cc) and the mixed composition (ca), the above-mentioned mixed composition (cc) is formed from the coating layer of the above-mentioned mixed composition (cc). The intermediate layer (c) forms the aforementioned water-repellent layer (r) from the coating layer of the aforementioned mixed composition (ca).

As a method of coating the aforementioned mixed composition (cc), a known method can be used, and a spin coating method or a dip coating method is preferable.

Next, the above-mentioned mixed composition (ca) for forming the water repellent layer (r) is applied to the coated surface of the above-mentioned mixed composition (cc) and dried, whereby the above-mentioned mixed composition (cc) can be The coating layer of ) forms the said intermediate layer (c), and the coating layer of the said mixed composition (ca) forms the said water repellent layer (r). The aforementioned intermediate layer (c) may be formed during the coating process of the aforementioned mixed composition (cc), or may be formed after coating, and the aforementioned intermediate layer (c) and the aforementioned water repellent layer (r) may be formed simultaneously. . Examples of the method for applying the composition for forming the water repellent layer (r) include dip coating, roll coating, bar coating, spin coating, spray coating, die coating, and gravure coating. Wait.

After applying the composition for forming the water repellent layer (r), the laminate of the present invention can be produced by allowing it to stand in the atmosphere at room temperature for, for example, 1 hour or more (usually 24 hours or less). In this invention, the normal temperature is 5-60 degreeC, Preferably it is the temperature range of 15-40 degreeC. The humidity condition at the time of standing still at normal temperature can be set to 50 to 90% RH. In addition, after applying the composition for forming the water repellent layer (r), it may be heated to a temperature exceeding 60°C (usually 100°C or lower. It may be 80°C or lower) and maintained for 5 minutes to 60 minutes (preferably 20 minutes to 40 minutes).

Moreover, the 2nd method of manufacturing the laminated body of this invention comprises vapor-depositing the said organosilicon compound (C) on the said base material (s) to form the intermediate layer (c), and coating the said intermediate layer (c) on the said intermediate layer (c). The composition (ca) is mixed and cured, and the said water repellent layer (r) is formed from the coating layer of the said mixed composition (ca). When the aforementioned organosilicon compound (C) is vapor-deposited to form the aforementioned intermediate layer (c), the aforementioned organosilicon compound (C) may be simply vapor-deposited on the substrate (s), or the aforementioned organosilicon compound (C) The solid substance obtained by removing the solvent from the mixed composition with the solvent (that is, the aforementioned organosilicon compound (C)) is vapor-deposited on the substrate (s). After applying the composition for forming the water repellent layer (r), it is sufficient to operate in the same manner as in the first method described above.

Before applying the composition (cc) or vapor-depositing the organosilicon compound (C), the substrate (s) is preferably subjected to a hydrophilization treatment in advance. Examples of the hydrophilization treatment include hydrophilization treatments such as corona treatment, plasma treatment, ultraviolet treatment, and ion cleaning treatment, and plasma treatment and ion cleaning treatment are more preferred. By performing a hydrophilization treatment such as plasma treatment, functional groups such as OH groups and COOH groups can be formed on the surface of the substrate, and when such functional groups are formed on the surface of the substrate, the interlayer (c) and the Adhesion of the said base material (s).

<Flexible Display Device>

The present invention also provides a flexible display device including the optical laminate of the present invention. The laminate of the present invention can preferably be used as a front panel, sometimes referred to as a window film, in a flexible display device. The flexible display device is preferably formed of a laminate for a flexible display device and an organic EL display panel, and the laminate for a flexible display device is arranged on the viewing side of the organic EL display panel and is configured to be bendable. The laminate for a flexible display device may further contain a polarizing plate (preferably a circular polarizing plate), a touch sensor, and the like, and the lamination order of these is arbitrary, but it is preferable to press the window film (that is, the laminate of the present invention), the polarized light from the viewing side, and the like. plate, touch sensor in the order, or laminated in the order of window film, touch sensor, polarizer. When a polarizing plate is present at a position closer to the viewing side than the touch sensor, it is difficult to observe the pattern of the touch sensor and the visibility of the displayed image becomes good, which is preferable. Each member can be laminated using an adhesive, a pressure-sensitive adhesive, or the like. In addition, the flexible display device may include a light-shielding pattern formed on at least one surface of any one of the above-mentioned window film, polarizer, and touch sensor.

＜Circular polarizer＞

As described above, the flexible display device of the present invention preferably includes a polarizing plate, particularly a circular polarizing plate. The circularly polarizing plate is a functional layer having a function of transmitting only a right-handed circularly polarized light component or a left-handed circularly polarized light component by laminating a λ/4 retardation plate on a linear polarizing plate. For example, it can be used to convert external light into right-handed circularly polarized light, block the external light that is reflected by the organic EL panel and become left-handed circularly polarized light, and only transmit the light-emitting component of the organic EL, thereby suppressing the influence of reflected light , thereby making it easy to view the image. In order to achieve the function of circularly polarized light, the absorption axis of the linear polarizer and the slow axis of the λ/4 retardation plate need to be 45 degrees in theory, but in practical applications it is 45±10 degrees. The linear polarizer and the λ/4 retardation plate do not necessarily have to be stacked adjacent to each other, and the relationship between the absorption axis and the slow axis may satisfy the aforementioned range. It is preferable to achieve complete circularly polarized light at all wavelengths, but this is not necessary in practical applications. Therefore, the circularly polarizing plate in the present invention also includes an elliptically polarizing plate. It is also preferable that a λ/4 retardation film is further laminated on the viewing side of the linear polarizing plate so that the outgoing light becomes circularly polarized light, thereby improving visibility in a state of wearing polarized sunglasses.

The linear polarizer is a functional layer having a function of passing light vibrating in the direction of the transmission axis and blocking polarized light of a vibration component perpendicular thereto. The linear polarizer may be a single linear polarizer or a structure including a linear polarizer and a protective film bonded to at least one surface of the linear polarizer. The thickness of the linear polarizing plate may be 200 μm or less, and preferably 0.5 to 100 μm. When the thickness of the linearly polarizing plate is within the aforementioned range, the flexibility of the linearly polarizing plate tends to be less likely to decrease.

The linear polarizer may be a film-type polarizer produced by dyeing and stretching a polyvinyl alcohol (hereinafter, abbreviated as PVA)-based film in some cases. The polarizing performance can be exhibited by adsorbing a dichroic dye such as iodine on the PVA-based film oriented by stretching, or by stretching the dichroic dye in a state of being adsorbed on PVA to orient the dichroic dye. In the production of the above-mentioned film-type polarizer, steps such as swelling, crosslinking by boric acid, washing by aqueous solution, and drying may be included. The stretching and dyeing process may be performed as a PVA-based film alone, or may be performed in a state of being laminated with another film such as polyethylene terephthalate. The thickness of the PVA-based film to be used is preferably 10 to 100 μm, and the stretching ratio is preferably 2 to 10 times.

Moreover, as another example of the said polarizer, the liquid crystal coating type polarizer formed by apply|coating a liquid crystal polarizing composition is mentioned. The liquid crystal polarizing composition may contain a liquid crystal compound and a dichroic dye compound. The aforementioned liquid crystalline compound only needs to have a property of exhibiting a liquid crystal state, and in particular, when it has a high-order alignment state such as smectic, it is preferable because it can exhibit high polarization performance. In addition, the liquid crystal compound preferably has a polymerizable functional group.

The dichroic dye compound is a dye that is aligned together with the liquid crystal compound and exhibits dichroism, may have a polymerizable functional group, and the dichroic dye itself may have liquid crystallinity.

Any of the compounds contained in the liquid crystal polarizing composition has a polymerizable functional group. The aforementioned liquid crystal polarizing composition may further contain an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a crosslinking agent, a silane coupling agent, and the like.

The said liquid crystal polarizing layer can be manufactured by apply|coating a liquid crystal polarizing composition on an alignment film, and forming a liquid crystal polarizing layer. Compared with the film-type polarizer, the liquid crystal polarizing layer can be formed to have a thinner thickness, and the thickness thereof is preferably 0.5 to 10 μm, and more preferably 1 to 5 μm.

The said orientation film can be manufactured by apply|coating an orientation film forming composition on a base material, and providing orientation by rubbing, polarized light irradiation, etc., for example. The aforementioned alignment film forming composition contains an alignment agent, and may further contain a solvent, a crosslinking agent, an initiator, a dispersing agent, a leveling agent, a silane coupling agent, and the like. As said alignment agent, polyvinyl alcohol, polyacrylate, polyamic acid, and polyimide are mentioned, for example. When using the orientation agent which provides orientation by polarized light irradiation, it is preferable to use the orientation agent containing a cinnamate group. The weight average molecular weight of the polymer which can be used as the said alignment agent is about 10,000-1,000,000, for example. The thickness of the aforementioned alignment film is preferably 5 to 10,000 nm, and more preferably 10 to 500 nm from the viewpoint of sufficiently exhibiting the alignment regulating force.

The liquid crystal polarizing layer may be laminated after being peeled from the base material, or may be laminated directly. It is also preferable that the above-mentioned base material plays a role as a transparent base material of a protective film, a retardation plate, and a window film.

The protective film may be a transparent polymer film, and the same materials and additives as those used in the transparent base material of the window film can be used. In addition, it may be a coating-type protective film obtained by coating a cationic curing composition such as an epoxy resin, and a radical curing composition such as an acrylate, and curing it. The protective film may contain plasticizers, ultraviolet absorbers, infrared absorbers, pigments, colorants such as dyes, optical brighteners, dispersants, heat stabilizers, light stabilizers, antistatic agents, and antioxidants as required. , lubricants, solvents, etc. The thickness of the protective film is preferably 200 μm or less, and more preferably 1 to 100 μm. When the thickness of a protective film is in the said range, there exists a tendency for the flexibility of this film to be hard to fall.

The aforementioned λ/4 retardation plate is a film that provides a retardation of λ/4 in the direction perpendicular to the advancing direction of the incident light (the in-plane direction of the film). The aforementioned λ/4 retardation plate may be a stretched retardation plate produced by stretching a polymer film such as a cellulose-based film, an olefin-based film, and a polycarbonate-based film. The aforementioned λ/4 retardation plate may contain retardation modifiers, plasticizers, ultraviolet absorbers, infrared absorbers, pigments, colorants such as dyes, optical brighteners, dispersants, heat stabilizers, light Stabilizers, antistatic agents, antioxidants, lubricants, solvents, etc.

The thickness of the stretched retardation plate is preferably 200 μm or less, and more preferably 1 to 100 μm. When the thickness of the stretched retardation plate is within the aforementioned range, there is a tendency that the flexibility of the stretched retardation plate is less likely to decrease.

Moreover, as another example of the said λ/4 retardation plate, the liquid crystal coating type retardation plate formed by apply|coating a liquid crystal composition is mentioned.

The liquid crystal composition includes a liquid crystal compound exhibiting a liquid crystal state such as nematic, cholesteric, and smectic. The aforementioned liquid crystal compound has a polymerizable functional group.

The aforementioned liquid crystal composition may further contain an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a crosslinking agent, a silane coupling agent, and the like.

The liquid crystal coating-type retardation plate can be produced by coating a liquid crystal composition on a substrate and curing it to form a liquid crystal retardation layer in the same manner as the liquid crystal polarizing layer. Compared with the stretched retardation film, the liquid crystal coated retardation film can be formed with a thinner thickness. The thickness of the liquid crystal polarizing layer is preferably 0.5 to 10 μm, and more preferably 1 to 5 μm.

The liquid crystal coating-type retardation plate may be laminated after being peeled from the base material, or the base material may be directly laminated. It is also preferable that the above-mentioned base material plays a role as a transparent base material of a protective film, a retardation plate, and a window film.

In general, the shorter the wavelength, the greater the birefringence, and the longer the wavelength, the smaller the birefringence is, there are many materials. In this case, since the retardation of λ/4 cannot be achieved in the entire visible light region, the in-plane retardation is preferably 100 to 180 nm, more preferably 130 to 130 nm, so as to be λ/4 in the vicinity of 560 nm with high visibility. 150nm way design. From the viewpoint of improving visibility, an inverse dispersion λ/4 retardation plate using a material having a birefringence wavelength dispersion characteristic opposite to that of usual is preferable. As such a material, for example, the stretched retardation plate can use the material described in JP 2007-232873 A, and the like, and the liquid crystal coating-type retardation can use the material described in JP 2010-30979 A, etc. Material.

In addition, as another method, a technique for obtaining a wide-band λ/4 phase difference plate by combining with a λ/2 phase difference plate is also known (for example, Japanese Patent Laid-Open No. 10-90521, etc.). The λ/2 retardation plate can also be manufactured using the same materials and methods as the λ/4 retardation plate. The combination of the stretch-type retardation plate and the liquid crystal coating type retardation plate is arbitrary, and the thickness can be reduced by using both the liquid crystal coating type retardation plate.

For the aforementioned circularly polarizing plate, in order to improve the visibility in the oblique direction, a method of laminating a positive C plate is known (for example, Japanese Patent Laid-Open No. 2014-224837, etc.). The positive C plate may be a liquid crystal coating type retardation plate or a stretched type retardation plate. The retardation in the thickness direction of the retardation plate is preferably -200 to -20 nm, and more preferably -140 to -40 nm.

＜Touch sensor＞

As described above, the flexible display device of the present invention preferably includes a touch sensor. A touch sensor can be used as an input mechanism. As a touch sensor, various systems, such as a resistive film system, a surface acoustic wave system, an infrared system, an electromagnetic induction system, an electrostatic capacitance system, are mentioned, Preferably, an electrostatic capacitance system is mentioned.

The electrostatic capacitance type touch sensor can be divided into an active area and an inactive area located at the periphery of the active area. The active area is an area corresponding to an area (display portion) on the display panel that displays a screen, and is an area that senses the user's touch, and the inactive area is an area corresponding to an area (non-display portion) of the display device that does not display a screen. The touch sensor may include: a substrate having flexible properties; a sensing pattern formed on an active area of the substrate; and a drive for connecting the sensing pattern to the outside via a pad portion and formed on an inactive area of the substrate Each sensing line connected to the circuit. As the substrate having flexible properties, the same material as the transparent substrate of the aforementioned window film can be used.

The sensing pattern may include a first pattern formed along the first direction and a second pattern formed along the second direction. The first pattern and the second pattern are arranged in mutually different directions. The first pattern and the second pattern are formed on the same layer, and in order to sense the touched position, the patterns must be electrically connected. The first pattern is a form in which a plurality of cell patterns are connected to each other through a joint, and the second pattern is a structure in which a plurality of cell patterns are separated from each other into an island form. Therefore, in order to electrically connect the second patterns, another bridge is required. electrode. As the electrode used for connection of the second pattern, a known transparent electrode can be applied. Examples of the raw material of the transparent electrode include indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), indium zinc tin oxide (IZTO), indium gallium zinc oxide ( IGZO), cadmium tin oxide (CTO), PEDOT (poly(3,4-ethylenedioxythiophene), poly(3,4-ethylenedioxythiophene)), carbon nanotube (CNT), graphene, metal wire, etc. , preferably ITO can be mentioned. These can be used individually or in mixture of 2 or more types. Metals that can be used for the wire are not particularly limited, and examples thereof include silver, gold, aluminum, copper, iron, nickel, titanium, selenium, chromium, and the like, which may be used alone or in combination of two or more.

The bridge electrode can be formed on the upper part of the above-mentioned insulating layer via an insulating layer on the upper part of the sensing pattern, and the bridge electrode can be formed on the substrate, and the insulating layer and the sensing pattern can be formed thereon. The bridge electrode may be formed of the same material as the sensing pattern, or may be formed of molybdenum, silver, aluminum, copper, palladium, gold, platinum, zinc, tin, titanium, or an alloy of two or more of these.

The first pattern and the second pattern must be electrically insulated, so an insulating layer is formed between the sensing pattern and the bridge electrode. The insulating layer may be formed only between the contacts of the first pattern and the bridge electrodes, or may be formed as a layer covering the entire sensing pattern. In the case of a layer covering the entire sensing pattern, the bridge electrode may connect the second pattern through a contact hole formed in the insulating layer.

For the aforementioned touch sensor, as a method for appropriately compensating for the difference in transmittance between the pattern area where the sensing pattern is formed and the non-pattern area where the sensing pattern is not formed (specifically, it is caused by the difference in refractive index in these areas) The difference in light transmittance), an optical adjustment layer may be further included between the substrate and the electrode. The optical adjustment layer may contain an inorganic insulating substance or an organic insulating substance. The optical adjustment layer can be formed by apply|coating the photocurable composition containing a photocurable organic binder and a solvent on a board|substrate. The aforementioned photocurable composition may further contain inorganic particles. The refractive index of an optical adjustment layer can be improved by the said inorganic particle.

The said photocurable organic binder can contain the copolymer of each monomer, such as an acrylate type monomer, a styrene type monomer, and a carboxylic acid type monomer, in the range which does not impair the effect of this invention. The aforementioned photocurable organic binder may be, for example, a copolymer containing repeating units different from each other, such as an epoxy group-containing repeating unit, an acrylate repeating unit, and a carboxylic acid repeating unit.

As said inorganic particle, a zirconia particle, a titanium dioxide particle, an alumina particle, etc. are mentioned, for example.

The said photocurable composition may further contain each additive, such as a photoinitiator, a polymerizable monomer, and a curing adjuvant.

<Adhesive layer>

Each layer (window film, circular polarizer, touch sensor) forming the laminate for a flexible image display device and the film members (linear polarizer, λ/4 retardation plate, etc.) constituting each layer can be bonded with an adhesive . As the adhesive, water-based adhesives, organic solvent-based, solvent-free adhesives, solid adhesives, solvent-volatile adhesives, moisture-curable adhesives, and heat-curable adhesives can be used , anaerobic curing type, active energy ray curing type adhesive, curing agent mixed type adhesive, hot melt type adhesive, pressure sensitive adhesive (adhesive), rewet type adhesive, etc. As the adhesive to be used, an aqueous solvent-volatile adhesive, an active energy ray-curable adhesive, or a pressure-sensitive adhesive can be preferably used. The thickness of the adhesive bond layer can be appropriately adjusted according to the required adhesive force and the like, but is preferably 0.01 to 500 μm, and more preferably 0.1 to 300 μm. In the laminated body for flexible image display devices, there are a plurality of adhesive layers, and the thickness and type of each may be the same or different.

As the aforementioned water-based solvent-volatile adhesive, polyvinyl alcohol-based polymers, water-soluble polymers such as starch, and polymers in a water-dispersed state such as ethylene-vinyl acetate-based emulsions and styrene-butadiene-based emulsions can be used. main agent polymer. In addition to the aforementioned main ingredient polymer and water, a crosslinking agent, a silane-based compound, an ionic compound, a crosslinking catalyst, an antioxidant, a dye, a pigment, an inorganic filler, an organic solvent, and the like may be blended. In the case of bonding with the aforementioned water-based solvent-volatile adhesive, the aforementioned water-based solvent-volatile adhesive can be injected between the layers to be adhered, and the layers to be bonded can be pasted together and then dried to provide adhesion. sex. When the above-mentioned water-based solvent-volatile adhesive is used, the thickness of the adhesive layer is preferably 0.01 to 10 μm, and more preferably 0.1 to 1 μm. When the aforementioned water-based solvent-volatile adhesive is used for multiple layers, the thickness and type of each layer may be the same or different.

The aforementioned active energy ray-curable adhesive can be formed by curing an active energy ray-curable composition containing a reactive material capable of forming an adhesive layer by irradiating an active energy ray. The active energy ray-curable composition may contain at least one polymer of the same radically polymerizable compound and cationically polymerizable compound as the compound contained in the hard coat composition. As the radically polymerizable compound, the same compounds as the radically polymerizable compound in the hard coat composition can be used.

As the aforementioned cationically polymerizable compound, the same compound as the cationically polymerizable compound in the hard coat composition can be used.

As a cationically polymerizable compound that can be used in the active energy ray-curable composition, an epoxy compound is particularly preferable. In order to reduce the viscosity as an adhesive composition, it is also preferable to contain a monofunctional compound as a reactive diluent.

The active energy ray composition may contain a monofunctional compound in order to reduce viscosity. Examples of the monofunctional compound include acrylate-based monomers having one (meth)acryloyl group in one molecule, and compounds having one epoxy group or oxetanyl group in one molecule, for example Glycidyl (meth)acrylate and the like.

The active energy ray composition may further contain a polymerization initiator. As this polymerization initiator, a radical polymerization initiator, a cationic polymerization initiator, a radical and a cationic polymerization initiator, etc. are mentioned, These can be suitably selected and used. These polymerization initiators can be decomposed by at least one of active energy ray irradiation and heating to generate radicals or cations, thereby enabling radical polymerization and cationic polymerization to proceed. An initiator capable of initiating at least any one of radical polymerization and cationic polymerization by active energy ray irradiation described in the description of the hard coat composition can be used.

The aforementioned active energy ray-curable composition may further contain an ion trapping agent, an antioxidant, a chain transfer agent, an adhesion imparting agent, a thermoplastic resin, a filler, a fluid viscosity modifier, a plasticizer, an antifoaming agent solvent, an additive, and a solvent. In the case of adhering two to-be-adhered layers with the above-mentioned active energy ray-curable adhesive, the adhesion may be performed by applying the above-mentioned active energy ray-curable composition to one of the to-be-adhered layers or After both, they are bonded together, and an active energy ray is irradiated to one or both of the to-be-adhered layers to be cured. When using the said active energy ray-curable adhesive, the thickness of the adhesive layer becomes like this. Preferably it is 0.01-20 micrometers, More preferably, it is 0.1-10 micrometers. When the above-mentioned active energy ray-curable adhesive is used to form a plurality of adhesive layers, the thickness and type of each layer may be the same or different.

The above-mentioned adhesives are classified into acrylic adhesives, urethane-based adhesives, rubber-based adhesives, silicone-based adhesives, and the like according to the main ingredient polymer, and any of them can be used. In the adhesive, in addition to the main polymer, crosslinking agents, silane-based compounds, ionic compounds, crosslinking catalysts, antioxidants, tackifiers, plasticizers, dyes, pigments, and inorganic fillers may be blended Wait. An adhesive can be formed by dissolving and dispersing each component constituting the adhesive in a solvent to obtain an adhesive composition, applying the adhesive composition on a substrate, and then drying it. layer adhesive layer. The adhesive layer may be directly formed, or an adhesive layer formed separately on the substrate may be transferred. In order to cover the adhesive surface before bonding, it is also preferable to use a release film. When the active energy ray-curable adhesive is used, the thickness of the adhesive layer is preferably 0.1 to 500 μm, and more preferably 1 to 300 μm. When using multiple layers of the aforementioned adhesives, the thickness and type of each layer may be the same or different.

＜Shading pattern＞

The aforementioned light-shielding pattern may be used as at least a part of a bezel or a housing of the aforementioned flexible image display device. The wiring arranged at the edge portion of the flexible image display device is hidden by the light-shielding pattern so as to be difficult to be observed, thereby improving the visibility of the image. The aforementioned light shielding pattern may be in the form of a single layer or a multilayer. The color of the light-shielding pattern is not particularly limited, and may be various colors such as black, white, and metallic color. The light-shielding pattern may be formed of a pigment for expressing color, and a polymer such as acrylic resin, ester resin, epoxy resin, polyurethane, and silicone. These may be used individually, or may be used as a mixture of 2 or more types. The aforementioned light-shielding pattern can be formed by various methods such as printing, photolithography, and inkjet. The thickness of the light-shielding pattern is preferably 1 to 100 μm, and more preferably 2 to 50 μm. In addition, it is also preferable to provide a shape such as an inclination in the thickness direction of the light-shielding pattern.

Example

Hereinafter, an Example is given and this invention is demonstrated more concretely. The present invention is not limited to the following examples, and of course can be implemented with appropriate modifications within the scope of the gist described above and below, and all of them are included in the technical scope of the present invention.

The layers or laminates obtained in the following Examples and Comparative Examples were evaluated by the following methods.

Measurement of the surface Si ratio of the substrate (s) and the surface fluorine ratio of the water repellent layer (r)

Using JFS-9010 manufactured by Japan Electronics Co., Ltd., under the conditions of excitation X-ray: MgKα, X-ray output power of 110W, photoelectron flying angle of 45°, and path energy of 50eV, the water repellent layer (r ) of fluorine (F1s) and various elements in silicon of the substrate (s).

Determination of arithmetic mean height Sa

Using a laser microscope (OLS4000, manufactured by Olympus), the surface of the water-repellent layer (r) of the laminate was observed at a magnification of 20 times. The arithmetic mean height Sa was evaluated in accordance with ISO25178. The arithmetic mean height Sa is the mean value of N=2.

Contact angle and slip angle

3.0 μL of water droplets were added dropwise to the water-repellent layer (r) of the obtained laminate, and the amount of liquid was measured by the θ/2 method using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., DM700): 3.0 μL of water contact angle.

In addition, 6.0 μL of water droplets were dropped on the water-repellent layer (r) of the obtained laminate, and the above-mentioned contact angle measuring apparatus (manufactured by Kyowa Interface Science Co., Ltd., DM700) was carried out by the sliding method (amount of water droplets: 6.0 μL, inclined Method: continuous inclination, slippage detection: after slippage, slippage determination distance: 0.25 mm) The dynamic water repellency properties (slip angle) of the water repellent layer (r) surface of the laminate were measured.

surface reflectance

The incident angle 12° and Spectral reflectance at a wavelength of 530 nm at a reflection angle of 12°. The reflectance was calculated by subtracting 4.2% of the surface reflection loss and 4.2% of the back reflection loss from this value. In addition, the surface reflectance on the surface on the side of the intermediate layer (c) of the base material (s) was also measured in the same manner.

Wear resistance test

Using a steel wool tester (manufactured by Daiei Seiki Co., Ltd.) equipped with steel wool #0000 (manufactured by Bonstar Corporation), a load of 1000 g was applied in a state where the steel wool was in contact with the surface (water repellent layer (r)) of the laminate. The abrasion test was performed, and the test was repeated until peeling and damage were visually confirmed, and the abrasion resistance was evaluated by the number of tests when peeling and damage were confirmed. In addition, the confirmation of the occurrence of peeling and damage was performed under the condition of illuminance of 1000 lux.

Thickness determination

The thickness of the base material (s) was measured using DIGIMICRO (model number: MFC-101A) manufactured by Nikon Corporation. In addition, in each of Examples and Comparative Examples, the thickness of the water repellent layer (r) was several nm, and the thickness of the intermediate layer (c) was about 5 to 30 nm.

Example 1

N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and chloropropane described in Japanese Patent Laid-Open No. 2012-197330, which are represented by the following formula as the organosilicon compound (C), were mixed at room temperature. A solution of 0.25 mass % of a reactant (trade name; X-12-5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.) and 99.75 mass % of hexane as a solvent (E) was stirred to obtain an intermediate A solution for layer (c) formation.

[Chemical formula 24]

Next, as a base material (s), an AR film having a thickness of 84 μm was prepared. The AR film is a film obtained by alternately laminating SiO ₂ and a metal oxide (which is a metal oxide other than SiO ₂ ) on a resin layer by a vacuum deposition method, and making the outermost surface SiO ₂ . The surface Si ratio of the substrate (s) measured by the above method was 31.5 atomic %. The surface of the AR film was activated by atmospheric pressure plasma treatment, and on the activated surface, an OPTICOAT MS-A100 (spin coater) manufactured by MIKASA Co., Ltd. was used with a coating liquid amount of 200 μl, a rotation speed of 2000 rpm, The above-mentioned solution for forming the intermediate layer (c) was applied under the condition that the number of rotation seconds was 20 seconds to obtain the intermediate layer (c).

Next, as the organosilicon compound (A), OPTOOL (registered trademark) UF503 (containing 20% by mass of the organosilicon compound (A) and 80% by mass of Novec 7200 as the solvent) manufactured by Daikin Industries, Ltd. was used as the organosilicon compound (A). Organosilicon compound (B) FAS13E (C ₆ F ₁₃ -C ₂ H ₄ -Si(OC ₂ H ₅ ) ₃ , manufactured by Tokyo Chemical Industry Co., Ltd.), FC-3283 (C ₉ F ₂₁ ) as solvent (D) N, Fluorinert, manufactured by 3M Co., Ltd.), and stirred at room temperature for a predetermined time to obtain a solution for forming a water repellent layer (r). Here, OPTOOL (registered trademark) UF503 is an organosilicon compound in which a monovalent group having a perfluoropolyether structure and a hydrolyzable group are each bonded to a silicon atom. The ratio (solid content) of the organosilicon compound (A) in 100 mass % of solutions for water repellent layer (r) formation was 0.085 mass %, and the ratio of the organosilicon compound (B) was 0.05 mass %. The solution for forming a water repellent layer (r) was applied on the intermediate layer (c) using a sprayer manufactured by Apeiros Co., Ltd. The spraying conditions were as follows, scanning speed: 600 mm/sec, spacing: 5 mm, liquid volume: 6 cc/min, atomizing air: 350 kPa, gap: 70 mm. Then, it baked at 80 degreeC for 30 minutes, and obtained the laminated body which consists of a base material (s), an intermediate layer (c), and a water repellent layer (r) in this order.

Example 2

Except having changed the substrate (s) into an AR film having a surface Si ratio of 31.3 atomic %, it was carried out in the same manner as in Example 1 to obtain a substrate (s), an intermediate layer (c), and a water-repellent layer ( r) of the laminate.

Example 3

Except having used butyl acetate as a solvent (E), it carried out similarly to Example 2, and obtained the laminated body which consists of a base material (s), an intermediate layer (c), and a water repellent layer (r) in this order.

Example 4

Except having changed the base material (s) into a hard coat film having a thickness of 45 μm, it was carried out in the same manner as in Example 1 to obtain the base material (s), the intermediate layer (c), and the water repellent layer (r) in this order. Laminate. The above-mentioned hard coat film is a film obtained by laminating an acrylic hard coat layer having a surface Si ratio of 1.8 atomic % on a resin layer composed of polyethylene terephthalate. A film obtained by activation treatment by atmospheric pressure plasma treatment in the same manner as in Example 1 was carried out.

Example 5

The organic silicon compound (C) was changed to KBM-903 (manufactured by Shin-Etsu Chemical Co., Ltd.), and butyl acetate was used as the solvent (E) in the same manner as in Example 1 to obtain sequentially containing radicals. A laminate of the material (s), the intermediate layer (c), and the water repellent layer (r).

Comparative Example 1

Except having changed the base material (s) into an acrylic hard coat layer with a thickness of 60 μm and a surface Si ratio of 0 atomic %, it was carried out in the same manner as in Example 1 to obtain a base material (s), an intermediate layer ( c), the laminate of the water repellent layer (r).

Comparative Example 2

Except having changed the solvent (E) into methyl ethyl ketone, it carried out similarly to the comparative example 1, and obtained the laminated body which consists of a base material (s), an intermediate layer (c), and a water repellent layer (r) in this order.

Table 1 shows the results of evaluating the laminates obtained in Examples and Comparative Examples by the above-described method.

[Table 1]

Industrial Availability

The laminate of the present invention can be used in display devices such as touch panel displays, optical elements, semiconductor elements, building materials, nanoimprint technology, solar cells, window glass for automobiles, buildings, metal products such as cooking utensils, ceramic products such as tableware, It is industrially useful because it is suitably formed into a film on plastic automobile parts and the like. In addition, it is also suitable for use in items such as kitchens, bathrooms, washstands, mirrors, and various members around the dressing room.

Claims (7)

1. A laminate comprising a substrate(s), an intermediate layer (c), and a water-repellent layer (r) in this order, wherein the laminate satisfies the following requirements (1) and (2),

(1) a reflectance obtained by subtracting a surface reflection loss and a back reflection loss from a reflectance obtained by calculating a spectral reflectance of 530nm at an incident angle of 12 DEG and a reflection angle of 12 DEG measured on the side surface of the water-repellent layer (r) by using a 2-degree field of view (C light source) according to JIS Z8701 is 4.5% or less;

(2) the thickness of the laminate is 500 [ mu ] m or less.

2. The laminate according to claim 1, which further satisfies the following requirement (3),

(3) the surface fluorine element ratio on the water-repellent layer (r) side is 30 atomic% or more.

3. The laminate according to claim 1 or 2, which further satisfies at least 1 of the following requirements (4) and (5),

(4) the arithmetic average height Sa of the water repellent layer (r) side is 0.03-1.00 μm;

(5) the water-repellent layer (r) has a water slip angle of 25 DEG or less.

4. The laminate according to any one of claims 1 to 3, wherein the surface Si ratio of the outermost layer of the substrate(s) on the side of the intermediate layer (c) is 1 atomic% or more.

5. The laminate according to any one of claims 1 to 4, wherein the water-repellent layer (r) is a cured layer of a mixed composition (ca) of an organosilicon compound (A) represented by formula (a1) and an organosilicon compound (B) represented by formula (B1),

[ chemical formula 1]

In the formula (a1), the first and second groups,

Rf ^a1 is a 2-valent perfluoropolyether structure with oxygen atoms at two ends,

R ¹¹ 、R ¹² and R ¹³ Each independently an alkyl group having 1 to 20 carbon atoms, R ¹¹ When there are plural, plural R ¹¹ May be different from each other, R ¹² When there are plural, plural R ¹² May be different from each other, R ¹³ When there are plural, plural R ¹³ May be different from each other in that,

E ¹ 、E ² 、E ³ 、E ⁴ and E ⁵ Each independently being a hydrogen atom or a fluorine atom, E ¹ When there are plural ones, plural ones E ¹ May be different from each other, E ² When there are plural ones, plural ones E ² May be different from each other, E ³ When there are plural ones, plural ones E ³ May be different from each other, E ⁴ A plurality ofIn case of a plurality of E ⁴ May be different from each other, E ⁵ When there are plural ones, plural ones E ⁵ May be different from each other in that,

G ¹ and G ² Each independently a 2-10 valent organosiloxane group having a siloxane bond,

J ¹ 、J ² and J ³ Each independently is a hydrolyzable group or- (CH) ₂ ) _e6 -Si(OR ¹⁴ ) ₃ E6 is 1 to 5, R ¹⁴ Is methyl or ethyl, J ¹ When there are plural, plural J ¹ May be different from each other, J ² When there are plural, plural J ² May be different from each other, J ³ When there are plural, plural J ³ May be different from each other in that,

L ¹ and L ² Each independently a C1-12 valent linking group which may contain an oxygen atom, a nitrogen atom or a fluorine atom, L ¹ In the case where there are plural L' s ¹ May be different from each other, L ² In the case where there are plural L' s ² May be different from each other in that,

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,

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 1-3;

[ chemical formula 2]

In the formula (b1), the first and second groups,

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

R ^b11 、R ^b12 、R ^b13 and R ^b14 Each independently is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^b11 When there are plural, plural R ^b11 May be different from each other, R ^b12 When there are plural, plural R ^b12 May be different from each other, R ^b13 When there are plural, plural R ^b13 May be each different, R ^b14 When there are plural, plural R ^b14 May be different from each other in that,

Rf ^b11 、Rf ^b12 、Rf ^b13 and Rf ^b14 Each independently an alkyl group having 1 to 20 carbon atoms in which 1 or more hydrogen atoms are replaced by fluorine atoms or a fluorine atom, Rf ^b11 When there are plural Rf ^b11 May be different from each other, Rf ^b12 When there are plural Rf ^b12 May be different from each other, Rf ^b13 When there are plural Rf ^b13 May be different from each other, Rf ^b14 When there are plural Rf ^b14 May be different from each other in that,

R ^b15 is an alkyl group having 1 to 20 carbon atoms, R ^b15 When there are plural, plural R ^b15 May be different from each other in that,

A ¹ is-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 fluoroalkyl group having 1 to 4 carbon atoms, and A is a fluorine-containing alkyl group having 1 to 4 carbon atoms ¹ When there are plural A ¹ May be different from each other in that,

A ² is a hydrolyzable group, A ² When there are plural A ² May be different from each other in that,

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

c is an integer of 1 to 3,

for Rf ^b10 -、-Si(A ² ) _c (R ^b15 ) _3-c B11 pieces of C (R) ^b11 )(R ^b12 ) H, b 12- { C (Rf) ^b11 )(Rf ^b12 )}-、b13Individual- { Si (R) ^b13 )(R ^b14 ) H, b 14- { Si (Rf) ^b13 )(Rf ^b14 ) H, b 15-A ¹ To said, as long as Rf ^b10 -、-Si(A ² ) _c (R ^b15 ) _3-c Become terminal, no perfluoropolyether structure is formed, and-O-is not linked to-O-or-F, arranged in an arbitrary order and bonded.

6. The laminate according to any one of claims 1 to 5, wherein the intermediate layer (C) is a cured layer of a mixed composition (cc) of an organosilicon compound (C) represented by any one of the following formulae (C1) to (C3) or a vapor-deposited layer of the organosilicon compound (C),

[ chemical formula 3]

In the formula (c1), the metal oxide,

R ^x11 、R ^x12 、R ^x13 、R ^x14 each independently is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^x11 When there are plural, plural R ^x11 May be different from each other, R ^x12 When there are plural, plural R ^x12 May be different from each other, R ^x13 When there are plural, plural R ^x13 May be different from each other, R ^x14 When there are plural, plural R ^x14 May be different from each other in that,

Rf ^x11 、Rf ^x12 、Rf ^x13 、Rf ^x14 each independently an alkyl group having 1 to 20 carbon atoms in which 1 or more hydrogen atoms are replaced by fluorine atoms or a fluorine atom, Rf ^x11 When there are plural Rf ^x11 May be different from each other, Rf ^x12 When there are plural Rf ^x12 May be different from each other, Rf ^x13 When there are plural Rf ^x13 May be different from each other, Rf ^x14 When there are plural Rf ^x14 May be different from each other in that,

R ^x15 is an alkyl group having 1 to 20 carbon atoms, R ^x15 When there are plural, plural R ^x15 May be different from each other in that,

X ¹¹ is a hydrolyzable group, X ¹¹ When there are plural, plural X ¹¹ May be different from each other in that,

Y ¹¹ is-NH-or-S-, Y ¹¹ When there are plural, plural Y ¹¹ May be different from each other in that,

Z ¹¹ vinyl, alpha-methylvinyl, styryl, methacryloyl, acryloyl, amino, isocyanate, isocyanurate, epoxy, ureido, or mercapto,

p1 is an integer of 1 to 20, p2, p3 and p4 are each independently an integer of 0 to 10, p5 is an integer of 1 to 10,

p6 is an integer of 1 to 3,

Z ¹¹ in the case of other than amino, Y ¹¹ At least 1 of which is-NH-, Y ¹¹ In the case of all being-S-, Z ¹¹ Is an amino group, and the amino group,

for Z ¹¹ -、-Si(X ¹¹ ) _p6 (R ^x15 ) _3-p6 P1 pieces of C (R) ^x11 )(R ^x12 ) } -, p 2- { C (Rf) ^x11 )(Rf ^x12 ) H, p 3- { Si (R) ^x13 )(R ^x14 ) } -, p 4- { Si (Rf) ^x13 )(Rf ^x14 ) H, p 5-Y ¹¹ As long as Z ¹¹ -and-Si (X) ¹¹ ) _p6 (R ^x15 ) _3-p6 To be terminal, and-O-is not linked to-O-, and is arranged and bonded in an arbitrary order;

[ chemical formula 4]

In the formula (c2), the metal oxide,

R ^x20 and R ^x21 Each independently is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^x20 When there are plural, plural R ^x20 May be different from each other, R ^x21 When there are plural, plural R ^x21 May be different from each other in that,

Rf ^x20 and Rf ^x21 Each independently an alkyl group having 1 to 20 carbon atoms in which 1 or more hydrogen atoms are replaced by fluorine atoms or a fluorine atom, Rf ^x20 When there are plural Rf ^x20 May be different from each other, Rf ^x21 When there are plural Rf ^x21 May be different from each other in that,

R ^x22 and R ^x23 Each independently an alkyl group having 1 to 20 carbon atoms, R ^x22 And R ^x23 When there are plural, plural R ^x22 And R ^x23 May be different from each other in that,

X ²⁰ and X ²¹ Each independently is a hydrolyzable group, X ²⁰ And X ²¹ When there are plural, plural X ²⁰ And X ²¹ May be different from each other in that,

p20 are each independently an integer of 1 to 30, p21 are each independently an integer of 0 to 30, at least 1 of the repeating units designated p20 or p21 and enclosed in parentheses is replaced by an amine skeleton-NR ¹⁰⁰ -, R in the amine skeleton ¹⁰⁰ Is a hydrogen atom or an alkyl group,

p22 and p23 are each independently an integer of 1 to 3,

for p 20- { C (R) ^x20 )(R ^x21 ) } -, p 21- { C (Rf) ^x20 )(Rf ^x21 ) -for example, it is not necessary that p20 or p21 be consecutive, but rather that they be arranged and bonded in any order, with both ends being-Si (X) ²⁰ ) _p22 (R ^x22 ) _3-p22 and-Si (X) ²¹ ) _p23 (R ^x23 ) _3-p23 ；

[ chemical formula 5]

In the formula (c3), the metal oxide,

Z ³¹ 、Z ³² each independentlyA reactive functional group other than a hydrolyzable group and a hydroxyl group,

R ^x31 、R ^x32 、R ^x33 、R ^x34 each independently is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^x31 When there are plural, plural R ^x31 May be different from each other, R ^x32 When there are plural, plural R ^x32 May be different from each other, R ^x33 When there are plural, plural R ^x33 May be different from each other, R ^x34 When there are plural, plural R ^x34 May be different from each other in that,

Rf ^x31 、Rf ^x32 、Rf ^x33 、Rf ^x34 each independently an alkyl group having 1 to 20 carbon atoms in which 1 or more hydrogen atoms are replaced by fluorine atoms or a fluorine atom, Rf ^x31 When there are plural Rf ^x31 May be different from each other, Rf ^x32 When there are plural Rf ^x32 May be different from each other, Rf ^x33 When there are plural Rf ^x33 May be different from each other, Rf ^x34 When there are plural Rf ^x34 May be different from each other in that,

Y ³¹ is-NH-, -N (CH) ₃ ) -or-O-, Y ³¹ When there are plural, plural Y ³¹ May be different from each other in that,

X ³¹ 、X ³² 、X ³³ 、X ³⁴ each independently is-OR ^c (R ^c Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an amino group C _1-3 Alkyl di C _1-3 Alkoxysilyl group), X ³¹ When there are plural, plural X ³¹ May be different from each other, X ³² When there are plural, plural X ³² May be different from each other, X ³³ When there are plural, plural X ³³ May be different from each other, X ³⁴ When there are plural, plural X ³⁴ May be different from each other in that,

p31 is an integer of 0 to 20, p32, p33 and p34 are each independently an integer of 0 to 10, p35 is an integer of 0 to 5, p36 is an integer of 1 to 10, p37 is 0 or 1,

as long as Z is satisfied ³¹ And Z ³² At least one of which is amino, or Y ³¹ is-NH-or-N (CH) ₃ ) -and ends with Z ³¹ -and Z ³² -, -O-is not linked to-O-, then p 31- { C (R) ^x31 )(R ^x32 ) } -, p 32- { C (Rf) ^x31 )(Rf ^x32 ) H, p 33- { Si (R) ^x33 )(R ^x34 ) } -, p 34- { Si (Rf) ^x33 )(Rf ^x34 ) H, p 35-Y ³¹ -, p 36- { Si (X) ³¹ )(X ³² ) -O } -, p 37- { Si (X) ³³ )(X ³⁴ ) -arranged in any order and bonded.

7. A flexible display device comprising the laminate according to any one of claims 1 to 6, a polarizing plate, a touch sensor, and a display panel.