KR20220140827A - Laminate and flexible display devices - 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 surface reflection loss from the reflectance calculated by the 2 degree field of view (C light source) of JIS Z8701 for 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 (r) side, The reflectance minus the back reflection loss is 4.5% or less. (2) The thickness of the laminate is 500 μm or less.

Description

Laminate and flexible display devices

[0001] The present invention relates to a laminate and a flexible display device.

[0002] Since the surface free energy of a fluorine-based water-repellent film typified by a film formed from a composition containing a compound having a perfluoropolyether structure is very small, a display device such as a touch panel display, an optical element, a semiconductor element It is used as an antifouling coating, a water and oil repellent coating, etc. in various fields, such as a building material, a window glass of an automobile and a building, etc.

[0003] The water-repellent film is usually used to form on a substrate, and when the composition for forming a water-repellent film is applied to the substrate, after forming another layer such as a primer layer on the substrate in advance, the composition is It may be applied to form an antifouling coating or a water and oil repellent coating.

[0004] For example, in Patent Document 1, a hard coat layer (X), a primer layer (Y) and a surface layer (Z) are sequentially laminated on at least one surface of a substrate, wherein the surface layer (Z) is 110° or more. A hard coat film having a water contact angle is disclosed. In order to form the surface layer (Z), it is preferable to use a fluorine-based compound having a polyperfluoropolyether chain, and to form the primer layer (Y), 3-acryloxypropyltrimethoxysilane, etc. It is stated that silane compounds are preferred.

[0005] 1. Japanese Patent Laid-Open No. 2015-120253

[0006] In a laminate having a water repellent layer on a substrate, in order to maintain good water repellency, wear resistance when evaluated from the water repellent layer exposed on the surface side is required. Accordingly, 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, and which is excellent in abrasion resistance even if it is a thin film.

[0007] The present inventors have discovered that by adjusting the reflection characteristics on the surface of the laminate, good wear resistance can be realized while being a thin film. Specifically, the present invention that has achieved the above object is as follows.

[1] A laminate comprising a base material (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 surface reflection loss from the reflectance calculated by the 2 degree field of view (C light source) of JIS Z8701 for 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, and The reflectance minus the back reflection loss is 4.5% or less.

(2) The thickness of the laminate is 500 μm or less.

[2] The laminate according to [1], further satisfying the requirements of (3) below.

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

[3] The laminate according to [1] or [2], further satisfying at least one of the requirements of the following (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 sliding 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 intermediate layer (c) side of the base material (s) is 1 atomic% or more.

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

In the above formula (a1),

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

R ¹¹ , R ¹² , and R ¹³ are each independently an alkyl group having ¹ to ²⁰ carbon atoms ^. R ¹² may be different from each other, and when there are two or more R ¹³ , a plurality of R ¹³ may be different from each other,

E ¹ , E ² , E ³ , E ⁴ , and E ^{5 each} independently represent ^a hydrogen atom or ^a fluorine atom. When a plurality of E ² may be different from each other, a plurality of E ^{3 may be respectively different when a plurality of E 3 are} present, and a plurality of E ⁴ may be respectively different when a plurality of E ⁴ are present, and E When a plurality of ⁵ is present, a plurality of E ⁵ may 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 1-5, R ¹⁴ is a methyl group or an ethyl group, J When ^two or more ^1s exist, several J< ¹ > may differ, respectively, when ^two or more J2 exists, some J2 may differ, respectively, and when ^two or more J3 exists, some ^J3 is respectively different. you can do it,

L ¹ and L ² are each independently a divalent linking group having 1 to 12 carbon atoms which may contain an oxygen atom, a nitrogen atom, or a fluorine atom, and when two or more L ¹ are present, a plurality of L ¹ may be respectively different, and when two or more L ² exist, a plurality of L ² may be respectively different,

d11 is 1 to 9,

d12 is 0 to 9,

a10 and a14 are each independently 0-10,

a11 and a15 are each independently 0 or 1,

a12 and a16 are each independently 0-9,

a13 is 0 or 1,

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

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

In the above formula (b1),

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

R ^b11 , R ^b12 , R ^b13 and R ^b14 are each independently a hydrogen ^atom or an alkyl group having 1 to 4 carbon ^{atoms .} When there is a plurality of them, a plurality of R ^b12 may be different from each other, and R ^b13 may be When there is a plurality of R ^b13 may be different from each other, and when there are a plurality of R ^b14 , a plurality of R ^b14 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 ^; may be different from each other, and when a plurality of Rf ^b12 exist, a plurality of Rf ^b12 may be different from each other, and Rf ^b13 is When there are multiple Rf ^b13 may be different from each other, and when there are a plurality of Rf ^b14 , a plurality of Rf ^b14 may be different from each other,

R ^b15 is an alkyl group having 1 to 20 carbon ^{atoms ;}

A ¹ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, wherein R is a hydrogen atom, an alkyl group having ¹ to 4 carbon atoms, or a fluorine-containing alkyl group having ¹ to 4 carbon atoms;

A2 is a hydrolysable group, and when ^two or ^more A2s exist, some ^A2 may differ, respectively,

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

c is an integer of 1 to 3,

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

[6] The intermediate layer (c) is a cured layer of a mixed composition (cc) of an organosilicon compound (C) represented by any of the following formulas (c1) to (c3) or a vapor deposition layer of the organosilicon compound (C) The laminate according to any one of [1] to [5].

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 .} When there is a plurality of them, a plurality of R ^x12 may be different from each other, and R ^x13 may be When there is a plurality of R ^x13 may be different from each other, and when there are a plurality of R ^x14 , a plurality of R ^x14 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, and when a plurality of Rf ^x11 exists, a plurality of Rf ^x11 is Each may be different, and when a plurality of Rf ^x12 exist, a plurality of Rf ^x12 may be different, respectively, and Rf ^x13 is If there are multiple Rf ^x13 may be different from each other, and when a plurality of Rf ^x14 exist, a plurality of Rf ^x14 may be different from each other,

R ^x15 is an alkyl group having 1 to 20 carbon atoms, and when two or more R ^x15 are present, a plurality of R ^x15 may be different,

X ¹¹ is a hydrolysable group, and when two or more X ¹¹ are present, a plurality of X ¹¹ may be different from each other,

Y ¹¹ is -NH- or -S-, and when two or more Y ¹¹ is present, a plurality of Y ¹¹ may be different,

Z ¹¹ is a vinyl group, α-methylvinyl group, styryl group, methacryloyl group, acryloyl group, amino group, isocyanate group, isocyanurate group, epoxy group, ureido group, or mercapto group,

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

p6 is an integer of 1-3,

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

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 -, Z ¹¹ - and -Si(X ¹¹ ) ) _p6 (R ^x15 ) _3-p6 becomes the terminal, and as long as -O- is not connected with -O-, they are arranged in an arbitrary order to bind.

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 two or more R ^x20 exist, a plurality of R ^x20 may be different from each other, and a plurality of R ^x21 when two or more R x21 exist. R ^x21 of may be different from each other,

Rf ^x20 and Rf ^x21 are each independently an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted with fluorine atoms, and when two or more Rf ^x20 exist, a plurality of Rf ^x20 may be different from each other, and Rf When a plurality of ^x21 exist, a plurality of Rf ^x21 may be different from each other,

R ^x22 and R ^x23 are each independently an alkyl group having 1 to 20 carbon atoms, and R ^x22 and R ^x23 are When there are a plurality of R ^x22 and R ^x23 may be different from each other,

X ²⁰ and X ²¹ are each independently a hydrolysable group, and when a plurality of X ²⁰ and X ²¹ exist, a plurality of X ²⁰ and X ²¹ may be different,

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 enclosed in parentheses by adding p20 or p21 is substituted with an amine skeleton -NR ¹⁰⁰ - and 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,

p20 pieces of -｛C(R ^x20 )(R ^x21 )｝- and p21 pieces of -｛C(Rf ^x20 )(Rf ^x21 )｝- do not have to be consecutive, and p20 or p21 pieces are arranged in an arbitrary order. It binds, and both ends become -Si(X ²⁰ ) _p22 (R ^x22 ) _3-p22 and -Si(X ²¹ ) _p23 (R ^x23 ) _3-p23 .

In the above formula (c3),

Z ³¹ , 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 .} When there are a plurality of R ^x32 , each of a plurality of R x32 may be different, when a plurality of R ^x33 exist, a plurality of R ^x33 may be respectively different, and when a plurality of R ^x34 exist, a plurality of R ^x34 may be respectively different ,

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, Each may be different, and when a plurality of Rf ^x32 exist, a plurality of Rf ^x32 may be respectively different, when a plurality of Rf ^x33 exist, a plurality of Rf ^x33 may be respectively different, and when a plurality of Rf ^x34 exist, a plurality Rf ^x34 of may be different from each other,

Y ³¹ is -NH-, -N(CH ₃ )-, or -O-, and when two or more Y ³¹ , a plurality of Y ³¹ may be different,

X ³¹ , X ³² , X ³³ , X ³⁴ are each independently —OR ^c (R ^c is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aminoC _1-3 alkyldiC _1-3 alkoxysilyl group ), and when there are ^two or more X ³¹ , a ^plurality of X ³¹ may be ^respectively different; ³³ may be different from each other, and when there are two or more X ³⁴ , a plurality of X ³⁴ may 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, p37 is 0 or 1,

At least one of Z ³¹ and Z ³² is an amino group, or at least one of Y ³¹ satisfies the condition that -NH- or -N(CH ₃ )-, and ends are Z ³¹ - and Z ³² -, -O Unless - is linked to -O-, p31 -｛C(R ^x31 )(R ^x32 )｝-, p32 -｛C(Rf ^x31 )(Rf ^x32 )｝-, p33 -｛Si(R) ^x33 )(R ^x34 )｝-, p34 -｛Si(Rf ^x33 )(Rf ^x34 )｝-, p35 -Y ³¹ -, p36 -｛Si(X ³¹ )(X ³² )-O｝-, It is formed by combining p37 pieces of -｛Si(X ³³ )(X ³⁴ )｝- 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.

[0008] 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 an incident angle of 12° and a reflection angle of 12° measured from the water-repellent layer side surface. Since the spectral reflectance of wavelength 530 nm is 4.5% or less by subtracting the surface reflection loss and the back reflection loss from the reflectance calculated by the 2 degree field of view (C light source) of JIS Z8701, it is excellent in wear resistance, and furthermore, the thickness It is also equipped with the requirement of 500 micrometers or less, and abrasion resistance and a thin film are compatible.

[0009] 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 requirements of (1) and (2) below. .

(1) Surface reflection loss and back reflection loss from the reflectance calculated by the 2 degree field of view (C light source) of JIS Z8701 for 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 side surface The reflectance minus is 4.5% or less.

(2) The thickness of the laminate is 500 μm or less.

[0010] By satisfying the above requirement (1), good wear resistance can be realized. 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.

[0011] 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, and most preferably 100 μm or less, and 10 µm or more may be sufficient. By making the thickness of the said laminated body into predetermined or less, when using the laminated body of this invention for a touchscreen use, a sensitivity improves and visibility improves.

[0012] In addition, the laminate of the present invention preferably satisfies the above requirements (1) and (2) and further satisfies at least one of the following requirements (3) to (5). In particular, it is more preferable to satisfy the above requirements (1) and (2) and the following requirements (3), and more preferably satisfy all of the requirements (1) to (5).

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

By providing the requirement of (3) above, better water repellency can be realized. The surface fluorine element ratio is more preferably 40 atomic % or more, and still more preferably 50 atomic % or more. Although the upper limit of the said surface fluorine element ratio is not specifically limited, For example, it is 80 atomic%. The above-mentioned surface fluorine element ratio can be measured by the method described in Examples to be described later.

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

By providing the requirement of said (4), abrasion resistance can be improved more. Moreover, the requirement of said (4) is effective also for realization of 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, still more preferably 0.30 µm or less. Moreover, 0.04 micrometer or more may be sufficient as the said surface height Sa, and 0.05 micrometer or more may be sufficient as it. In addition, the arithmetic mean height Sa is computed based on ISO 25178.

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

In the requirement of said (5), as for the sliding angle of water, 20 degrees or less are more preferable, More preferably, it is 15 degrees or less, More preferably, it is 10 degrees or less. Although the lower limit of the said sliding angle of water is not specifically limited, For example, it is 1 degree.

[0016] The water-repellent layer (r) is preferably a cured layer of the mixed composition (ca) of the organosilicon compound (A) and the organosilicon compound (B).

[0017] I. Organosilicon compound (A)

The organosilicon compound (A) is a compound in which a monovalent group having a perfluoropolyether structure is bonded to a silicon atom and a hydrolyzable group is bonded to the silicon atom through or without a linking group. to be. The water-repellent layer (r) is preferably obtained by applying and curing the composition (ca), and has a structure derived from the organosilicon compound (A). As described above, the organosilicon compound (A) has a hydrolyzable group bonded to a silicon atom (which may be bonded via a linking group), and is a -SiOH group (Si and OH) of the organosilicon compound (A) resulting from hydrolysis. (may be bonded via a linking group) are dehydrated and condensed, so the water-repellent layer (r) usually has a condensed structure derived from the organosilicon compound (A). As said hydrolysable group, an alkoxy group, a halogen atom, a cyano group, an acetoxy group, an isocyanate group, etc. are mentioned.

[0018] The 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, for example, preferably 5 or more, more preferably 10 or more, and still more preferably 20 or more. The upper limit of the said carbon number is not specifically limited, For example, about 200 may be sufficient. The monovalent group having a perfluoropolyether structure of the organosilicon compound (A) preferably further has a perfluoroalkyl group at its free terminal.

[0019] The water-repellent layer (r) may be represented 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 is bonded to a silicon atom of a part of the polysiloxane skeleton with a perfluoroalkyl group at the free end thereof. The presence of the perfluoroalkyl group on the free end side improves water repellency.

[0020] The number of carbon atoms in the perfluoroalkyl group (especially the number of carbon atoms in the longest straight chain portion) is, for example, preferably 3 or more, more preferably 5 or more, and still more preferably 7 or more. Moreover, the upper limit of the said carbon number is not specifically limited, For example, even if it is about 20, the excellent water repellency characteristic is shown.

[0021] The perfluoroalkyl group may combine with a hydrocarbon group and/or a group in which at least a part of hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms to form a fluorine-containing group such as a fluoroalkyl group, for example, CF ₃ (CF ₂ ) _m -(CH ₂ ) _n -, CF ₃ (CF ₂ ) _m -C ₆ H ₄ -(m is all 1 to 10, preferably 3 to 7, n is all 1 to 5, preferably is 2 to 4), CF ₃ (CF ₂ ) _m -(CH ₂ ) _n - (m is all 1 to 10, preferably 3 to 7, n is all 1 to 5, Preferably it is 2-4). It is more preferable that the perfluoroalkyl group is directly bonded to the perfluoropolyether structure.

[0022] In the organosilicon compound (A), a monovalent group having a perfluoropolyether structure and a silicon atom may be bonded to each other via a suitable linking group, and the monovalent group having the perfluoropolyether without the linking group is You may couple|bond directly with a silicon atom. Examples of the linking group include a hydrocarbon group such as an alkylene group and an aromatic hydrocarbon group, a (poly)alkylene glycol group, or a group in which a part of their hydrogen atoms are substituted with a fluorine atom or a substituent, and a group suitably connected thereto. have. The number of carbon atoms in the linking group is, for example, 1 or more and 20 or less, and preferably 2 or more and 15 or less.

[0023] The hydrolyzable group has a function of bonding the organosilicon compounds (A) to each other or to the organosilicon compound (A) and active hydrogen (hydroxyl group, etc.) on the surface of the substrate through a hydrolysis/dehydration condensation reaction. Examples of such a hydrolyzable group include an alkoxy group (particularly an alkoxy group having 1 to 4 carbon atoms), a hydroxy group, an acetoxy group, and a halogen atom (particularly a chlorine atom). Preferable hydrolyzable groups are an alkoxy group and a halogen atom, and a methoxy group, an ethoxy group, and a chlorine atom are especially preferable.

[0024] The 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 the hydrolysable groups couple|bonded with a silicon atom should just be 1 or more, and although 2 or 3 may be sufficient, it is preferable that it is 2 or 3, and it is especially preferable that it is 3. When two or more hydrolysable groups are couple|bonded with the silicon atom, although different hydrolysable groups may couple|bond with the silicon atom, it is preferable that the same hydrolysable group couple|bonded with the silicon atom. Although the total number of the fluorine-containing group couple|bonded with a silicon atom is 4 normally, 2 or 3 (especially 3) may be sufficient. In the case of 3 or less, a monovalent group other than a hydrolysable group may be bonded to the remaining bonding hand, for example, an alkyl group (particularly an alkyl group having 1 to 4 carbon atoms), H, NCO, or the like may be bonded to the remaining bonding hand.

[0025] The monovalent group having a perfluoropolyether structure of the organosilicon compound (A) may have a straight chain shape, may have a side chain, and is preferably a straight chain shape.

[0026] The organosilicon compound (A) may be, for example, represented by the following formula (a).

[0027]

[0028] In the formula (a), D ¹ is a monovalent group having a perfluoropolyether structure, and the end of D ¹ bonded to D ² is -CF ₂ -O-*, -CFD ⁹ -* (* is a bond on the D ² side), D ² is a single bond or a divalent hydrocarbon group not substituted with a fluorine atom, D ³ is a trivalent hydrocarbon group not substituted with a fluorine atom, the hydrocarbon A part of the methylene group of the group may be substituted with 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 to 30, and n2 is 1 to 3. As a hydrolysable group of ^D8 , the thing mentioned above is mentioned.

[0029] The organosilicon compound (A) is preferably represented by the following formula (a1).

[0030]

[0031] In the formula (a1),

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

R ¹¹ , R ¹² , and R ¹³ are each independently (that is, R ¹¹ , R ¹² and R ¹³ may be the same or different) an alkyl group having 1 to 20 carbon atoms, and when two or more R ¹¹ are present A plurality of R ¹¹ may be different from each other, a plurality of R ¹² may be respectively different when there are two or more R ¹² , and a plurality of R ^{13 may be different when a plurality of R 13 are} present,

E ¹ , E ² , E ³ , E ⁴ , and E ^{5 each} independently represent ^a hydrogen atom or ^a fluorine atom. When a plurality of E ² may be different from each other, a plurality of E ^{3 may be respectively different when a plurality of E 3 are} present, and a plurality of E ⁴ may be respectively different when a plurality of E ⁴ are present, and E When a plurality of ⁵ is present, a plurality of E ⁵ may 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 1-5, R ¹⁴ is a methyl group or an ethyl group, J When ^two or more ^1s exist, several J< ¹ > may differ, respectively, when ^two or more J2 exists, some J2 may differ, respectively, and when ^two or more J3 exists, some ^J3 is respectively different. you can do it,

L ¹ and L ² are each independently ^a divalent linking group having ¹ to 12 carbon atoms which may contain an oxygen atom, a nitrogen atom, or a fluorine atom. may be, and when there are two or more L ² , a plurality of L ² may be different from each other,

d11 is 1 to 9,

d12 is 0 to 9,

a10 and a14 are each independently 0-10,

a11 and a15 are each independently 0 or 1,

a12 and a16 are each independently 0-9,

a13 is 0 or 1,

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

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

[0032] The organosilicon compound (A) has a perfluoropolyether structure represented by Rf ^a1 as represented by the formula (a1), and a hydrolyzable group represented by J ² or -(CH ₂ ) _e6 -Si(OR ¹⁴ ) ₃ (provided that R ¹⁴ is a methyl group or an ethyl group) has at least one. The perfluoropolyether structure is a structure in which all hydrogen atoms of the polyoxyalkylene group are substituted with fluorine atoms, can also be referred to as a perfluorooxyalkylene group, and can impart water repellency to the resulting film. Moreover, it is a compound which can become the matrix ^of the film obtained by bonding with J2 through the polymerization reaction (especially polycondensation reaction) with the said organosilicon compound (A) or another monomer.

[0033] Rf ^a1 is preferably -O-(CF ₂ CF ₂ O) _e4 -, or -O-(CF ₂ CF ₂ CF ₂ O) _e5 -. e4 and e5 are both 15-80.

[0034] R ¹¹ , R ¹² , and R ¹³ are each independently preferably an alkyl group having 1 to 10 carbon atoms.

[0035] L ¹ and L ² are each independently preferably a divalent linking group having 1 to 5 carbon atoms including a fluorine atom.

[0036] G ¹ and G ² are each independently preferably a divalent to pentavalent organosiloxane group having a siloxane bond.

[0037] J ¹ , J ² , and J ³ are each independently preferably a methoxy group, an ethoxy group, or -(CH ₂ ) _e6 -Si(OR ¹⁴ ) ₃ .

a10 is preferably 0 to 5 (more preferably 0 to 3), a11 is preferably 0, a12 is preferably 0 to 7 (more preferably 0 to 5), and a14 is 1 to 6 is preferable (more preferably 1 to 3), a15 is preferably 0, a16 is preferably 0 to 6, a21 to a23 are all preferably 0 or 1 (more preferably all 0), As for d11, 1-5 are preferable (more preferably, 1-3), d12 has preferable 0-3 (more preferably 0 or 1), and all of e1-e3 have 3 preferable. Moreover, as for a13, 1 is preferable.

[0039] In the organosilicon compound (A), Rf ^a1 of the formula (a1) is -O-(CF ₂ CF ₂ CF ₂ O) _e5 -, e5 is 35-50, and L ¹ and L ² are 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, J ¹ , J ² , and J ³ is all a methoxy group or an ethoxy group (especially a methoxy group), a10 is 1-3, a11 is 0, a12 is 0-5, a13 is 1, a14 is 2-5, a15 is 0, , a16 is 0 to 6, a21 to a23 are each independently 0 or 1 (more preferably a21 to a23 are all 0), d11 is 1, d12 is 0 or 1, and e1 to e3 are It is preferable to use all three compounds.

[0040] In the organosilicon compound (A), in the formula (a1), Rf ^a1 is -O-(CF ₂ CF ₂ CF ₂ O) _e5 -, e5 is 25-40, L ¹ is a fluorine atom and A divalent linking group having 3 to 6 carbon atoms including an oxygen atom, L ² is a perfluoroalkylene group having 1 to 3 carbon atoms, E ² , E ³ are both hydrogen atoms, E ⁵ is a fluorine atom, and J ² is -(CH ₂ ) _e6 -Si(OCH ₃ ) ₃ , e6 is 2-4, 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 a21 to a23 are all 0), d11 is 1, d12 is 0, and e2 is It is also preferable to use a compound of three.

[0041] Also, the organosilicon compound (A) is preferably a compound represented by the following formula (a2-1).

[0042]

[0043] In the formula (a2-1),

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

Rf ^a22 , 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, and when a plurality of Rf ^a22 is present, a plurality of Rf ^a22 may be different from each other, and when a plurality of Rf ^a23 exist, a plurality of Rf ^a23 may be respectively different, when a plurality of Rf ^a24 exist, a plurality of Rf ^a24 may be respectively different, and when a plurality of Rf ^a25 exists A plurality of Rf ^a25 may 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 ^; When a plurality of R 21 s are present, a plurality of R ²¹ may be respectively different, a plurality of R ^{22 may be respectively different when a plurality of R 22 are} present, and a plurality of R ²³ may be respectively different when a plurality of R ²³ are present. ,

R ²⁴ is an alkyl group having 1 to 20 carbon atoms, and when two or more R ²⁴ are present, a plurality of R ²⁴ may be different,

M ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when two or more M ¹ are present, a plurality of M ¹ may be different,

M ² is a hydrogen atom or a halogen atom,

M ³ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-(R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluorine-containing alkyl group having 1 to 4 carbon atoms), and when there are two or more M ³ , the plurality of M ³ may be different from each other,

M ⁴ is a hydrolysable group, and when there are two or more 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 sum of f11, f12, f13, f14, and f15 is 13 or more,

f16 is an integer from 1 to 20,

f17 is an integer from 0 to 2,

g1 is an integer of 1 to 3,

Rf ^a21 -, M ² -, f11 -｛C(R ²⁰ )(R ²¹ )｝-, f12 -｛C(Rf ^a22 )(Rf ^a23 )｝-, f13 -｛Si(R ²² )( R ²³ )｝-, f14 -｛Si(Rf ^a24 )(Rf ^a25 )｝-, f15 -M ³ -, and f16 -[CH ₂ C(M ¹ )｛(CH ₂ ) _f17 -Si( M ⁴ ) _g1 (R ²⁴ ) _3-g1 f]- is listed in the order that Rf ^a21 -, M ² - are terminated, at least in part to form a perfluoropolyether structure, and -O- is Unless linked with -O- to -F, they are arranged in any order to bond. That is, in the formula (a2-1), f11 pieces of -{C(R ²⁰ )(R ²¹ )}- are always continuous, f12 pieces of -{C(Rf ^a22 )(Rf ^a23 )}- are consecutive, and f13 consecutive -bSi(R ²² )(R ²³ )｝-, f14 consecutive -bSi(Rf ^a24 )(Rf ^a25 )｝-, f15 consecutive -M ³ -, f16 consecutive - [CH ₂ C(M ¹ )｛(CH ₂ ) _f17 -Si(M ⁴ ) _g1 (R ²⁴ ) _{3-g1 f} ]- does not mean that they are consecutive, in this order, but -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 )( It is possible for each to be listed in any order, such as Rf ^a23 )-M ³ -Si(R ²² )(R ²³ )-C(Rf ^a22 )(Rf ^a23 )- and the like.

[0044] 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 purple having 1 to 5 carbon atoms It is a luoroalkyl group.

[0045] 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 with a fluorine atom, more preferably all is a fluorine atom.

[0046] R ²⁰ , R ²¹ , R ²² , and R ²³ are each independently preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably all hydrogen atoms.

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

[0048] M ¹ is preferably, each independently, a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably all hydrogen atoms.

[0049] M ² is preferably a hydrogen atom.

[0050] M ³ is preferably -C(=O)-O-, -O-, -OC(=O)-, and more preferably all of -O-.

[0051] M ⁴ is preferably an alkoxy group or a halogen atom, more preferably a methoxy group, an ethoxy group, or a chlorine atom.

[0052] Preferably, f11, f13, and f14 each are 1/2 or less of f12, more preferably 1/4 or less, still more preferably f13 or f14 is 0, particularly preferably f13 and f14 is 0.

[0053] f15 is preferably 1/5 or more of the total value of f11, f12, f13, and f14, and less than or equal to the total value of f11, f12, f13, and f14.

[0054] f12 is preferably 20 to 600, more preferably 20 to 200, still more preferably 50 to 200 (more preferably 30 to 150, particularly preferably 50 to 150, most preferably is 80-140). f15 is preferably 4-600, more preferably 4-200, still more preferably 10-200 (more preferably 30-60). 20-600 are preferable, as for the total value of f11, f12, f13, f14, f15, 20-200 are more preferable, 50-200 are still more preferable.

[0055] f16 is preferably 1 to 18. More preferably, it is 1-15. More preferably, it is 1-10.

f17 is preferably 0 to 1.

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

[0058] f11 -｛C(R ²⁰ )(R ²¹ )｝-, f12 -｛C(Rf ^a22 )(Rf ^a23 )｝-, f13 -｛Si(R ²² )(R ²³ )｝- , the order of f14 -｛Si(Rf ^a24 )(Rf ^a25 )｝-, and f15 -M ³ - are arbitrary in the formula, as long as they are listed in the order of forming a perfluoropolyether structure at least in part. However, it is preferable that the repeating unit enclosed in parentheses after adding f12 on the most fixed end side (the side bonding to a silicon atom) (ie, -｛C(Rf ^a22 )(Rf ^a23 )｝-) is on the free end side It is located on the free end side of the repeating unit enclosed in parentheses with f11 (ie, -c(R ²⁰ )(R ²¹ )｝-), and more preferably the repeats enclosed in parentheses by attaching f12 and f14 on the most fixed end side. The units (that is, -｛C(Rf ^a22 )(Rf ^a23 )｝-, and -｛Si(Rf ^a24 )(Rf ^a25 )｝-) are repeating units enclosed in parentheses by adding f11 and f13 on the most free end side. (that is, -bC(R ²⁰ )(R ²¹ )b-, and -bSi(R ²² )(R ²³ ){-) are located on the free end side.

[0059] In Formula (a2-1), Rf ^a21 is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ^a22 , Rf ^a23 , Rf ^a24 , Rf ^a25 are all fluorine atoms, and M ³ are all -O -, M ⁴ is all methoxy group, ethoxy group or chlorine atom (particularly methoxy group or ethoxy group), M ¹ , M ² are all hydrogen atoms, f11 is 0, f12 is 30 to 150 (more preferably 80 to 140), f15 is preferably 30 to 60, f13 and f14 are 0, f17 is 0 to 1 (particularly 0), g1 is 3, and f16 is 1 to 10.

[0060] The organosilicon compound (A) is also preferably a compound represented by the following formula (a2-2).

[0061]

[0062] In the 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 ^; may be different from each other, and when a plurality of Rf ^a27 exist, a plurality of Rf ^a27 may be respectively different, when a plurality of Rf ^a28 exist, a plurality of Rf ^a28 may be respectively different, and when a plurality of Rf ^a29 exists A plurality of Rf ^a29 may 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 ^. When two or more R 26 may be present, a plurality of R ²⁶ may be respectively different, when two or more R ²⁷ exist, a plurality of R ²⁷ may be respectively different, and when two or more R ²⁸ exist, a plurality of R ²⁸ may be respectively different ,

R ²⁹ and R ³⁰ are each independently an alkyl group having ¹ to ²⁰ carbon ^{atoms .} Each of these may be different,

M ⁷ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, R is a hydrogen atom, an alkyl group having ¹ to ⁴ carbon atoms, or a fluorine-containing alkyl group having 1 to 4 carbon atoms;

M ⁵ and M ⁹ are each independently a hydrogen atom or an alkyl group having ¹ to ⁴ carbon atoms ^. M ⁹ may be different from each other,

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

M ⁸ and M ¹¹ are each independently a hydrolysable group, and when two or more M ⁸ , each of a plurality of M ⁸ may be different, and when a plurality of M ¹¹ exist, a plurality of M ¹¹ are each different you can do it,

f21, f22, f23, f24, and f25 are each independently an integer from 0 to 600, and the sum of f21, f22, f23, f24, and f25 is 13 or more,

f26, and f28 are each independently an integer of 1 to 20,

f27, and f29 are each independently an integer of 0 to 2,

g2, g3 are each independently an integer of 1 to 3,

M ¹⁰ -, M ⁶ -, f21 -｛C(R ²⁵ )(R ²⁶ )｝-, f22 -｛C(Rf ^a26 )(Rf ^a27 )｝-, f23 -｛Si(R ²⁷ )( R ²⁸ )｝-, f24 -｛Si(Rf ^a28 )(Rf ^a29 )｝-, f25 -M ⁷ -, f26 -[CH ₂ C(M ⁵ )｛(CH ₂ ) _f27 -Si(M ⁸ ) _g2 (R ²⁹ ) _3-g2 a], and f28 -[CH ₂ C(M ⁹ )｛(CH ₂ ) _f29 -Si(M ¹¹ ) _g3 (R ³⁰ ) _3-g3 , M ¹⁰ -, M ⁶ - become a terminal, and are arranged in an order to form a perfluoropolyether structure at least in part, and -O- is arranged in an arbitrary order and bonded together, unless -O- is continuous. Regarding the arrangement and bonding in an arbitrary order, it is the same as that described in the above formula (a2-1), and it is not limited to the meaning that each repeating unit is sequentially arranged in the order as described in the above formula (a2-2). does not

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

[0064] More specifically, as the organosilicon compound (A), a compound of the following formula (a3) may be mentioned.

[0065]

[0066] In 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. 2-4 are preferable respectively independently, and, as for carbon number of ^R30 , ^R31 , ^R32 , ^R33 , 2-3 are more preferable. h1 is 5 to 70, h2 is 1 to 5, and h3 is 1 to 10. 10-60 are preferable, as for h1, 20-50 are more preferable, 1-4 are preferable, as for h2, 1-3 are more preferable, 1-8 are preferable and, as for h3, 1-8 are more preferable. .

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

[0068]

[0069] In Formula (a4), R ⁴⁰ is a perfluoroalkyl group having 2 to 5 carbon atoms, R ⁴¹ is a perfluoroalkylene group having 2 to 5 carbon atoms, and R ⁴² is an alkyl having 2 to 5 carbon atoms A fluoroalkylene group in which some of the hydrogen atoms of the ene group are substituted with fluorine, R ⁴³ and R ⁴⁴ are each independently an alkylene group having 2 to 5 carbon atoms, and R ⁴⁵ is a methyl group or an ethyl group. k1, k2, and k3 are each independently an integer of 1-5.

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

[0071] Examples of the organosilicon compound (A) include a compound represented by the following formula (1) or a compound having a structure similar to the compound, Optool (registered trademark) manufactured by DAIKIN INDUSTRIES, LTD. UF503 etc. are mentioned.

[0072] Examples of the compound represented by the formula (1) include those synthesized by the methods described in Synthesis Examples 1 and 2 of Japanese Patent Application Laid-Open No. 2014-15609, r is 43 and s is 1 to 6 It is an integer and has a number average molecular weight of about 8000.

[0073] As the analogous structure, a structure in which the number of carbon atoms of the hydrocarbon group or the number of carbon atoms of the hydrocarbon group substituted with a fluorine atom of the formula (1) is different, a structure in which a perfluoropolyether structure and a silicon atom are bonded without a linking group, purple A structure in which another hydrocarbon group (including a hydrocarbon group in which at least some of the hydrogen atoms are substituted with fluorine atoms) is interposed at any position of the linking group between the luoropolyether structure and the silicon atom, the silicon atom and the hydrolyzable group are bonded through the linking group Although the structure, the structure in which the values of r and s differ, etc. are mentioned, it is not limited to these structures.

[0074] II. Organosilicon compound (B)

The organosilicon compound (B) represented by the following formula (b1) has a hydrolyzable group represented by A ² as will be described later, and the -SiOH group of the organosilicon compound (B) generated by hydrolysis is usually a hydrogen Since the -SiOH group of the organosilicon compound (A) produced by decomposition and/or the -SiOH group of the organosilicon compound (B) produced by hydrolysis is dehydrated and condensed, in a preferred embodiment, the cured layer of the mixed composition (ca) The water-repellent layer (r) has a condensed structure derived from the organosilicon compound (B) together with the condensed structure derived from the organosilicon compound (A). As said hydrolysable group, an alkoxy group, a halogen atom, a cyano group, an acetoxy group, an isocyanate group, etc. are mentioned.

[0075]

[0076] In the formula (b1),

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

R ^b11 , R ^b12 , R ^b13 , and R ^b14 are each independently a hydrogen ^atom or an alkyl group having 1 to 4 carbon ^{atoms .} When there is a plurality of them, a plurality of R ^b12 may be different from each other, and R ^b13 may be When there is a plurality of R ^b13 may be different from each other, and when there are a plurality of R ^b14 , a plurality of R ^b14 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 ^; may be different from each other, and when a plurality of Rf ^b12 exist, a plurality of Rf ^b12 may be different from each other, and Rf ^b13 is When there are multiple Rf ^b13 may be different from each other, and when there are a plurality of Rf ^b14 , a plurality of Rf ^b14 may be different from each other,

R ^b15 is an alkyl group having 1 to 20 carbon ^{atoms ;}

A ¹ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, wherein R is a hydrogen atom, an alkyl group having ¹ to 4 carbon atoms, or a fluorine-containing alkyl group having ¹ to 4 carbon atoms;

A2 is a hydrolysable group, and when ^two or ^more A2s exist, some ^A2 may differ, respectively,

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

c is an integer of 1 to 3,

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

[0077] 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).

[0078] R ^b11 , R ^b12 , R ^b13 , and R ^b14 are preferably a hydrogen atom.

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

[0080] A ¹ is preferably -O-, -C(=O)-O-, or -OC(=O)-.

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

[0082] b11 is preferably 1 to 30, more preferably 1 to 25, still more preferably 1 to 10, particularly preferably 1 to 5, and most preferably 1 to 2.

[0083] b12 is preferably 0 to 15, more preferably 0 to 10.

[0084] b13 is preferably 0 to 5, more preferably 0 to 2.

[0085] b14 is preferably 0 to 4, more preferably 0 to 2.

[0086] b15 is preferably 0 to 4, more preferably 0 to 2.

[0087] c is preferably 2-3, more preferably 3.

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

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

[0090] In addition, when FAS13E used as compound (B) in the Examples to be described later is represented by Formula (b1), R ^b11 and R ^b12 are all hydrogen atoms, b11 is 2, b13, b14, and b15 are all 0, c is 3, A ² is an ethoxy group, and Rf ^b10 -｛C(Rf ^b11 )(Rf ^b12 )｝ _b12 - serves as a terminal and is determined to be C ₆ F ₁₃ -.

[0091] Specifically, as the compound represented by the formula (b1), CF ₃ -Si-(OCH ₃ ) ₃ , C _j F _2j+1 -Si-(OC ₂ H ₅ ) ₃ (j is 1 to 12 an integer of), among which C ₄ F ₉ -Si-(OC ₂ H ₅ ) ₃ , C ₆ F ₁₃ -Si-(OC ₂ H ₅ ) ₃ , C ₇ F ₁₅ -Si-(OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ -Si-(OC ₂ H ₅ ) ₃ is preferred. Also, CF ₃ CH ₂ O(CH ₂ ) _k SiCl ₃ , CF ₃ CH ₂ O(CH ₂ ) _k Si(OCH ₃ ) ₃ , CF ₃ CH ₂ O(CH ₂ ) _k Si(OC ₂ H ₅ ) ₃ , CF ₃ (CH ₂ ) ₂ Si(CH ₃ ) ₂ (CH ₂ ) _k SiCl ₃ , CF ₃ (CH ₂ ) ₂ Si(CH ₃ ) ₂ (CH ₂ ) _k Si(OCH ₃ ) ₃ , CF ₃ ( CH ₂ ) ₂ Si(CH ₃ ) ₂ (CH ₂ ) _k Si(OC ₂ H ₅ ) ₃ , CF ₃ (CH ₂ ) ₆ Si(CH ₃ ) ₂ (CH ₂ ) _k SiCl ₃ , CF ₃ (CH ₂ ) ) ₆ Si(CH ₃ ) ₂ (CH ₂ ) _k Si(OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₆ Si(CH ₃ ) ₂ (CH ₂ ) _k Si(OC ₂ H ₅ ) ₃ , CF ₃ COO (CH ₂ ) _k SiCl ₃ , CF ₃ COO(CH ₂ ) _k Si(OCH ₃ ) ₃ , CF ₃ COO(CH ₂ ) _k Si(OC ₂ H ₅ ) ₃ (k is all 5-20 and preferably 8 to 15). Also, CF ₃ (CF ₂ ) _m -(CH ₂ ) _n SiCl ₃ , CF ₃ (CF ₂ ) _m -(CH ₂ ) _n Si(OCH ₃ ) ₃ , CF ₃ (CF ₂ ) _m -(CH ₂ ) _n Si(OC ₂ H ₅ ) ₃ can also be mentioned (m is all 1-10, Preferably it is 3-7, all n are 1-5, Preferably it is 2-4). CF ₃ (CF ₂ ) _p -(CH ₂ ) _q -Si-(CH ₂ CH=CH ₂ ) ₃ may be mentioned (p is all 2-10, preferably 2-8, q is all 1 -5, preferably 2-4). Also, CF ₃ (CF ₂ ) _p -(CH ₂ ) _q SiCH ₃ Cl ₂ , CF ₃ (CF ₂ ) _p -(CH ₂ ) _q SiCH ₃ (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) _p -( CH ₂ ) _q SiCH ₃ (OC ₂ H ₅ ) ₂ (p is all 2 to 10, preferably 3 to 7, q is all 1 to 5, preferably 2 to 4) .

[0092] Among the compounds represented by the formula (b1), a compound represented by the following formula (b2) is preferable.

[0093]

In 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 mixed composition (ca) is a composition in which the organosilicon compound (A) and the organosilicon compound (B) are mixed, and the organosilicon compound (A) and the organosilicon compound (B) are mixed. It is obtained by mixing, and when components other than the said organosilicon compound (A) and the said organosilicon compound (B) are mixed, the said organosilicon compound (A) and the said organosilicon compound (B) and other components It is obtained by mixing. The mixed composition (ca) includes those that have undergone a reaction after mixing, for example, during storage.

[0096] III. Solvent (D)

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

As the fluorine-based solvent, in addition to the above, hydrochlorofluorocarbons such as Asahi Clean (registered trademark) AK225 (manufactured by AGC Inc.), Asahi Clean (registered trademark) AC2000 (manufactured by Asahi Glass Co., Ltd.), etc. of hydrofluorocarbon and the like can be used.

[0098] As the solvent (D), it is preferable to use at least a fluorinated amine-based solvent. In addition, as the solvent (D), it is preferable to use two or more types of fluorine-based solvents, and it is preferable to use a fluorinated amine-based solvent and a fluorinated hydrocarbon-based solvent (especially a fluorinated aliphatic hydrocarbon-based solvent).

[0099] The amount of the organosilicon compound (A) in the mixed composition (ca) is, for example, 0.01% by mass or more, preferably 0.03% by mass or more, and more preferably, based on 100% by mass of the total composition. is 0.05 mass % or more, and is 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.

[0100] The amount of the organosilicon compound (B) in the mixed composition (ca) is, for example, 0.01% by mass or more, preferably 0.03% by mass or more, and 0.3% by mass based on 100% by mass of the total composition. % or less, and more preferably 0.2 mass % or less.

[0101] 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 further preferably 2.0 or less. and more preferably 1.5 or less, still more preferably 1.0 or less.

[0102] The amounts of the organosilicon compounds (A) and (B) can be adjusted when preparing the composition. You may compute the quantity of the said organosilicon compound (A) and (B) from the analysis result of a composition.

[0103] In addition, the mixed composition (ca) for forming the water-repellent layer (r), in the range that does not impair the effects of the present invention, a silanol condensation catalyst, an antioxidant, a rust preventive agent, an ultraviolet absorber, a light stabilizer, an anti-mold agent, Various additives, such as an antibacterial agent, a bioadhesion inhibitor, a deodorant, a pigment, a flame retardant, and an antistatic agent, may be mixed.

[0104] The thickness of the water-repellent layer (r) is, for example, about 1-1000 nm.

[0105] The intermediate layer (c) is a mixture composition (cc) of an organosilicon compound (C) having a silicon atom and an amino group or an amine skeleton (-NR ¹⁰⁰ -, R ¹⁰⁰ is a hydrogen atom or an alkyl group) It is a layer or a vapor deposition layer of the said organosilicon compound (C), and an intermediate|middle layer (c) has an amino group or an amine skeleton. In a preferred embodiment, a hydrolyzable group or a hydroxy group is bonded to a silicon atom of the organosilicon compound (C), and is produced by hydrolysis of a Si-OH group or a hydrolysable group bonded to a silicon atom of the organosilicon compound (C). Since -SiOH groups of the organosilicon compound (C) are dehydrated and condensed, the intermediate layer (c) preferably has a condensed structure derived from the organosilicon compound (C). The intermediate layer (c) may function as a primer layer of the water-repellent layer (r). As a hydrolysable 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. It is preferable that the C1-C4 alkoxy group or the hydroxyl group couple|bonded with the silicon atom of the organosilicon compound (C).

[0106] The organosilicon compound (C) is preferably a compound represented by any of the following formulas (c1) to (c3).

[0107] IV-1. Organosilicon compound (C) represented by the following formula (c1) (hereinafter, organosilicon compound (C1)

[0108] 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 .} When there is a plurality of them, a plurality of R ^x12 may be different from each other, and R ^x13 may be When there is a plurality of R ^x13 may be different from each other, and when there are a plurality of R ^x14 , a plurality of R ^x14 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, and when a plurality of Rf ^x11 exists, a plurality of Rf ^x11 is Each may be different, and when a plurality of Rf ^x12 exist, a plurality of Rf ^x12 may be different, respectively, and Rf ^x13 is If there are multiple Rf ^x13 may be different from each other, and when a plurality of Rf ^x14 exist, a plurality of Rf ^x14 may be different from each other,

R ^x15 is an alkyl group having 1 to 20 carbon atoms, and when two or more R ^x15 are present, a plurality of R ^x15 may be different,

X ¹¹ is a hydrolysable group, and when two or more X ¹¹ are present, a plurality of X ¹¹ may be different from each other,

Y ¹¹ is -NH- or -S-, and when two or more Y ¹¹ is present, a plurality of Y ¹¹ may be different,

Z ¹¹ is a vinyl group, α-methylvinyl group, styryl group, methacryloyl group, acryloyl group, amino group, isocyanate group, isocyanurate group, epoxy group, ureido group, or mercapto group,

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

p6 is an integer of 1-3,

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

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 -, Z ¹¹ - and -Si(X ¹¹ ) ) _p6 (R ^x15 ) _3-p6 becomes the terminal, and as long as -O- is not connected with -O-, they are arranged in an arbitrary order to bind.

[0109] It is preferable that R ^x11 , R ^x12 , R ^x13 , and R ^x14 are hydrogen atoms.

[0110] 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.

[0111] It is preferable that R ^x15 is an alkyl group having 1 to 5 carbon atoms.

[0112] 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.

[0113] Y ¹¹ is preferably -NH-.

[0114] 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.

[0115] p1 is preferably 1 to 15, more preferably 2 to 10. As for p2, p3, and p4, respectively independently, 0-5 are preferable, More preferably, all are 0-2. As for p5, 1-5 are preferable, More preferably, it is 1-3. As for p6, 2-3 are preferable, More preferably, it is 3.

[0116] As the organosilicon compound (C), in the formula (c1), both R ^x11 and R ^x12 are hydrogen atoms, Y ¹¹ is -NH-, and X ¹¹ is an alkoxy group (particularly a methoxy group or an ethoxy group) ), Z ¹¹ is an amino group or a mercapto group, p1 is 1 to 10, p2, p3 and p4 are all 0, p5 is 1 to 5 (particularly 1 to 3), and p6 is 3 using a compound It is preferable to do

[0117] The organosilicon compound (C1) is preferably represented by the following formula (c1-2).

[0118]

[0119] In the above formula (c1-2),

X ¹² is a hydrolysable group, and when there are two or more X ¹² , a plurality of X ¹² may be different,

Y ¹² is -NH-,

Z ¹² is an amino group or a mercapto group,

R ^x16 is an alkyl group having 1 to 20 carbon atoms, and when two or more R ^x16 are present, a 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.

[0120] 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.

[0121] Z ¹² is preferably an amino group.

[0122] 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.

[0123] p is preferably an integer of 2-3, and more preferably 3.

[0124] q is preferably an integer of 2-3, and r is preferably an integer of 2-4.

[0125] IV-2. Organosilicon compound (C) represented by the following formula (c2) (hereinafter, organosilicon compound (C2))

[0126]

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 two or more R ^x20 exist, a plurality of R ^x20 may be different from each other, and a plurality of R ^x21 when two or more R x21 exist. R ^x21 of may be different from each other,

Rf ^x20 and Rf ^x21 are each independently an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted with fluorine atoms, and when two or more Rf ^x20 exist, a plurality of Rf ^x20 may be different from each other, and Rf When a plurality of ^x21 exist, a plurality of Rf ^x21 may be different from each other,

R ^x22 and R ^x23 are each independently an alkyl group having 1 to 20 carbon atoms, and R ^x22 and R ^x23 are When there are a plurality of R ^x22 and R ^x23 may be different from each other,

X ²⁰ and X ²¹ are each independently a hydrolysable group, and when a plurality of X ²⁰ and X ²¹ exist, a plurality of X ²⁰ and X ²¹ may be different,

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

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

p20 pieces of -｛C(R ^x20 )(R ^x21 )｝- and p21 pieces of -｛C(Rf ^x20 )(Rf ^x21 )｝- do not have to be consecutive, and p20 or p21 pieces are arranged in an arbitrary order and combined and -Si(X ²⁰ ) _p22 (R ^x22 ) _3-p22 and -Si(X ²¹ ) _p23 (R ^x23 ) _3-p23 at both ends.

[0127] It is preferable that R ^x20 and R ^x21 are hydrogen atoms.

[0128] 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.

[0129] R ^x22 and R ^x23 are preferably an alkyl group having 1 to 5 carbon atoms.

[0130] 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, still more preferably a methoxy group or an ethoxy group.

[0131] The amine skeleton -NR ¹⁰⁰ - may be present in at least one molecule as described above, and any of the repeating units enclosed in parentheses by adding p20 or p21 may be substituted with the amine skeleton, but adding p20 to parentheses It is preferably part of a bound repeating unit. Two or more amine skeletons may exist, and, as for the number of amine skeletons in that case, it is preferable that it is 1-10, It is more preferable that it is 1-5, It is still more preferable that it is 2-5. Moreover, in this case, it is preferable to have an alkylene group between mutually adjacent amine skeletons, It is preferable that carbon number of this alkylene group is 1-10, and it is more preferable that it is 1-5. The carbon number of the alkylene group between the amine skeletons adjacent to each other is included in the total number of p20 or p21.

[0132] In the amine skeleton -NR ¹⁰⁰ -, when R ¹⁰⁰ is an alkyl group, the carbon number is preferably 5 or less, and more preferably 3 or less. It is preferable that amine skeleton -NR ¹⁰⁰ - is -NH- (R ¹⁰⁰ is a hydrogen atom).

[0133] p20 is preferably 1 to 15, more preferably 1 to 10, excluding the number of repeating units substituted with an amine skeleton.

[0134] p21 is preferably 0 to 5, more preferably 0 to 2, except for the number of repeating units substituted with an amine skeleton.

[0135] As for p22 and p23, 2-3 are preferable, More preferably, it is 3.

[0136] As the organosilicon compound (C2), in the above formula (c2), R ^x20 and R ^x21 are both hydrogen atoms, X ²⁰ and X ²¹ are alkoxy groups (particularly methoxy or ethoxy groups), and p20 is a repeating unit enclosed in parentheses is substituted with at least one amine skeleton -NR ¹⁰⁰ -, R ¹⁰⁰ is a hydrogen atom, and p20 is 1 to 10 (provided that the number of repeating units substituted with an amine skeleton is excluded) ), p21 is 0, and p22 and p23 are 3, preferably used.

[0137] In addition, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and chloropropyltri described in Japanese Patent Application Laid-Open No. 2012-197330, which are used as compound (C) in the Examples to be described later When the reactant of methoxysilane (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, p20 is 8, and p21 is 0, two amine skeletons (both R ¹⁰⁰ is a hydrogen atom), both ends are the same, p22 and p23 are 3, and X ²⁰ and X ²¹ are methoxy groups.

[0138] The organosilicon compound (C2) is preferably a compound represented by the following formula (c2-2).

[0139]

[0140] In the above formula (c2-2),

X ²² and X ²³ are each independently a hydrolysable group, and when two or more X ²² and X ²³ exist, a plurality of X ²² and X ²³ may be different from each other,

R ^x24 and R ^x25 are each independently an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^x24 and R ^x25 exist, a plurality of R ^x24 and R ^x25 may be different, respectively;

-C _w H _2w -, at least one of a part of the methylene group is substituted with an amine skeleton -NR ¹⁰⁰ -, R ¹⁰⁰ is a hydrogen atom or an alkyl group,

w is an integer from 1 to 30 (with the proviso that the number of methylene groups substituted with an amine skeleton is excluded),

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

[0141] 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 an alkoxy group having 1 to 4 carbon atoms (especially a methoxy group or an ethoxy group). more preferably.

[0142] A plurality of amine skeletons -NR ¹⁰⁰ - may exist, and in that case, the number of amine skeletons is preferably 1 to 10, more preferably 1 to 5, and still more preferably 2 to 5. . Further, in this case, it is preferable to have an alkylene group between the amine skeletons adjacent to each other. It is preferable that it is 1-10, and, as for carbon number of the said alkylene group, it is more preferable that it is 1-5. Carbon number of the alkylene group between mutually adjacent amine skeletons is included in the total number of w.

[0143] In the amine skeleton -NR ¹⁰⁰ -, when R ¹⁰⁰ is an alkyl group, the carbon number is preferably 5 or less, and more preferably 3 or less. It is preferable that amine skeleton -NR ¹⁰⁰ - is -NH- (R ¹⁰⁰ is a hydrogen atom).

[0144] 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.

[0145] It is preferable that p24 and p25 are integers of 2-3, and it is more preferable that it is 3.

[0146] w is preferably 1 or more, more preferably 2 or more, more preferably 20 or less, and more preferably 10 or less.

[0147] IV-3. Organosilicon compound (C) represented by the following formula (c3) (hereinafter, organosilicon compound (C3))

[0148]

In the above formula (c3),

Z ³¹ and Z ³² are each independently a reactive functional group other than a hydrolysable group and a hydroxy group. Examples of the reactive functional group include a vinyl group, α-methylvinyl group, styryl group, methacryloyl group, acryloyl group, amino group, epoxy group, ureido group, and mercapto group. As Z ³¹ and Z ³² , an amino group, a mercapto group, or a methacryloyl group is preferable, and an amino group is particularly preferable.

[0149] R ^x31 , R ^x32 , R ^x33 , R ^x34 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when there are a plurality of R ^x31 , a plurality of R ^x31 may be different, When a plurality of R ^x32 exist, a plurality of R ^x32 may be respectively different, when a plurality of R ^x33 exist, a plurality of R ^x33 may be respectively different, and when a plurality of R ^x34 exist, a plurality of R ^x34 each may be different. It is preferable that it is a hydrogen atom or a C1-C2 alkyl group, and, as ^{for Rx31} , ^Rx32 , ^Rx33 , ^Rx34 , it is more preferable that it is a hydrogen atom.

[0150] Rf ^x31 , Rf ^x32 , Rf ^x33 , 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, Each of Rf ^x31 may be different, and when a plurality of Rf ^x32 exist, a plurality of Rf ^x32 may be respectively different, and when a plurality of Rf ^x33 exist, a plurality of Rf ^x33 may be respectively different, and a plurality of Rf ^x34 is present. In this case, a 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 in which one or more hydrogen atoms are substituted with a fluorine atom, or a fluorine atom.

[0151] Y ³¹ is -NH-, -N(CH ₃ )-, or -O-, and when a plurality of Y ³¹ is present, a plurality of Y ³¹ may be different from each other. Y ³¹ is preferably -NH-.

[0152] X ³¹ , X ³² , X ³³ , X ³⁴ are each independently -OR ^c (R ^c is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or aminoC _{1-3 alkyldiC 1-3} alkoxysilyl group), and when a plurality of X ³¹ is present, a plurality of X ³¹ may be respectively different, a plurality of X ^{32 may be respectively different when a plurality of X 32 are} present, and when a plurality of X ³³ is present, A plurality of X ³³ may be different from each other, and when a plurality of X ³⁴ are present, a plurality of X ³⁴ may be respectively different. X ³¹ , X ³² , X ³³ , and X ³⁴ are preferably -OR ^c wherein 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.

[0153] 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, , p37 is 0 or 1. As for p31, 1-15 are preferable, More preferably, it is 3-13, More preferably, it is 5-10. As for p32, p33, and p34, respectively independently, 0-5 are preferable, More preferably, all are 0-2. As for p35, 1-5 are preferable, More preferably, it is 1-3. As for p36, 1-5 are preferable, More preferably, it is 1-3. As for p37, 1 is preferable.

[0154] The organosilicon compound (C3) satisfies the condition that at least one of Z ³¹ and Z ³² is an amino group, or that at least one of Y ³¹ is -NH- or -N(CH ₃ )-, and has a terminal Z ³¹ - and Z ³² -, p31 -｛C(R ^x31 )(R ^x32 )｝-, p32 -｛C(Rf ^x31 )(Rf ^x32 ), unless -O- is linked with -O- )｝-, p33 -｛Si(R ^x33 )(R ^x34 )｝-, p34 -｛Si(Rf ^x33 )(Rf ^x34 )｝-, p35 -Y ³¹ -, p36 -｛Si(X) ³¹ )(X ³² )-O｝-, and p37 pieces of -｛Si(X ³³ )(X ³⁴ )｝- are arranged and combined in an arbitrary order. p31 pieces of -｛C(R ^x31 )(R ^x32 )｝- do not need to be continuously bonded to -｛C(R ^x31 )(R ^x32 )｝-, and may be bonded through other units in the middle; A total of p31 pieces is sufficient. The same applies to units grouped by p32 to p37.

[0155] In the organosilicon compound (C3), Z ³¹ and Z ³² are amino groups, R ^x31 and R ^x32 are hydrogen atoms, p31 is 3-13 (preferably 5-10), R ^x33 and R ^x34 are all hydrogen atoms, Rf ^x31 to Rf ^x34 are all alkyl groups having 1 to 10 carbon atoms or fluorine atoms in which one or more hydrogen atoms are substituted with fluorine atoms, p32 to p34 are all 0 to 5, 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 1 is preferred. .

[0156] The organosilicon compound (C3) is preferably represented by the following formula (c3-2).

[0157]

[0158] In formula (c3-2), Z ³¹ , Z ³² , X ³¹ , X ³² , X ³³ , X ³⁴ , Y ³¹ have the same meaning as those in formula (c3), and p41 to p44 are, Each is independently an integer of 1 to 6, and p45 and 46 are each independently 0 or 1.

[0159] 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 more preferably R ^c is a hydrogen atom. Y ³¹ is preferably -NH-. 2 or more are preferable, and, as for p41-p44, 5 or less are preferable, and 4 or less are more preferable. It is preferable that both p45 and p46 are 0.

[0160] The mixed composition (cc) is a composition in which the organosilicon compound (C) is mixed, and the organosilicon compound (C) may be one type or two or more types. A mixed composition (cc) is obtained by mixing an organosilicon compound (C), and when components other than an organosilicon compound (C) are mixed, it is obtained by mixing an organosilicon compound (C) and another component. . The mixed composition (cc) includes those that have undergone a reaction after mixing, for example, during storage.

[0161] As an example in which the reaction proceeded during storage of the mixed composition (cc), the mixed composition (cc) may include a condensate of the organosilicon compound (C), and more specifically, the mixed composition (cc) contains the condensate of the organosilicon compound (C). The composition (cc) may include an organosilicon compound (C3') in which the organosilicon compound (C3) is condensed and bonded in at least any one of X ³¹ to X ³⁴ described above.

[0162] The organosilicon compound (C3') has two or more structures (c31-1) represented by the following formula (c31-1), and the structures (c31-1) are the following *3 or *4 As a compound bonded in a chain or cyclic form, the bond in *3 or *4 below is by condensation of X ³¹ or X ³² of two or more of the organosilicon compounds (C3). will,

In *1 and *2 of the following formula (c31-1), at least one of the units grouped by p31, p32, p33, p34, p35, (p36)-1, and p37 of the following formula (c31-2) is optional, respectively A group bonded in the order of and having a terminal Z- is bonded, and for each of the plurality of structures (c31-1), the groups bonding to *1 and *2 may be different,

When a plurality of the structures (c31-1) are chained together, the terminal *3 is a hydrogen atom, and *4 is a hydroxyl group.

[0163]

[0164]

[0165] In the above formula (c31-2),

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

R ^x31 , R ^x32 , R ^x33 , R ^x34 , Rf ^x31 , Rf ^x32 , Rf ^x33 , R ^f34 , Y ³¹ , X ³¹ , X ³² , X ³³ , X ³⁴ , p31 to p37 are in the formula (c3) These symbols have the same meaning.

[0166] When the organosilicon compound (C3) is a compound represented by the above formula (c3-2), as the organosilicon compound (C3'), the structure represented by the following formula (c31-3) is, for example, *3 or *4, the compound bonded in a chain form or a ring form is mentioned. When the structures represented by the following formula (c31-3) are chained together, the terminal *3 is a hydrogen atom, and the terminal *4 is a hydroxyl group.

[0167]

[0168] All the symbols in the formula (c31-3) have the same meaning as the symbols in the formula (c3-2).

[0169] The organosilicon compound (C3') is preferably a compound in which 2 to 10 (preferably 3 to 8) structures represented by the above formula (c31-3) are bonded.

[0170] V. Solvent (E)

As for the said mixed composition (cc), it is preferable that the solvent (E) is mixed. The solvent (E) is not particularly limited, and for example, water, an alcohol-based solvent, a ketone-based solvent, an ether-based solvent, a hydrocarbon-based solvent, an ester-based solvent, etc. can be used. In particular, water, an alcohol-based solvent, a ketone-based solvent, and a hydrocarbon system solvents are preferred.

[0171] Examples of the alcohol-based solvent include methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol.

Acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. are mentioned as a ketone type solvent.

Examples of the ether solvent include diethyl ether, dipropyl ether, tetrahydrofuran, and 1,4-dioxane.

Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents such as pentane and hexane, alicyclic hydrocarbon solvents such as cyclohexane, and aromatic hydrocarbon solvents such as benzene, toluene and xylene.

Examples of the ester solvent include ethyl acetate, propyl acetate, and butyl acetate.

[0172] When the total amount of the composition (cc) is 100% by mass, the total amount of the organosilicon compound (C) is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, still more preferably is 0.02 mass % or more, more preferably 0.1 mass % or more, and further preferably 5 mass % or less, more preferably 3 mass % or less, still more preferably 2 mass % or less. The quantity of said organosilicon compound (C) can be adjusted at the time of preparation of a composition. You may compute the quantity of the said organosilicon compound (C) from the analysis result of a composition. In addition, in this specification, when the range of the quantity, mass ratio, or molar ratio of each component is described, the said range can be adjusted at the time of preparation of a composition similarly to the above.

[0173] 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), specifically, in the visible light region of 380 to 780 nm, the intermediate layer ( In terms of the c) side, it is preferable that the reflectance is a layer exhibiting a reflective characteristic reduced to about 5.0% or less, more preferably 4.80% or less, and still more preferably 4.5% or less. You may evaluate this reflectance by the spectral reflectance of wavelength 530 nm.

[0174] In the substrate (s), at least in the outermost layer on the intermediate layer (c) side, it is preferable that the surface Si ratio is 1 atomic% or more, and the substrate (s) is preferably an organic material or an inorganic material. When the surface Si ratio is greater than or equal to a predetermined level, 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 abrasion resistance of the water-repellent layer (r) side surface of the laminate of the present invention This 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.

[0175] The base material (s) may be composed of one type of material, or may be composed of two 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, acrylic-styrene copolymer resins, cellulose resins, polyolefin resins, vinyl resins (polyethylene, Thermoplastic resins, such as polyvinyl chloride, polystyrene, vinylbenzyl chloride-type resin, polyvinyl alcohol, etc.); or thermosetting resins such as phenol resins, urea resins, melamine resins, epoxy resins, unsaturated polyesters, silicone resins, and urethane resins; or resin materials such as engineering plastics such as polyamide-based resins, polyimide-based resins, and polyamideimide-based resins, or oxides of metals such as titanium, zirconium, aluminum, niobium, tantalum, lanthanum, or silicon.

[0176] When the substrate (s) is composed of one type of material, the resin layer may be a layer having a surface Si ratio of 1 atomic% or more, or a metal oxide layer such as silica.

[0177] When the substrate (s) is composed of two or more materials, a protective layer (hereinafter referred to as a hard coating layer) installed on the resin layer to protect the article from scratches for applications requiring abrasion resistance, such as displays of electronic devices. In some cases, it is preferable that the installed one. As a material which comprises the said resin layer, the above-mentioned thermosetting resin, a thermoplastic resin, or an engineering plastics can be used, and a polyester resin is especially preferable. The hard-coat layer mentioned above is a layer which has surface hardness, The hardness is 2H or more in pencil hardness, for example. A single layer structure may be sufficient as a hard-coat layer, and a multilayer structure may be sufficient as it. The hard coat layer includes a hard coat layer resin, and the hard coat layer resin includes, for example, an acrylic resin, an epoxy resin, a urethane resin, a vinyl benzyl chloride resin, a vinyl resin, a silicone resin, or a mixture thereof. , electron beam curing type, or thermosetting type resin, and as described above, in the resin for forming these hard coat layers, it is preferable that the surface Si ratio is 1 atomic% or more. In particular, in order for a hard-coat layer to express high hardness, it is preferable that surface Si ratio is 1 atomic% or more containing an acrylic resin. It is also preferable to contain an epoxy resin from the point that the tendency for adhesiveness with the said water-repellent layer (r) which sandwiched the said intermediate|middle layer (c) to become favorable can be seen.

[0178] The hard coat layer may further contain an ultraviolet absorber, or may contain a metal oxide such as silica or alumina, or an inorganic filler such as polyorganosiloxane. By including such an inorganic filler, adhesiveness with the said water-repellent layer (r) which sandwiched the said intermediate|middle layer (c) can be improved.

[0179] When the base material (s) is composed of two or more materials, the antireflection layer may be provided on the resin layer, and it is also preferable that the antireflection layer is additionally provided on the hard coat layer provided on the resin layer, In this case, the resin layer, the hard coat layer, the antireflection layer, the intermediate layer (c), and the water repellent layer (r) are laminated in this order. As a 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 in a visible light region of 380 to 780 nm, a layer exhibiting a reflective characteristic in which the reflectance is reduced to about 5% or less. The structure of the antireflection layer is not particularly limited, and may have a single layer structure or a multilayer structure. In the case of a multilayer structure, a structure in which a low-refractive-index layer and a high-refractive-index layer are alternately laminated is preferable, and the total number of layers is preferably 2 to 20. 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 (that is, silica). As the antireflection layer having a multilayer structure, 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 base material (s) is SiO ₂ is preferable. The antireflection layer can be formed by, for example, a vapor deposition method.

[0180] In the base material (s), the above-described reflective properties and/or the material may be satisfied at least in the outermost layer on the intermediate layer (c) side of the base material (s), preferably, the base material What is necessary is just to satisfy with the thickness of 10% or more (thickness of the said base material (s)) from the outermost layer on the side of the intermediate|middle layer (c) of (s), More preferably, what is necessary is just to satisfy with the thickness of 40% or more, and the base material (s) It is more preferable to be satisfied in the whole.

[0181] 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, particularly preferably 30 to 90 μm.

[0182] The water contact angle (initial contact angle) when the laminate of the present invention is evaluated according to the method described in Examples to be described later is, for example, 105° or more, more preferably 110° or more, and, for example, 125 ° or less.

[0183] Next, a method for manufacturing the laminate of the present invention will be described.

[0184] A first method of manufacturing a laminate of the present invention includes (i) a step of applying the mixed composition (cc) on a substrate (s), (ii) on the coated surface of the mixed composition (cc), A step of applying the mixed composition (ca), (iii) a step of curing the mixed composition (cc) and the mixed composition (ca), from the coating layer of the mixed composition (cc) to the intermediate layer (c) ), and the water-repellent layer (r) is formed from the application layer of the mixed composition (ca).

[0185] As a method of applying the mixed composition (cc), it can be carried out by a known method, but a spin coating method or a dip coating method is preferable.

[0186] Next, the mixed composition (ca) for forming the water-repellent layer (r) is applied to the coated surface of the mixed composition (cc) and dried, from the application layer of the mixed composition (cc) to the intermediate layer (c) and to form the water-repellent layer (r) from the application layer of the mixed composition (ca). The intermediate layer (c) may be formed during or after application of the mixed composition (cc), or the intermediate layer (c) and the water-repellent layer (r) may be formed simultaneously. As a method of applying the composition for forming the water-repellent layer (r), for example, a dip coating method, a roll coating method, a bar coating method, a spin coating method, a spray coating method, a die coating method, a gravure coating method, etc. are mentioned.

[0187] After coating the composition for forming the water-repellent layer (r), the laminate of the present invention can be manufactured by allowing the composition to stand at room temperature and in the air, for example, for 1 hour or more (normally 24 hours or less). In this invention, normal temperature is 5-60 degreeC, Preferably it is the temperature range of 15-40 degreeC. The humidity condition at the time of leaving still at normal temperature is good also as 50-90 %RH. Further, after the composition for forming the water-repellent layer (r) is applied, it is heated to a temperature exceeding 60°C (usually 100°C or lower, 80°C or lower may be acceptable) for 5 minutes to 60 minutes (preferably 20 minutes to 40 minutes) may be maintained.

[0188] In the second method of manufacturing the laminate of the present invention, an intermediate layer (c) is formed by depositing the organosilicon compound (C) on the substrate (s), and on the intermediate layer (c) , The mixture composition (ca) is applied and cured to form the water repellent layer (r) from the application layer of the mixture composition (ca). When vapor-depositing the organosilicon compound (C) to form the intermediate layer (c), the organosilicon compound (C) single body may be vapor-deposited on the base material (s), or the organosilicon compound (C) and You may vapor-deposit the solid substance obtained by removing a solvent from the mixed composition of a solvent (that is, the said organosilicon compound (C)) on the base material (s). After apply|coating the composition for water-repellent layer (r) formation, what is necessary is just to carry out similarly to the said 1st method.

[0189] Before applying the composition (cc) or before depositing the organosilicon compound (C), it is preferable to perform a hydrophilization treatment on the substrate (s). As said hydrophilization process, hydrophilization processes, such as a corona process, a plasma process, an ultraviolet process, and an ion cleaning process, are mentioned, A plasma process and an ion cleaning process are more preferable. 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 in particular, when such functional groups are formed on the surface of the substrate, the intermediate layer (c) and the substrate ( s) adhesion between them may be further improved.

[0190] <Flexible display device>

This invention also provides the flexible display apparatus provided with the optical laminated body of this invention. The laminate of the present invention can be preferably used as a front plate in a flexible display device, and the front plate is sometimes called a window film. The flexible display device preferably includes a flexible display device laminate and an organic EL display panel, and the flexible display device laminate is disposed on the visual recognition side with respect to the organic EL display panel, and is bent made possible. The laminate for a flexible display device may further contain a polarizing plate (preferably a circularly polarizing plate), a touch sensor, and the like, and the lamination order of these may be arbitrary, but a window film (that is, the laminate of the present invention) from the viewer side , It is preferable to laminate in order of a polarizing plate, a touch sensor, or a window film, a touch sensor, and a polarizing plate. When a polarizing plate exists on the visual recognition side rather than a touch sensor, since it becomes difficult to visually confirm the pattern of a touch sensor, and the visibility of a display image improves, it 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 layer of the window film, the polarizing plate, and the touch sensor.

[0191] <Circular Polarizer>

It is preferable that the flexible display device of this invention is equipped with a circularly-polarizing plate among a polarizing plate as mentioned above. A circularly polarizing plate is a functional layer which has a function which transmits only a right or left circularly polarizing component by laminating|stacking a λ/4 retardation plate on a linear polarizing plate. For example, it is used to convert external light into right circularly polarized light, block external light that is reflected from the organic EL panel to become left circularly polarized light, and transmit only the luminescent component of the organic EL to suppress the effect of reflected light and make the image easier to see. In order to achieve the circular polarization function, the absorption axis of the linear polarizing plate and the slow axis of the λ/4 retarder need to be 45 degrees theoretically, but in practice they are 45±10 degrees. The linear polarizing plate and the λ/4 retardation plate are not necessarily stacked adjacent to each other, and the relationship between the absorption axis and the retardation axis may satisfy the above-described range. Although it is desirable to achieve perfect circular polarization over all wavelengths, it is not necessary for practical use, so the circularly polarizing plate in the present invention also includes an elliptically polarizing plate. It is also preferable to further laminate a λ/4 retardation film on the visual recognition side of the linear polarizing plate, and to improve the visibility in a state in which polarized sunglasses are worn by making the emitted light circularly polarized light.

[0192] A linear polarizing plate is a functional layer having a function of passing light vibrating in the transmission axis direction, but blocking polarization of a vibration component perpendicular thereto. The linear polarizing plate may be configured to include a linear polarizer alone or a linear polarizer and a protective film adhered to at least one surface thereof. The thickness of the said linear polarizing plate may be 200 micrometers or less, Preferably it is 0.5-100 micrometers. When the thickness of the linear polarizing plate is within the above range, the flexibility of the linear polarizing plate tends to be less likely to decrease.

[0193] The linear polarizer may be a film-type polarizer manufactured by dyeing and stretching a polyvinyl alcohol (hereinafter, sometimes abbreviated as PVA)-based film. When a dichroic dye such as iodine is adsorbed to a PVA-based film orientated by stretching or stretched in a state adsorbed to PVA, the dichroic dye is orientated to exhibit polarization performance. In manufacture of the said film polarizer, you may have other processes, such as swelling, bridge|crosslinking by boric acid, washing|cleaning by aqueous solution, and drying. The extending|stretching and dyeing process may be performed individually with a PVA-type film, and may be performed in the state laminated|stacked with other films, such as polyethylene terephthalate. The thickness of the PVA-based film 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 include a liquid crystal compound and a dichroic dye compound. The said liquid crystalline compound should just have the property which shows a liquid crystal state, especially since high polarization performance can be exhibited when it has high-dimensional orientation states, such as a smectic phase, it is preferable. Moreover, it is preferable that a liquid crystalline compound has a polymerizable functional group.

The said dichroic dye compound is a pigment|dye which orientates with the said liquid crystalline compound, and shows dichroism, may have a polymerizable functional group, and may have liquid crystalline in dichroic dye itself.

Any of the compounds contained in the liquid crystal polarizing composition have a polymerizable functional group. The liquid crystal polarizing composition may further include 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 polarizing layer is prepared by coating a liquid crystal polarizing composition on an alignment layer to form a liquid crystal polarizing layer. A liquid crystal polarizing layer can form thinly in thickness compared with a film polarizer, The thickness becomes like this. Preferably it is 0.5-10 micrometers, More preferably, it is 1-5 micrometers.

[0194] The alignment layer is prepared by, for example, coating an alignment layer forming composition on a substrate and imparting alignment property by rubbing, polarized light irradiation, or the like. The 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 aligning agent, polyvinyl alcohol, polyacrylates, polyamic acids, and polyimides are mentioned, for example. When using the aligning agent which provides orientation by polarized light irradiation, it is preferable to use the aligning agent containing a cinnamate group. The weight average molecular weight of the polymer used as the alignment agent is, for example, about 10,000 to 1,000,000. The thickness of the said alignment film becomes like this. Preferably it is 5-10,000 nm, More preferably, it is 10-500 nm from the point which orientation regulating force is fully expressed.

The liquid crystal polarizing layer may be laminated by peeling and transferring from the substrate, or may be laminated on the substrate as it is. It is also preferable that the said base material plays a role as a transparent base material of a protective film, a retardation plate, and a window film.

[0195] As the protective film, any transparent polymer film may be used, and the same materials or additives used for the transparent substrate of the window film may be used. Moreover, the protective film of the coating type obtained by apply|coating and hardening|curing cation curing compositions, such as an epoxy resin, and radical curing compositions, such as an acrylate, may be sufficient. The protective film may contain, if necessary, a plasticizer, an ultraviolet absorber, an infrared absorber, a colorant such as a pigment or dye, an optical brightener, a dispersant, a heat stabilizer, a light stabilizer, an antistatic agent, an antioxidant, a lubricant, a solvent, and the like. . The thickness of this protective film becomes like this. Preferably it is 200 micrometers or less, More preferably, it is 1-100 micrometers. When the thickness of a protective film exists in said range, there exists a tendency for the softness|flexibility of this film to fall easily.

[0196] The λ/4 retardation plate is a film that imparts a retardation of λ/4 in a direction perpendicular to the traveling direction of incident light (in-plane direction of the film). The λ/4 retardation plate may be a stretched retardation plate manufactured by stretching a polymer film such as a cellulose-based film, an olefin-based film, or a polycarbonate-based film. The λ/4 retardation plate is, if necessary, a retardation regulator, a plasticizer, an ultraviolet absorber, an infrared absorber, a colorant such as a pigment or dye, an optical brightener, a dispersant, a heat stabilizer, a light stabilizer, an antistatic agent, an antioxidant, a lubricant, a solvent etc. may be included.

The thickness of the said stretched retardation plate becomes like this. Preferably it is 200 micrometers or less, More preferably, it is 1-100 micrometers. When the thickness of the stretched retardation plate is within the above range, the flexibility of the stretched retardation plate tends to be less likely to decrease.

Moreover, as another example of the said λ/4 retardation plate, a liquid crystal coating type retardation plate formed by 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 said liquid crystalline compound has a polymerizable functional group.

The liquid crystal composition may further include 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 manufactured by coating and curing a liquid crystal composition on a substrate to form a liquid crystal retardation layer, similarly to the liquid crystal polarizing layer. The liquid-crystal-coated retardation plate can be formed to have a thinner thickness than the stretch-type retardation plate. The thickness of the said liquid crystal polarizing layer becomes like this. Preferably it is 0.5-10 micrometers, More preferably, it is 1-5 micrometers.

The liquid-crystal-coated retardation plate may be laminated by peeling off the substrate and transferring it, or the substrate may be laminated as it is. It is also preferable that the said base material plays a role as a transparent base material of a protective film, a retardation plate, and a window film.

[0197] In general, there are many materials exhibiting a birefringence having a greater birefringence for a shorter wavelength and a smaller birefringence for a longer wavelength. In this case, since a phase difference of λ/4 cannot be achieved in the entire visible light region, the in-plane phase difference is preferably 100 to 180 nm, more preferably 130 to 150 nm so that it becomes λ/4 in the vicinity of 560 nm with high visibility. is designed to be A reverse dispersion λ/4 retardation plate using a material having the opposite birefringence wavelength dispersion characteristic is preferable from the viewpoint of improving visibility. As such a material, for example, those described in Japanese Patent Application Laid-Open No. 2007-232873 and the like for a stretched retardation plate and those described in Japanese Patent Laid-Open No. 2010-30979 for a liquid crystal coating type retarder can be used.

As another method, there is also known a technique for obtaining a broadband ?/4 retarder by combining it with a ?/2 retarder (eg, Japanese Patent Laid-Open No. H10-90521, etc.). The λ/2 retarder is also manufactured by the same material method as the λ/4 retarder. Although the combination of the stretched retardation plate and the liquid crystal coating type retardation plate is arbitrary, the thickness can be made thin by using the liquid crystal coating type retardation plate in both.

A method of stacking positive C plates on the circular polarizing plate in order to increase visibility in an oblique direction is known (eg, Japanese Patent Application 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, more preferably -140 to -40 nm.

[0198] <Touch sensor>

It is preferable that the flexible display device of this invention is equipped with a touch sensor as mentioned above. A touch sensor is used as an input means. As a touch sensor, various modalities, such as a resistive film system, a surface acoustic wave system, an infrared system, an electromagnetic induction system, and a capacitive system, are mentioned, Preferably, a capacitive system is mentioned.

The capacitive touch sensor is divided into an active area and an inactive area located outside the active area. The active area is an area corresponding to the area where the screen is displayed (display unit) of the display panel, and is an area in which a user's touch is sensed, and the inactive area is an area corresponding to the area in which the screen is not displayed (non-display unit) of the display device. . The touch sensor includes a substrate having flexible characteristics, a sensing pattern formed in an active region of the substrate, and each sensing line formed in an inactive region of the substrate and connected to an external driving circuit through the sensing pattern and the pad part. may include As the substrate having flexible properties, the same material as the transparent substrate of the window film can be used.

[0199] The sensing pattern may include a first pattern formed in a first direction and a second pattern formed in a second direction. The first pattern and the second pattern are arranged in different directions. The first pattern and the second pattern are formed on the same layer, and in order to sense a touched point, each pattern must be electrically connected. In the first pattern, a plurality of unit patterns are connected to each other through a joint, but in the second pattern, a plurality of unit patterns are separated from each other in an island form. electrode is required. A well-known transparent electrode can be applied to the electrode for connection of a 2nd pattern. Examples of the material for 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), and cadmium tin oxide (CTO). ), PEDOT (poly(3,4-ethylenedioxythiophene)), carbon nanotubes (CNT), graphene, metal wire, and the like, and preferably ITO. These can be used individually or in mixture of 2 or more types. The metal used for the metal wire is not particularly limited, and examples thereof include silver, gold, aluminum, copper, iron, nickel, titanium, telenium, chromium, and the like, and these may be used alone or in combination of two or more. .

The bridge electrode may be formed on the insulating layer by interposing an insulating layer on the sensing pattern, the bridge electrode may be formed on a substrate, and the insulating layer and the sensing pattern may 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 thereof.

Since the first pattern and the second pattern must be electrically insulated, an insulating layer is formed between the sensing pattern and the bridge electrode. The insulating layer may be formed only between the joint portion of the first pattern and the bridge electrode, 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.

[0200] In the touch sensor, a difference in transmittance between a pattern region in which a sensing pattern is formed and a non-pattern region in which a sensing pattern is not formed, specifically, a light transmittance caused by a difference in refractive index in these regions An optical adjustment layer may be further included between the substrate and the electrode as a means for properly compensating for the difference in . The optical control layer may include an inorganic insulating material or an organic insulating material. The optical control layer may be formed by coating a photocurable composition including a photocurable organic binder and a solvent on a substrate. The photocurable composition may further include inorganic particles. The refractive index of the optical control layer may be increased by the inorganic particles.

The photocurable organic binder may include, for example, a copolymer of each monomer such as an acrylate-based monomer, a styrene-based monomer, or a carboxylic acid-based monomer within a range that does not impair the effects of the present invention. The photocurable organic binder may be, for example, a copolymer containing different repeating units, 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 titania 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 hardening adjuvant.

[0201] <Adhesive layer>

Each layer (window film, circularly polarizing plate, touch sensor) forming the laminate for the flexible image display device and the film member (linear polarizing plate, λ/4 retardation plate, etc.) constituting each layer can be bonded by an adhesive. Examples of the adhesive include a water-based adhesive, an organic solvent-based adhesive, a solvent-free adhesive, a solid adhesive, a solvent volatilization adhesive, a moisture-curing adhesive, a heat-curing adhesive, an anaerobic curing adhesive, an active energy ray curing adhesive, and a curing agent mixed adhesive. , a heat-melting adhesive, a pressure-sensitive adhesive (adhesive), a rewritable adhesive, etc., which are commonly used adhesives, etc. can be used, preferably a water-based solvent volatilization adhesive, an active energy ray-curable adhesive, an adhesive Can be used. The thickness of an adhesive bond layer can be suitably adjusted according to the adhesive force requested|required etc., Preferably it is 0.01-500 micrometers, More preferably, it is 0.1-300 micrometers. Although a some contact bonding layer exists in the said laminated body for flexible image display apparatuses, each thickness and kind may be same or different.

[0202] As the water-based solvent volatilization type adhesive, a water-dispersed polymer such as a polyvinyl alcohol-based polymer, a water-soluble polymer such as starch, an ethylene-vinyl acetate-based emulsion, and a styrene-butadiene-based emulsion can be used as the main polymer. can In addition to the main polymer and water, a crosslinking agent, a silane compound, an ionic compound, a crosslinking catalyst, an antioxidant, a dye, a pigment, an inorganic filler, an organic solvent, etc. may be blended. In the case of bonding with the water-based solvent volatilization adhesive, the water-based solvent volatilization type adhesive may be injected between the adherend layers to bond the adherend layers, followed by drying to impart adhesion. When using the said water-based solvent volatilization type adhesive agent, the thickness of the adhesive layer becomes like this. Preferably it is 0.01-10 micrometers, More preferably, it is 0.1-1 micrometer. When using the said water-system solvent volatilization type adhesive agent for multiple layers, the thickness and the kind of each layer may be same or different.

[0203] The active energy ray-curable adhesive can be formed by curing an active energy ray-curable composition containing a reactive material that forms an adhesive layer by irradiating an active energy ray. The said active energy ray hardening composition can contain the polymer of at least 1 sort(s) of the same radically polymerizable compound and a cationically polymerizable compound as what is contained in a hard-coat composition. As the said radically polymerizable compound, the compound similar to the radically polymerizable compound in a hard-coat composition can be used.

The said cationically polymerizable compound can use the compound similar to the cationically polymerizable compound in a hard-coat composition.

As a cationically polymerizable compound used for an active energy ray hardening composition, an epoxy compound is especially preferable. It is also preferable to include a monofunctional compound as a reactive diluent in order to lower the viscosity as an adhesive composition.

[0204] The active energy ray composition may include a monofunctional compound in order to decrease the viscosity. As the monofunctional compound, an acrylate-based monomer having one (meth)acryloyl group in one molecule, or a compound 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. Examples of the polymerization initiator include a radical polymerization initiator, a cationic polymerization initiator, a radical and a cationic polymerization initiator, and these are appropriately selected and used. These polymerization initiators are decomposed|disassembled by at least 1 sort(s) of active energy ray irradiation and heating, generate|occur|produce a radical or a cation, and advance radical polymerization and cationic polymerization. In the base material of a hard-coat composition, the initiator which can start at least any one of radical polymerization or cationic polymerization by active energy ray irradiation can be used.

The active energy ray curing composition may further include an ion scavenger, an antioxidant, a chain transfer agent, a adhesion imparting agent, a thermoplastic resin, a filler, a flow viscosity modifier, a plasticizer, an antifoaming agent solvent, an additive, and a solvent. When adhering two to-be-adhesive layers with the said active energy ray hardening-type adhesive agent, after apply|coating the said active energy ray hardening composition to any one or both of to-be-adhesive layers, and bonding, to either adherent layer or both to-be-adhesive layers It can adhere|attach by irradiating and hardening an active energy ray. When using the said active energy ray hardening-type adhesive agent, 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 using the said active energy ray hardening-type adhesive agent for several contact bonding layer formation, the thickness and the kind of each layer may be same or different.

[0205] The pressure-sensitive adhesive is classified into an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, and the like, depending on the main polymer, and any of them may be used. You may mix|blend a crosslinking agent, a silane compound, an ionic compound, a crosslinking catalyst, antioxidant, a tackifier, a plasticizer, dye, a pigment, an inorganic filler, etc. with an adhesive in addition to a main polymer. Each component constituting the pressure-sensitive adhesive is dissolved and dispersed in a solvent to obtain a pressure-sensitive adhesive composition, and the pressure-sensitive adhesive composition is applied on a substrate and then dried to form an adhesive layer adhesive layer. The pressure-sensitive adhesive layer may be directly formed or may be transferred separately from the substrate. In order to cover the adhesive surface before adhesion, it is also preferable to use a release film. When using the said active energy ray hardening-type adhesive agent, the thickness of the adhesive layer becomes like this. Preferably it is 0.1-500 micrometers, More preferably, it is 1-300 micrometers. When using the said adhesive in multiple layers, the thickness and the kind of each layer may be same or different.

[0206] <Light-shielding pattern>

The light blocking pattern may be applied as at least a part of a bezel or a housing of the flexible image display device. By blocking the wiring arranged on the edge of the flexible image display device by the light-shielding pattern and making it difficult to visually confirm, the visibility of the image is improved. The light-shielding pattern may be in the form of a single layer or a multilayer. The color in particular of a light-shielding pattern is not restrict|limited, Various colors, such as black, white, and a metallic color, may be sufficient. The light-shielding pattern may be formed of a pigment for realizing a color, and a polymer such as an acrylic resin, an ester-based resin, an epoxy-based resin, polyurethane, or silicone. It can also be used individually or in mixture of 2 or more types of these. The light-shielding pattern may be formed by various methods such as printing, lithography, and inkjet. The thickness of the light-shielding pattern is preferably 1 to 100 µm, more preferably 2 to 50 µm. Moreover, it is also preferable to provide a shape, such as an inclination, in the thickness direction of a light shielding pattern.

Example

[0207] Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited by the following examples, and it is, of course, possible to carry out the present invention with appropriate modifications within the range suitable for the above and the following purposes, and all of these are included in the technical scope of the present invention.

[0208] Each layer or laminate obtained in the following Examples and Comparative Examples was evaluated by the following method.

[0209] Measurement of the surface Si ratio of the substrate (s) and the surface fluorine ratio of the water-repellent layer (r)

JEOL Ltd. Using manufactured JFS-9010 type, excitation X-ray: MgKα, X-ray output is 110 W, photoelectron escape angle is 45°, pass energy is 50 eV, fluorine (F1s) in water repellent layer (r), substrate (s) Various elements of silicon were measured.

[0210] Measurement of the arithmetic mean height Sa

Using a laser microscope (OLS4000, manufactured by Olympus Corporation), the surface of the water-repellent layer (r) of the laminate was observed at a magnification of 20 times. Arithmetic mean height Sa was evaluated based on ISO 25178. Arithmetic mean height Sa was made into the average value of N=2.

[0211] Contact angle and slip angle

On the water-repellent layer (r) of the obtained laminated body, 3.0 microliters of water drops were dripped, and the (theta)/2 method was used using the contact angle measuring apparatus (made by Kyowa Interface Science Co., Ltd., DM700). In this way, the contact angle of water of the liquid volume: 3.0 µL was measured.

Furthermore, on the water-repellent layer (r) of the obtained laminated body, 6.0 microliters of water drops were dripped, and using the said contact angle measuring apparatus (Kyowa Interface Science Co., Ltd. make, DM700), sliding method (滑落 method; sliding method) method) (water drop amount: 6.0 μL, inclination method: continuous inclination, slip detection: slip after slipping, slip determination distance: 0.25 mm), dynamic water-repellent properties (slip angle) of the water-repellent layer (r) surface of the laminate ) was measured.

[0212] Surface Reflectance

KONICA MINOLTA, INC. Using a manufactured colorimeter (CM-3700A, light source: D65), 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 (r) side of the laminate was 2 degrees of JIS Z8701. It calculated|required by visual field (C light source). 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 of the intermediate|middle layer (c) side surface of the base material (s) was carried out similarly and measured.

[0213] Wear-resistance test

Using a steel wool tester (manufactured by Daiei Seiki co., Ltd.) equipped with steel wool #0000 (manufactured by BONSTAR), the steel wool is in contact with the surface (water repellent layer (r)) of the laminate In, a wear test was performed by applying a load of 1000 g, and the test was repeated until peeling and scratching was confirmed visually, and the abrasion resistance was evaluated by the number of tests when peeling and scratching were confirmed. In addition, the confirmation of the presence or absence of peeling and a flaw was performed by the illumination intensity of 1000 lux.

[0214] thickness measurement

The thickness of the substrate (s) was measured using DIGIMICRO (model number: MFC-101A) manufactured by Nikon Corporation. In addition, in any of the 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.

[0215] Example 1

A reaction product of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and chloropropyltrimethoxysilane described in Japanese Patent Application Laid-Open No. 2012-197330, represented by the following formula as the organosilicon compound (C) ( A solution obtained by mixing 0.25 mass % of X-12-5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.) and 99.75 mass % of hexane as a solvent (E) was stirred at room temperature to form an intermediate layer (c) A solution was obtained.

[0216]

[0217] Next, as the substrate (s), an AR film having a thickness of 84 μm was prepared. The said AR film is a film which laminated|stacked SiO2 and _a metal oxide (however, other _than SiO2) alternately by the vacuum vapor deposition method on the resin layer, and made _the outermost surface SiO2. The surface Si ratio of the substrate (s) measured by the method described above was 31.5 atomic%. The surface of the AR film was activated by atmospheric pressure plasma treatment, and the solution for forming the intermediate layer (c) was applied to the activated surface using OPTICOAT MS-A100 (spin coater) manufactured by Mikasa Corporation in an amount of 200 μl, The intermediate layer (c) was obtained by applying the coating under the conditions of a rotation speed of 2000 rpm and the number of rotation seconds of 20 seconds.

[0218] Next, as the organosilicon compound (A), Optool (registered trademark) UF503 manufactured by DAIKIN INDUSTRIES, LTD. (20 mass % of the organosilicon compound (A) and 80 mass % of Novec7200 as a solvent are included. ), FAS13E (C ₆ F ₁₃ -C ₂ H ₄ -Si(OC ₂ H ₅ ) ₃ , manufactured by Tokyo Chemical Industry Co., Ltd.) as an organosilicon compound (B), FC-3283 (D) as a solvent (D) C ₉ F ₂₁ N, fluorine nut, manufactured by 3M Company) was mixed 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 the solution 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 spray coater manufactured by API Corporation. The spray coating conditions were: scan speed: 600 mm/sec, pitch: 5 mm, liquid amount: 6 cc/min, atomizing air: 350 kPa, gap: 70 mm. Then, it baked at 80 degreeC for 30 minutes, and obtained the laminated body containing the base material (s), the intermediate|middle layer (c), and the water repellent layer (r) in this order.

[0219] Example 2

In the same manner as in Example 1 except that the substrate (s) was changed to an AR film having a surface Si ratio of 31.3 atomic%, the substrate (s), the intermediate layer (c), and the water-repellent layer (r) were laminated in this order got a sieve

[0220] Example 3

As a solvent (E), it carried out similarly to Example 2 except having used butyl acetate, and obtained the laminated body which contains the base material (s), the intermediate|middle layer (c), and the water-repellent layer (r) in this order.

[0221] Example 4

In the same manner as in Example 1 except that the base material (s) was changed to a hard coat film having a thickness of 45 µm, a laminate including the base material (s), the intermediate layer (c), and the water repellent layer (r) in this order got it The hard coat film is a film in which an acrylic hard coat layer having a surface Si ratio of 1.8 atomic% is laminated on a resin layer composed of polyethylene terephthalate, and the same activation treatment by atmospheric pressure plasma treatment as in Example 1 is performed on the acrylic hard coat layer What was applied to the surface was used.

[0222] Example 5

In the same manner as in Example 1, except that the organosilicon compound (C) was changed to KBM-903 (manufactured by Shin-Etsu Chemical Co., Ltd.) and butyl acetate was used as the solvent (E), the substrate ( s), an intermediate layer (c), and a water-repellent layer (r) were obtained in this order.

[0223] Comparative Example 1

In the same manner as in Example 1, except that the base material (s) was changed to an acrylic hard coat layer having a thickness of 60 µm and a surface Si ratio of 0 atomic%, the base material (s), the intermediate layer (c), and the water repellent layer (r) were A laminate included in this order was obtained.

[0224] Comparative Example 2

Except having changed the solvent (E) to methyl ethyl ketone, it carried out similarly to Comparative Example 1, and obtained the laminated body which contains the base material (s), the intermediate|middle layer (c), and the water repellent layer (r) in this order.

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

[0226] [Table 1]

[0227] The laminate of the present invention is a display device such as a touch panel display, an optical element, a semiconductor element, a building material, a nanoimprint technology, a solar cell, a window glass of an automobile or building, a metal product such as a cooking utensil, a tableware, etc. It can form a film suitably for a ceramic product, a plastic automobile part, etc., and is useful industrially. Moreover, it is used suitably also for the article of each member around a kitchen, a bathroom, a sink, a mirror, and a toilet.

Claims (7)

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 surface reflection loss from the reflectance calculated by the 2 degree field of view (C light source) of JIS Z8701 for 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, and The reflectance minus the back reflection loss is 4.5% or less.
(2) The thickness of the laminate is 500 μm or less. According to claim 1,
Furthermore, the laminated body which satisfies the requirements of the following (3).
(3) The surface element ratio of fluorine on the side of the water-repellent layer (r) is 30 atomic% or more. 3. The method of claim 1 or 2,
Further, the laminate satisfying at least one of the requirements of the following (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 sliding angle of the water on the water repellent layer (r) side (滑落角; sliding angle) is 25 ° or less. 4. The method according to any one of claims 1 to 3,
The laminated body of the said base material (s), and the surface Si ratio of the outermost layer on the side of the said intermediate|middle layer (c) is 1 atomic% or more. 5. The method according to any one of claims 1 to 4,
The said water-repellent layer (r) is a cured layer of the mixed composition (ca) of the organosilicon compound (A) represented by the following formula (a1) and the organosilicon compound (B) represented by the following formula (b1).

In the above formula (a1),
Rf ^a1 is a divalent perfluoropolyether structure in which both ends are oxygen atoms,
R ¹¹ , R ¹² , and R ¹³ are each independently an alkyl group having ¹ to ²⁰ carbon atoms ^. R ¹² may be different from each other, and when there are two or more R ¹³ , a plurality of R ¹³ may be different from each other,
E ¹ , E ² , E ³ , E ⁴ , and E ^{5 each} independently represent ^a hydrogen atom or ^a fluorine atom. When a plurality of E ² may be different from each other, a plurality of E ^{3 may be respectively different when a plurality of E 3 are} present, and a plurality of E ⁴ may be respectively different when a plurality of E ⁴ are present, and E When a plurality of ⁵ is present, a plurality of E ⁵ may 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 1-5, R ¹⁴ is a methyl group or an ethyl group, J When ^two or more ^1s exist, several J< ¹ > may differ, respectively, when ^two or more J2 exists, some J2 may differ, respectively, and when ^two or more J3 exists, some ^J3 is respectively different. you can do it,
L ¹ and L ² are each independently a divalent linking group having 1 to 12 carbon atoms which may contain an oxygen atom, a nitrogen atom, or a fluorine atom, and when two or more L ¹ are present, a plurality of L ¹ may be respectively different, and when two or more L ² exist, a plurality of L ² may be respectively different,
d11 is 1 to 9,
d12 is 0 to 9,
a10 and a14 are each independently 0-10,
a11 and a15 are each independently 0 or 1,
a12 and a16 are each independently 0-9,
a13 is 0 or 1,
a21, a22, and a23 are each independently 0-2,
e1, e2, and e3 are each independently 1-3.

In the above formula (b1),
Rf ^b10 is an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom or a fluorine atom,
R ^b11 , R ^b12 , R ^b13 and R ^b14 are each independently a hydrogen ^atom or an alkyl group having 1 to 4 carbon ^{atoms .} When there is a plurality of them, a plurality of R ^b12 may be different from each other, and R ^b13 may be When there is a plurality of R ^b13 may be different from each other, and when there are a plurality of R ^b14 , a plurality of R ^b14 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 ^; may be different from each other, and when a plurality of Rf ^b12 exist, a plurality of Rf ^b12 may be different from each other, and Rf ^b13 is When there are multiple Rf ^b13 may be different from each other, and when there are a plurality of Rf ^b14 , a plurality of Rf ^b14 may be different from each other,
R ^b15 is an alkyl group having 1 to 20 carbon ^{atoms ;}
A ¹ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, wherein R is a hydrogen atom, an alkyl group having ¹ to 4 carbon atoms, or a fluorine-containing alkyl group having ¹ to 4 carbon atoms;
A2 is a hydrolysable group, and when ^two or ^more A2s exist, some ^A2 may differ, respectively,
b11, b12, b13, b14 and b15 are each independently an integer from 0 to 100;
c is an integer of 1 to 3,
Rf ^b10 -, -Si(A ² ) _c (R ^b15 ) _3-c , b11 -｛C(R ^b11 )(R ^b12 )｝-, b12 -｛C(Rf ^b11 )(Rf ^b12 )｝- , b13 -｛Si(R ^b13 )(R ^b14 )｝-, b14 -｛Si(Rf ^b13 )(Rf ^b14 )｝-, b15 -A ¹ -, Rf ^b10 -, -Si(A ² ) ) _c (R ^b15 ) _3-c becomes a terminal, does not form a perfluoropolyether structure, and is bonded in any order, unless -O- is connected with -O- to -F . 6. The method according to any one of claims 1 to 5,
The intermediate layer (c) is a cured layer of a mixed composition (cc) of an organosilicon compound (C) represented by any of the following formulas (c1) to (c3), or a layered product which is a vapor deposition layer of the organosilicon compound (C) .

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 .} When there is a plurality of them, a plurality of R ^x12 may be different from each other, and R ^x13 may be When there is a plurality of R ^x13 may be different from each other, and when there are a plurality of R ^x14 , a plurality of R ^x14 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, and when a plurality of Rf ^x11 exists, a plurality of Rf ^x11 is Each may be different, and when a plurality of Rf ^x12 exist, a plurality of Rf ^x12 may be different, respectively, and Rf ^x13 is If there are multiple Rf ^x13 may be different from each other, and when a plurality of Rf ^x14 exist, a plurality of Rf ^x14 may be different from each other,
R ^x15 is an alkyl group having 1 to 20 carbon atoms, and when two or more R ^x15 are present, a plurality of R ^x15 may be different,
X ¹¹ is a hydrolysable group, and when two or more X ¹¹ are present, a plurality of X ¹¹ may be different from each other,
Y ¹¹ is -NH- or -S-, and when two or more Y ¹¹ is present, a plurality of Y ¹¹ may be different,
Z ¹¹ is a vinyl group, α-methylvinyl group, styryl group, methacryloyl group, acryloyl group, amino group, isocyanate group, isocyanurate group, epoxy group, ureido group, or mercapto group,
p1 is an integer of 1 to 20, p2, p3, and p4 are each independently an integer of 0 to 10, p5 is an integer of 1 to 10,
p6 is an integer of 1-3,
When Z ¹¹ is not an amino group, at least one of Y ¹¹ is -NH-, and when all of Y ¹¹ are -S-, Z ¹¹ is an amino group,
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 -, Z ¹¹ - and -Si(X ¹¹ ) ) _p6 (R ^x15 ) _3-p6 becomes the terminal, and as long as -O- is not connected with -O-, they are arranged in an arbitrary order to bind.

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 two or more R ^x20 exist, a plurality of R ^x20 may be different from each other, and a plurality of R ^x21 when two or more R x21 exist. R ^x21 of may be different from each other,
Rf ^x20 and Rf ^x21 are each independently an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted with fluorine atoms, and when two or more Rf ^x20 exist, a plurality of Rf ^x20 may be different from each other, and Rf When a plurality of ^x21 exist, a plurality of Rf ^x21 may be different from each other,
R ^x22 and R ^x23 are each independently an alkyl group having 1 to 20 carbon atoms, and R ^x22 and R ^x23 are When there are a plurality of R ^x22 and R ^x23 may be different from each other,
X ²⁰ and X ²¹ are each independently a hydrolysable group, and when a plurality of X ²⁰ and X ²¹ exist, a plurality of X ²⁰ and X ²¹ may be different,
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 enclosed in parentheses by adding p20 or p21 is substituted with an amine skeleton -NR ¹⁰⁰ - and 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,
p20 pieces of -｛C(R ^x20 )(R ^x21 )｝- and p21 pieces of -｛C(Rf ^x20 )(Rf ^x21 )｝- do not have to be consecutive, and p20 or p21 pieces are arranged in an arbitrary order. It binds, and both ends become -Si(X ²⁰ ) _p22 (R ^x22 ) _3-p22 and -Si(X ²¹ ) _p23 (R ^x23 ) _3-p23 .

In the above formula (c3),
Z ³¹ , 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 .} When there are a plurality of R ^x32 , each of a plurality of R x32 may be different, when a plurality of R ^x33 exist, a plurality of R ^x33 may be respectively different, and when a plurality of R ^x34 exist, a plurality of R ^x34 may be respectively different ,
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, Each may be different, and when a plurality of Rf ^x32 exist, a plurality of Rf ^x32 may be respectively different, when a plurality of Rf ^x33 exist, a plurality of Rf ^x33 may be respectively different, and when a plurality of Rf ^x34 exist, a plurality Rf ^x34 of may be different from each other,
Y ³¹ is -NH-, -N(CH ₃ )-, or -O-, and when two or more Y ³¹ , a plurality of Y ³¹ may be different,
X ³¹ , X ³² , X ³³ , X ³⁴ are each independently —OR ^c (R ^c is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aminoC _1-3 alkyldiC _1-3 alkoxysilyl group ), and when there are ^two or more X ³¹ , a ^plurality of X ³¹ may be ^respectively different; ³³ may be different from each other, and when there are two or more X ³⁴ , a plurality of X ³⁴ may 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, p37 is 0 or 1,
At least one of Z ³¹ and Z ³² is an amino group, or at least one of Y ³¹ satisfies the condition that -NH- or -N(CH ₃ )-, and ends are Z ³¹ - and Z ³² -, -O Unless - is linked to -O-, p31 -｛C(R ^x31 )(R ^x32 )｝-, p32 -｛C(Rf ^x31 )(Rf ^x32 )｝-, p33 -｛Si(R) ^x33 )(R ^x34 )｝-, p34 -｛Si(Rf ^x33 )(Rf ^x34 )｝-, p35 -Y ³¹ -, p36 -｛Si(X ³¹ )(X ³² )-O｝-, It is formed by combining p37 pieces of -｛Si(X ³³ )(X ³⁴ )｝- in an arbitrary order. 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.