WO2022168627A1

WO2022168627A1 - Layered body and method for producing same

Info

Publication number: WO2022168627A1
Application number: PCT/JP2022/002091
Authority: WO
Inventors: 友宏伊藤; 彩香櫻井; 知典宮本
Original assignee: 住友化学株式会社
Priority date: 2021-02-05
Filing date: 2022-01-21
Publication date: 2022-08-11
Also published as: TW202239597A; JP2022120794A

Abstract

The present invention provides a layered body including a substrate (s) and a water-repellent layer (r), the nitrogen content at the surface of the water-repellent layer (r) being 0.30-10 at% (inclusive). In this layered body, the surface of the water-repellent layer (r) is preferably configured so as to satisfy either condition from among (i) the water contact angle being 105° or greater and (ii) the water slipping angle being less than 45° after the surface has been subjected to a load of 200 g per area measuring 1.5 cm × 1.5 cm and then scraped 20,000 times.

Description

Laminate and its manufacturing method

The present invention relates to a laminate and its manufacturing method.

A film formed from a composition containing a compound having a fluoropolyether structure has a very low surface free energy, so it can be used in display devices such as touch panel displays, optical elements, semiconductor elements, building materials, and windows of automobiles and buildings. It is used as an antifouling coating or a water- and oil-repellent coating in various fields such as.

For example, Patent Document 1 discloses a compound (A) having a perfluoropolyether structure, an oxyalkylene unit in which at least part of the hydrogen atoms are substituted with fluorine atoms, and a compound having a hydroxy group, It discloses that a composition containing a compound (B) having a number average molecular weight of less than 10,000 and a fluorine-based solvent (C) is formed into a film on non-alkali glass by vacuum deposition.

JP 2019-143020 A

By the way, abrasion resistance is sometimes required for a film formed from a compound having a fluoropolyether structure. However, as a result of investigation by the present inventors, it has been found that the coating disclosed in Patent Document 1 has room for improvement in wear resistance.

Therefore, an object of the present invention is to provide a laminate including a base material and a water-repellent layer, the laminate having good abrasion resistance on the surface of the water-repellent layer, and a method for producing the same.

The invention that achieves the above-mentioned problems is as follows.
[1] A laminate comprising a substrate (s) and a water-repellent layer (r),
A laminate in which the water-repellent layer (r) has a nitrogen content of 0.30 atomic % or more and 10 atomic % or less.
[2] After rubbing the surface of the water-repellent layer (r) 20,000 times with a load of 200 g per area of 1.5 cm × 1.5 cm, (i) the water contact angle is 105° or more. and (ii) the water slide angle is less than 45°.
[3] The water-repellent layer (r) is
an organosilicon compound (A) having a fluoropolyether structure represented by the following formula (a1);
The laminate according to [1] or [2], which is a cured product of a mixed composition of an organosilicon compound (C) having an amino group or an amine skeleton represented by any one of the following formulas (c1) to (c3). .

In the above formula (a1),
Rf ^a26 , Rf ^a27 , Rf ^a28 , and Rf ^a29 are each independently a fluorinated alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom ^; When a plurality of Rf ^{a26 are present, a plurality of Rf a26} may be different, when a plurality of Rf ^a27 are present, a plurality of Rf ^a27 may be different, and when a plurality of Rf ^a28 are present, a plurality of Rf ^a28 may be different from each other, and when a plurality of Rf ^a29 are present, the plurality of Rf ^a29 may be different,
R ²⁵ and R ²⁶ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogenated alkyl group having 1 to 4 carbon atoms in which one or more hydrogen atoms are substituted with halogen atoms group, at least one of R ²⁵ and R ²⁶ ^bonded to one carbon ^atom is a hydrogen atom ^; When doing, multiple R ²⁶ may be different,
R ²⁷ and R ²⁸ are each independently a hydrogen atom, an alkyl group having ¹ to 4 carbon atoms, or a single bond ^; When a plurality of R ²⁸ are present, the plurality of R ²⁸ may be different,
R ²⁹ and R ³⁰ are each independently an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ²⁹ are present, the plurality of R ²⁹ may be different, and when a plurality of R ³⁰ are present may have different R ^30s ,
M ⁷ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, -C(=O)NR-, - CH═CH— or —C ₆ H ₄ — (phenylene group), 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 M ⁷ is When a plurality of M7 are present, the plurality of ^M7 may be different,
M ⁵ is a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and when multiple M ⁵ are present, the multiple M ⁵ may be different,
M ¹⁰ is a hydrogen atom or a halogen atom,
M ⁸ and M ⁹ are each independently a hydrolyzable group, a hydroxy group, or —(CH ₂ ) _e7 —Si(OR ¹⁴ ) ₃ , e7 is 1 to 5, and R ¹⁴ is a methyl group or an ethyl group, and when there are a plurality of M ⁸ , the plurality of M ⁸ may be different, and when there is a plurality of M ⁹ , the plurality of M ⁹ may be different,
f21, f22, f23, f24, and f25 are each independently an integer of 0 to 600, and the total value of f21, f22, f23, f24, and f25 is 13 or more,
f26 is an integer from 0 to 20,
f27 is each independently an integer of 0 to 2,
g21 is an integer of 1 to 3, g22 is an integer of 0 to 2, g21 + g22 ≤ 3,
g31 is an integer of 1 to 3, g32 is an integer of 0 to 2, g31 + g32 ≤ 3,
M ¹⁰ -, _-Si (M ⁹ ) g31 (H) _g32 (R ³⁰ ) _3-g31-g32 , f21 -{C(R ²⁵ )(R ²⁶ )}-units (U _a1 ), f22 -{C(Rf ^a26 )(Rf ^a27 )}-unit (U _a2 ), f23 -{Si(R ²⁷ )(R ²⁸ )}-unit (U _a3 ), f24-{Si(Rf ^a28 )(Rf ^a29 )}-units (U _a4 ), f25 -M ⁷ -units (U _a5 ), and f26 -[C(M ⁵ ){(CH ₂ ) _f27 -Si(M ⁸ ) _g21 (H) _g22 (R ²⁹ ) _3-g21-g22 }]-unit (U _a6 ) has M ¹⁰ - at one end in formula (a1), and -Si(M ⁹ ) _{g31 (H) g32} ₍ R ³⁰ ) _3-g31-g32 are the other ends, and are arranged in an order that forms a fluoropolyether structure at least in part, and each unit can be in any order as long as —O— is not continuous with —O— Join side by side.

In the above formula (c1),
R ^x11 , R ^x12 , R ^x13 , and R ^x14 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when multiple R ^x11 are present, the multiple R ^x11 are different. may be different when there are a plurality of R ^x12 , and when there are a plurality of R ^x13 , a plurality of R ^x13 may be different, and when ^there are a plurality of R ^x14 may be different from each other in a plurality of R ^x14 ,
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 fluorine atoms or a fluorine atom, and a plurality of Rf ^x11 are present When there are multiple Rf x11, the plurality of Rf ^x11 may be different, when there are multiple Rf ^x12 , the plurality of Rf ^x12 may be different, and when there is a plurality of Rf ^x13 , the plurality of Rf ^x13 may be different. may be different, and if there are multiple Rf ^x14 , the multiple Rf ^x14 may be different,
R ^x15 is an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^x15 are present, the plurality of R ^x15 may be different,
X ¹¹ is a hydrolyzable group, and when a plurality of X ¹¹ are present, the plurality of X ¹¹ may be different,
Y ¹¹ is -NH- or -S-, and when a plurality of Y ¹¹ are present, the 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 0 to 10,
p6 is an integer from 1 to 3,
having at least one Y ¹¹ which is —NH— if Z ¹¹ is not an amino group, and Z ¹¹ is an amino group if all Y ¹¹ are —S— or p5 is 0;
Z ¹¹ -, -Si(X ¹¹ ) _p6 (R ^x15 ) _3-p6 , p1 -{C(R ^x11 )(R ^x12 )}-units (U _c11 ), p2 -{C(Rf ^x11 ) (Rf ^x12 )}-unit (U _c12 ), p3-{Si(R ^x13 )(R ^x14 )}-unit (U _c13 ), p4-{Si(Rf ^x13 )(Rf ^x14 )} - unit (U _c14 ), p5 -Y ¹¹ - units (U _c15 ), Z ¹¹ - becomes one end of the compound represented by formula (c1), and -Si(X ¹¹ ) _p6 (R ^x15 ) Unless _3-p6 is the other end and —O— is not linked to —O—, each unit is linked in any order.

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 ^; When a plurality of R x21 are present, the plurality of R ^x21 may be different,
Rf ^x20 and Rf ^x21 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom, and when there are multiple Rf ^x20 , multiple Rf ^x20 may be different, and when there are a plurality of Rf ^x21 , a plurality of Rf ^x21 may be different,
R ^x22 and R ^x23 are each independently an alkyl group having 1 to 20 carbon atoms, and when there are a plurality of R ^x22 and R ^x23 , a plurality of R ^x22 and R ^x23 may be different,
X ²⁰ and X ²¹ are each independently a hydrolyzable group, and when multiple X ²⁰ and X ²¹ are present, multiple X ²⁰ and X ²¹ may be different,
p20 is an integer of 1 to 30, p21 is an integer of 0 to 30, and at least one of the repeating units bracketed with p20 or p21 is replaced 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-{C( ^Rx20 )( ^Rx21 )}-units ( _Uc20 ), p21-{C( ^Rfx20 )( ^Rfx21 )}-units ( _Uc21 ) are p20 units ( U _c20 ) or p21 units (U _c21 ) need not be contiguous, and each unit (U _c21 ) and unit (U _c20 ) can be arranged in any order and combined to form the formula (c2). One end of the compound is -Si(X ²⁰ ) _p22 (R ^x22 ) _3-p22 , and the other end is -Si(X ²¹ ) _p23 (R ^x23 ) _3-p23 .

In the above formula (c3),
Z ³¹ and Z ³² are each independently a reactive functional group other than a hydrolyzable group and a hydroxy group. The reactive functional group is a vinyl group, α-methylvinyl group, styryl group, methacryloyl group, acryloyl group, amino group, epoxy group, ureido group, or mercapto group,
R ^x31 , R ^x32 , R ^x33 and R ^x34 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when there are multiple R ^x31 , the multiple R ^x31 may be different. may be different when there ^{are a plurality of R x32} ^, and when there are a plurality of R ^{x33, a plurality of R x33} ^may be different, and when there are a plurality of R ^x34 may be different from each other in a plurality of R ^x34 ,
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 fluorine atoms or a fluorine atom, and a plurality of Rf ^x31 are present When there are multiple Rf x31, the plurality of Rf ^x31 may be different, and when there are multiple Rf ^x32 , the plurality of Rf ^x32 may be different, and when there are multiple Rf ^x33 , the plurality of Rf ^x33 may be different. may be different, and if there are multiple Rf ^x34 , the multiple Rf ^x34 may be different,
Y ³¹ is —NH—, —N(CH ₃ )— or —O—, and when there are a plurality of Y ³¹ , the plurality of Y ³¹ may be different,
X ³¹ , X ³² , X ³³ and X ³⁴ are each independently —OR ^c (R ^c is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or amino-C _1-3 alkyldi-C _1-3 alkoxysilyl is a group), and when a plurality of X ³¹ are present, the plurality of X ³¹ may be different, when a plurality of X ³² are present, the plurality of X ³² may be different, and X ³³ is When a plurality of X 33 are present, the plurality of X ³³ may be different, and when a plurality of X ³⁴ are present, the plurality of X ³⁴ may be different,
p31 is an integer of 0 to 20, p32, p33, and p34 are each independently an integer of 0 to 10, p35 is an integer of 0 to 5, and p36 is an integer of 1 to 10 and p37 is 0 or 1,
A compound that satisfies the condition that at least one of Z ³¹ and Z ³² is an amino group, or at least one of Y ³¹ is -NH- or -N(CH ₃ )-, and is represented by formula (c3) p31 -{C(R ^x31 )(R ^x32 )}-units, unless one end of is Z ³¹ - and the other end is Z ³² -, and -O- is not linked to -O- (U _c31 ), p32-{C(Rf ^x31 )(Rf ^x32 )}-units (U _c32 ), p33-{Si(R ^x33 )(R ^x34 )}-units (U _c33 ), p34 -{Si(Rf ^x33 )(Rf ^x34 )}-units (U _c34 ), p35 -Y ³¹ -units (U _c35 ), p36 -{Si(X ³¹ )(X ³² )-O }-unit (U _c36 ) and p37 -{Si(X ³³ )(X ³⁴ )}-units (U _c37 ) are arranged and bonded in any order.
[4] A window film or touch panel display comprising the laminate according to any one of [1] to [3].
[5] A method for producing a laminate having a substrate (s) and a water-repellent layer (r),
A mixed composition of an organosilicon compound (A) having a fluoropolyether structure, an organosilicon compound (C) having an amino group or an amine skeleton, and a solvent, wherein the organosilicon compound ( a step of heating a mixed composition in which the mass ratio of A) is more than 1% by mass and the mass ratio of the organosilicon compound (C) is 0.1% by mass or more; A method for producing a laminate, comprising the step of forming a water-repellent layer (r) by vacuum deposition on a substrate (s).
[6] Further comprising the step of forming a layer (X) different from the substrate (s) and the water-repellent layer (r) on the substrate (s),
The production method according to [5], wherein the mixed composition after heating is vacuum-deposited onto the layer (X) provided on the substrate (s) to form the water-repellent layer (r).
[7] further comprising a step of hydrophilizing the surface of the substrate (s) or the surface of the layer (X) provided on the substrate (s),
The production method according to [5] or [6], wherein the mixed composition after heating is vacuum-deposited on the hydrophilized surface of the substrate (s) or the hydrophilized surface of the layer (X).

According to the present invention, it is possible to realize a laminate that includes a base material and a water-repellent layer and has good wear resistance on the surface of the water-repellent layer, and a method for producing the same.

The laminate of the present invention includes a substrate (s) and a water-repellent layer (r), and the nitrogen content on the surface of the water-repellent layer (r) is 0.30 atomic % or more and 10 atomic % or less. It is a laminate.

1. Water-repellent layer (r)
The water-repellent layer (r) can be obtained by vapor deposition as described later, and such a layer has a surface nitrogen content of 0.30 atomic % or more and 10 atomic % or less. The nitrogen content is preferably 0.5 atomic % or more, more preferably 0.6 atomic % or more, and may be 8.0 atomic % or less, or 5.0 atomic % or less. , is preferably 2.0 atomic % or less, more preferably 1.0 atomic % or less. The surface of the water-repellent layer (r) for which the nitrogen content is specified is the surface opposite to the substrate (s). Also, the nitrogen content can be obtained by measuring the elements constituting the surface of the water-repellent layer (r) and their amounts by X-ray photoelectron spectroscopy (XPS). Elements constituting the surface of the water-repellent layer (r) measured by XPS are typically B, C, N, O, F, Si, P, S, Cl, particularly C, N, O, F , Si. The contents of B, C, N, O, F, Si, P, S, and Cl are respectively B1s spectrum, C1s spectrum, N1s spectrum, O1s spectrum, F1s spectrum, Si2p spectrum, P2p spectrum, S2p spectrum, Cl2p Calculated based on the spectrum.

As shown in the examples below, the above XPS measurement uses MgKα as the excitation X-ray, the X-ray output is 110 W, the photoelectron escape angle is 45 °, the pass energy is 50 eV, carbon (C1s) , nitrogen (N1s), oxygen (O1s), fluorine (F1s), silicon (2p), boron (B1s), phosphorus (P2p), sulfur (S2p), and chlorine (Cl2p). . If the sample is charged up during measurement, an electron gun for charge correction may be used as appropriate, and charge correction for the chemical shift of the measured spectrum can be performed using various standard samples. For example, among the C1s spectra, the spectra due to the C—C and C—H structures may be corrected with the energy standard of 284.0 eV.

Further, in a preferred embodiment of the present invention, the effect that the surface of the water-repellent layer (r) has good wear resistance can be exhibited. After rubbing 20,000 times with a load of 200 g per 1.5 cm area, (i) the water contact angle is 105° or more, and (ii) the water slide angle is less than 45°. meet at least one of the requirements of

The water contact angle of (i) above is more preferably 108° or more, more preferably 110° or more, and may be 120° or less. In addition, the water sliding angle of (ii) is more preferably 40° or less, still more preferably 35° or less, still more preferably 20° or less, particularly preferably 15° or less, and 5 ° or more.

When rubbing the film (r) in the abrasion resistance test, it is preferable to rub it with paper made of pulp material, and more preferably rub it with paper made of pulp material attached to an elastic body. Paper made of pulp material includes, for example, Kimwipe Wiper S-200. In the abrasion resistance test in this specification, the contact angle and the sliding angle were measured at approximately the center of the stroke area with a Kimwipe wiper S-200 at a stroke distance of 30 mm and a rubbing speed of 70 reciprocations/minute.

The initial contact angle on the surface of the water-repellent layer (r), that is, the contact angle after formation of the layer but not subjected to an abrasion resistance test is, for example, 105° or more, preferably 108° or more, and more preferably 110°. ° or more, and may be 125° or less. The initial sliding angle of the surface of the water-repellent layer (r) is preferably less than 18°, more preferably 17° or less, and may be 3° or more.

Both the initial contact angle and the contact angle after the abrasion resistance test were measured by dropping 1 μL of water droplets on the water-repellent layer (r) and using the droplet method using the θ/2 method. For any sliding angle after the abrasion test, 20 μL of water droplets are dropped on the water-repellent layer (r), and the sliding method (analysis method: tangential method, tilt method: continuous inclination, sliding detection: after sliding, movement judgment: forward angle, sliding judgment distance: 5 dots). The "dot" means a pixel at the resolution when photographing with a camera attached to DM700 used in the examples described later, and 1 dot is 0.01 mm in the examples described later.

In a preferred embodiment, the water-repellent layer (r) satisfies the water contact angle as described above, and such a water-repellent layer (r) also has good oil repellency. The thickness of the water-repellent layer (r) is, for example, 1 nm to 1000 nm.

The water-repellent layer (r) is, as described later, a mixed composition of an organosilicon compound (A) having a fluoropolyether structure, an organosilicon compound (C) having an amino group or an amine skeleton, and a solvent. A mixture composition in which the mass ratio of the organosilicon compound (A) to 100% by mass of the composition is more than 1% by mass and the mass ratio of the organosilicon compound (C) is 0.1% by mass or more is used as a base material. (s) or the layer (X) formed on the substrate (s) is preferably formed by vapor deposition and curing. Layer (r) can be formed. Therefore, the water-repellent layer (r) preferably has a structure derived from the organosilicon compound (A). As described below, in a preferred embodiment, the organosilicon compound (A) has a hydrolyzable group or a hydroxy group bonded to a silicon atom (which may be bonded via a linking group), and the organosilicon compound ( Since the —SiOH groups of A) or the —SiOH groups of the organosilicon compound (A) (Si and OH may be bonded via a linking group) formed by hydrolysis undergo dehydration condensation, the water-repellent layer ( r) generally preferably has a condensed structure between the organosilicon compounds (A). In addition, the water-repellent layer (r) contains —SiOH groups derived from the organosilicon compound (A), —SiOH groups derived from other compounds, or active hydrogen (hydroxyl groups) on the surface on which the water-repellent layer (r) is formed. etc.) are also preferably included. As will be described later, the organosilicon compound (A), in a preferred embodiment, has a fluoropolyether structure in which a monovalent group (hereinafter referred to as an FPE group) having an oxygen atom at the terminal on the bond side is linked via a linking group. Alternatively, it is bonded to the silicon atom without a linking group, and the other end of the FPE group is a fluorine-containing group having a perfluoroalkyl group. That is, the condensed structure between the organosilicon compounds (A) is such that the monovalent group (hereinafter referred to as the FPE group) having an oxygen atom at the end of the bond side of the fluoropolyether structure (hereinafter referred to as an FPE group) is linked via a linking group or It preferably contains a structure that is bonded to a silicon atom without a group intervening, and that the other end of the FPE group is a fluorine-containing group having a perfluoroalkyl group.

In addition, the water-repellent layer (r) preferably has a structure derived from the organosilicon compound (C). As described later, in a preferred embodiment, a hydrolyzable group is bonded to the silicon atom of the organosilicon compound (C), and the -SiOH group of the organosilicon compound (C) generated by hydrolysis of the hydrolyzable group Since they undergo dehydration condensation, the water-repellent layer (r) preferably has a condensed structure derived from the organosilicon compound (C). In addition, in the water-repellent layer (r), —SiOH groups (Si and OH may be bonded via a linking group; hereinafter the same) derived from the organosilicon compound (C) are It is also preferable to include a —SiOH group or a condensed structure formed by dehydration condensation with active hydrogen (such as a hydroxyl group) on the surface on which the water-repellent layer (r) is formed. Specifically, the water-repellent layer (r) contains at least one of a condensate of the organosilicon compounds (C) and a condensate of the organosilicon compound (C) and the organosilicon compound (A). is preferred.

That is, the water-repellent layer (r) contains a condensate of organosilicon compounds (A) having a fluoropolyether structure represented by the formula (a1) described later, and the following formulas (c1) to (c3) At least one condensate of organosilicon compounds (C) having an amino group or amine skeleton represented by any of preferably included.

Furthermore, when the mixed composition is mixed with an organosilicon compound (B) described later, the organosilicon compound (B) represented by the following formula (b1) is a hydrolyzable group represented by A ² or Having a hydroxy group, the —SiOH of the organosilicon compound (B) or the —SiOH group of the organosilicon compound (B) generated by hydrolysis is a —SiOH group derived from the organosilicon compound (A), an organosilicon Since dehydration condensation occurs with other —SiOH groups derived from the compound (B) or active hydrogen (such as a hydroxyl group) on the surface on which the water-repellent layer (r) is formed, in a preferred embodiment, the water-repellent layer (r) is an organic silicon It has a condensed structure derived from the organosilicon compound (B) together with the condensed structure derived from the compound (A).

2. Mixed composition 2-1. Organosilicon compound (A)
The organosilicon compound (A) contains a fluoropolyether structure. The fluoropolyether structure can also be referred to as a fluorooxyalkylene group, and means a structure in which both ends are oxygen atoms. Fluoropolyether structures have liquid repellency, such as water repellency or oil repellency. The fluoropolyether structure is preferably a perfluoropolyether structure.
The number of carbon atoms contained in the longest linear portion of the fluoropolyether structure is, for example, preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more. The upper limit of the number of carbon atoms is not particularly limited, and is, for example, 200, preferably 150. The number of silicon atoms in one molecule of the organosilicon compound (A) is preferably 1-10, more preferably 1-6.

The organosilicon compound (A) preferably contains a hydrolyzable group or a hydroxy group (hereinafter both are collectively referred to as a reactive group (k)) in addition to a fluoropolyether structure and a silicon atom, and the More preferably, the reactive group (k) is bonded to the silicon atom via a linking group or not via a linking group. The reactive group (k) is formed between the organosilicon compounds (A) through a hydrolysis/dehydration condensation reaction; the organosilicon compound (A) and another monomer; or the organosilicon compound (A) and the mixture composition has the function of bonding with active hydrogen (hydroxyl group, etc.) on the surface to which is applied through a condensation reaction. Examples of the hydrolyzable group include an alkoxy group, a halogen atom, a cyano group, an acetoxy group and an isocyanate group. The reactive group (k) is preferably an alkoxy group or a halogen atom, more preferably an alkoxy group having 1 to 4 carbon atoms or a chlorine atom, and particularly preferably a methoxy group or an ethoxy group.

In the embodiment in which the organosilicon compound (A) contains a fluoropolyether structure, a silicon atom and a reactive group (k), a monovalent group having an oxygen atom of the fluoropolyether structure at the terminal on the bond side (hereinafter referred to as an FPE group ) and the silicon atom is bonded via a linking group or not, and the silicon atom and the reactive group (k) are bonded via a linking group or not Bonding is preferred. When the FPE group and the silicon atom are bonded via a linking group, the silicon atom bonded to the reactive group (k) via the linking group or not via the linking group is the organosilicon compound (A) may be present in one molecule, and the number thereof is, for example, 1 or more and 10 or less.

The FPE group may be linear or may have a side chain, and preferably has a side chain. As an aspect having a side chain, it is particularly preferable that the fluoropolyether structure in the FPE group has a side chain. It preferably has a fluoroalkyl group as a side chain, and the fluoroalkyl group is more preferably a perfluoroalkyl group, still more preferably a trifluoromethyl group. The carbon number of the linking group linking the FPE group and the silicon atom is, for example, 1 or more and 20 or less, preferably 2 or more and 15 or less. The FPE group described above is preferably a group in which a fluorine-containing group having a fluoroalkyl group at its end and a perfluoropolyether structure are directly bonded. The fluorine-containing group may be a fluoroalkyl group or a group in which a linking group such as a divalent aromatic hydrocarbon group is bonded to a fluoroalkyl group, but is preferably a fluoroalkyl group. The fluoroalkyl group is preferably a perfluoroalkyl group, more preferably a perfluoroalkyl group having 1 to 20 carbon atoms.

Examples of the fluorine-containing group include CF ₃ (CF ₂ ) _p — (p is, for example, 1 to 19, preferably 1 to 10), CF ₃ (CF ₂ ) _m —(CH ₂ ) _n -, CF ₃ (CF ₂ ) _m -C ₆ H ₄ - (m is 1 to 10, preferably 3 to 7; n is 1 to 5, preferably 2 to 4; and CF ₃ (CF ₂ ) _p — or CF ₃ (CF ₂ ) _m —(CH ₂ ) _n — are preferred.

The reactive group (k) may be bonded to the silicon atom via a linking group, or may be directly bonded to the silicon atom without the linking group, and is directly bonded to the silicon atom. is preferred. The number of reactive groups (k) bonded to one silicon atom may be 1 or more, and may be 2 or 3, preferably 2 or 3, particularly 3 preferable. When two or more reactive groups (k) are attached to the silicon atom, different reactive groups (k) may be attached to the silicon atom, but the same reactive group (k) may be attached to the silicon atom. preferably combined. When the number of reactive groups (k) bonded to one silicon atom is 2 or less, the remaining bonds may be bonded with a monovalent group other than the reactive group (k), for example, An alkyl group (especially an alkyl group having 1 to 4 carbon atoms), H, NCO, etc. can be bonded.

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

In the above formula (a1),
Rf ^a26 , Rf ^a27 , Rf ^a28 , and Rf ^a29 are each independently a fluorinated alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom ^; When a plurality of Rf ^a26 are present, the plurality of Rf ^a26 may be different, when there are a plurality of Rf a27, the plurality of Rf ^a27 may be different, and when a plurality of Rf ^a28 are present, a plurality of Rf ^a28 may be different from each other, and when a plurality of Rf ^a29 are present, the plurality of Rf ^a29 may be different,
R ²⁵ and R ²⁶ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogenated alkyl group having 1 to 4 carbon atoms in which one or more hydrogen atoms are substituted with halogen atoms group, at least one of R ²⁵ and R ²⁶ ^bonded to one carbon ^atom is a hydrogen atom ^; When doing, multiple R ²⁶ may be different,
R ²⁷ and R ²⁸ are each independently a hydrogen atom, an alkyl group having ¹ to 4 carbon atoms, or a single bond ^; When a plurality of R ²⁸ are present, the plurality of R ²⁸ may be different,
R ²⁹ and R ³⁰ are each independently an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ²⁹ are present, the plurality of R ²⁹ may be different, and when a plurality of R ³⁰ are present may have different R ^30s ,
M7 is -O-, -C(=O)-O-, -OC(=O)-, -NR-, ^-NRC (=O)-, -C(=O)NR-, - CH═CH— or —C ₆ H ₄ — (phenylene group), 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 M ⁷ is When a plurality of M7 are present, the plurality of ^M7 may be different,
M ⁵ is a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and when multiple M ⁵ are present, the multiple M ⁵ may be different,
M ¹⁰ is a hydrogen atom or a halogen atom,
M ⁸ and M ⁹ are each independently a hydrolyzable group, a hydroxy group, or —(CH ₂ ) _e7 —Si(OR ¹⁴ ) ₃ , e7 is 1 to 5, and R ¹⁴ is a methyl group or an ethyl group, and when a plurality of M ⁸ are present, the plurality of M ⁸ may be different, and when a plurality of M ⁹ is present, the plurality of M ⁹ may be different,
f21, f22, f23, f24, and f25 are each independently an integer of 0 to 600, and the total value of f21, f22, f23, f24, and f25 is 13 or more,
f26 is an integer from 0 to 20,
each f27 is independently an integer of 0 to 2,
g21 is an integer of 1 to 3, g22 is an integer of 0 to 2, g21 + g22 ≤ 3,
g31 is an integer of 1 to 3, g32 is an integer of 0 to 2, g31 + g32 ≤ 3,
M ¹⁰ -, _-Si (M ⁹ ) g31 (H) _g32 (R ³⁰ ) _3-g31-g32 , f21 -{C(R ²⁵ )(R ²⁶ )}-units (U _a1 ), f22 -{C(Rf ^a26 )(Rf ^a27 )}-unit (U _a2 ), f23 -{Si(R ²⁷ )(R ²⁸ )}-unit (U _a3 ), f24-{Si(Rf ^a28 )(Rf ^a29 )}-units (U _a4 ), f25 -M ⁷ -units (U _a5 ), and f26 -[C(M ⁵ ){(CH ₂ ) _f27 -Si(M ⁸ ) _g21 (H) _g22 (R ²⁹ ) _3-g21-g22 }]-unit (U _a6 ) has M ¹⁰ - at one end in formula (a1), and -Si(M ⁹ ) _{g31 (H) g32} ₍ R ³⁰ ) _3-g31-g32 are the other ends, and are arranged in an order that forms a fluoropolyether structure at least in part, and each unit can be in any order as long as —O— is not continuous with —O— Join side by side. “Arranged in any order and bonded” means that the repeating units are not limited to being arranged consecutively in the order as described in formula (a1) above, and f21 -{C(R ²⁵ )( R ²⁶ )}-units (U _a1 ) do not need to be continuously bonded, and may be bonded via other units along the way. The same applies to the units (U _a2 ) to (U _a6 ) enclosed by f22 to f26.

Further, when at least one of R ²⁷ and R ²⁸ is a single bond, the single bond portion of the unit enclosed by f23 and —O— in M ⁷ are repeatedly bonded to form a branched or cyclic It can form siloxane bonds.

Rf ^a26 , Rf ^a27 , Rf ^a28 , and Rf ^a29 are preferably each independently a fluorine atom or a fluorinated alkyl group having 1 to 2 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms. More preferably, it is a fluorine atom or a fluorinated alkyl group having 1 to 2 carbon atoms in which all hydrogen atoms are substituted with fluorine atoms.
R ²⁵ and R ²⁶ are preferably each independently a hydrogen atom or a fluorine atom, and at least one of R ²⁵ and R ²⁶ bonded to one carbon atom is a hydrogen atom.
R ²⁷ and R ²⁸ are preferably each independently a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably all alkyl groups having 1 to 2 carbon atoms.
R ²⁹ and R ³⁰ are preferably C 1-5 alkyl groups, more preferably C 1-2 alkyl groups.
M ⁷ is preferably -C(=O)-O-, -O-, -O-C(=O)-, -CH=CH- or -C ₆ H ₄ - (phenylene group) . ^M5 is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably all hydrogen atoms.
^M10 is more preferably a fluorine atom.
^M8 and ^M9 are more preferably each independently an alkoxy group or a halogen atom, more preferably a methoxy group, an ethoxy group or a chlorine atom, particularly preferably a methoxy group or an ethoxy group.
Preferably, f21, f23, and f24 are each 1/2 or less of f22, more preferably 1/4 or less, still more preferably f23 or f24 is 0, and particularly preferably f24 is 0 .
f25 is preferably 1/5 or more of the total value of f21, f22, f23, and f24 and less than or equal to the total value of f21, f22, f23, and f24.
f21 is preferably 0-20, more preferably 0-15, even more preferably 1-15, and particularly preferably 1-10. f22 is preferably 5 to 600, more preferably 8 to 600, still more preferably 20 to 200, still more preferably 30 to 200, still more preferably 35 to 180, most preferably 40 to 180 is. f23 and f24 are preferably 0 to 5, more preferably 0 to 3, still more preferably 0. f25 is preferably 4-600, more preferably 4-200, even more preferably 10-200, still more preferably 30-60. The total value of f21, f22, f23, f24 and f25 is preferably 20-600, more preferably 20-250, even more preferably 50-230. f26 is preferably 0-18, more preferably 0-15, even more preferably 0-10, still more preferably 0-5. f27 is preferably 0 to 1, preferably 0. g21 and g31 are each independently preferably 2 to 3, more preferably 3. g22 and g32 are each independently preferably 0 or 1, more preferably 0.

In formula (a1) above, R ²⁵ and R ²⁶ are hydrogen atoms or fluorine atoms (at least one of R ²⁵ and R ²⁶ bonded to one carbon atom is a hydrogen atom), and R ²⁷ , R ²⁸ and R ²⁹ and R ³⁰ are each independently an alkyl group having 1 to 2 carbon atoms, and Rf ^a26 and Rf ^a27 are a fluorine atom or a fluorinated alkyl group having 1 to 2 carbon atoms in which all hydrogen atoms are substituted with fluorine atoms; , M ⁷ is -C(=O)-O-, -O-, -CH=CH-, or -C ₆ H ₄ - (phenylene group), and M ⁸ and M ⁹ are all methoxy and ethoxy groups or a chlorine atom (especially a methoxy group or an ethoxy group), M5 is a hydrogen atom, M10 is a fluorine atom, f21 is 1 to ¹⁰ (preferably 1 to ⁵ ), f22 is 30 to 200 (more preferably 40 to 180), f23 is 0 to 3, f24 is 0, f25 is 30 to 60, f26 is 0 to 6 (especially 0), f27 is 0 to 1 (especially preferably 0), g21 and g31 are 1 to 3, and g22 and g32 are 0 to 2 (both are preferably 0 or 1, more preferably 0) are preferably used as the organosilicon compound (A). .

In the above formula (a1), both R ²⁵ and R ²⁶ are hydrogen atoms, f21 is 1 to 15, both Rf ^a26 and Rf ^a27 are fluorine atoms, and f22 is 40 to 180 (especially 50 to 100), f23 and ^f24 are both ⁰ , M7 is —O—, ^f25 is 30 to ⁶⁰ , M5 is a hydrogen atom, M8 and M9 are all methoxy groups, compound ( ^a12 ) as the organosilicon compound (A).

The organosilicon compound (A) is preferably represented by the following formula (a2).

In the above formula (a2),
Rf ^a1 is a divalent fluoropolyether structure having oxygen atoms at both ends,
R ¹¹ , R ¹² , and R ¹³ are each independently an alkyl group having 1 to 20 carbon atoms, and when there are a plurality of R ¹¹ , the plurality of R ¹¹ may be different, and the plurality of R ¹² may be When present, multiple R ¹² may be different, and when multiple R ¹³ are present, multiple R ¹³ may be different,
E ¹ , E ² , E ³ , E ⁴ , and E ⁵ each independently represent a hydrogen atom or a fluorine atom, and when a plurality of E ¹ are present, the plurality of E ¹ may be different, and E When a plurality of ² are present, a plurality of E ² may be different, when a plurality of E ³ are present, a plurality of E ³ may be different, and when a plurality of E ⁴ is present, a plurality of E ⁴ may be different, and when multiple E ⁵ are present, the multiple E ⁵ may be different,
G ¹ and G ² are each independently a divalent to decavalent organosiloxane group having a siloxane bond,
J ¹ , J ² , and J ³ are each independently a hydrolyzable group, a hydroxy group, or —(CH ₂ ) _e7 —Si(OR ¹⁴ ) ₃ , e7 is 1 to 5, and R ¹⁴ is a methyl group or an ethyl group, and when there are a plurality of J ^1s , the plurality of J ^1s may be different, and when there are a plurality of J ^2s , the plurality of J ^2s may be different, and J When there are a plurality of ³ , the plurality of J ³ may be different,
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, a silicon atom or a fluorine atom, and -{C(R ²⁵ )(R ²⁶ )}-unit (U _a1 ),-{C(Rf ^a26 )(Rf ^a27 )}-unit (U _a2 ),-{Si(R ²⁷ )(R ²⁸ )}-unit (U _a3 ) Or, at least one -M ⁷ - unit (U _a5 ) is a linking group that is arranged in any order (R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , Rf ^a26 , Rf ^a27 and M ⁷ are the same as in formula (a1)),
a10 and a14 are each independently 0 or 1,
a11 and a15 are each independently 0 or 1,
a12 and a16 are each independently 0 to 9;
a13 is 0 to 4;
When a11 is 0, or when a11 is ¹ and G1 has a valence of 2, d11 is 1, and when a11 is ¹ and G1 has ^a valence of 3 to 10, d11 is the value of G1 is a number one less than the number,
When a15 is 0, or when a15 is 1 and G2 has a valence of ² , d12 is 1, and when a15 is ¹ and G2 has a valence of ³ to 10, d12 is the value of G2. is a number one less than the number,
a21 and a23 are each independently 0 to 2,
e11 is 1 to 3, e12 is 0 to 2, e11 + e12 ≤ 3,
e21 is 1 to 3, e22 is 0 to 2, e21 + e22 ≤ 3,
e31 is 1 to 3, e32 is 0 to 2, and e31+e32≦3.

Note that a10 is 0 means that the portion enclosed with a10 is a single bond, and even if a11, a12, a13, a14, a15, a16, a21 or a23 is 0 It is the same.

Rf ^a1 is preferably -O-(CF ₂ CF ₂ O) _e4 -, -O-(CF ₂ CF ₂ CF ₂ O) _e5 -, -O-(CF ₂ -CF(CF ₃ )O) _e6 - . Both e4 and e5 are 15 to 80, and e6 is 3 to 60 (more preferably 25 to 55). Rf ^a1 is also preferably a group in which hydrogen atoms are removed from hydroxyl groups at both ends of a structure obtained by randomly dehydrating and condensing p mol of perfluoropropylene glycol and q mol of perfluoromethanediol, and p + q is 15-80. Rf ^a1 is —O—(CF ₂ CF ₂ CF ₂ O) _e5 — and e5 is 15 to 80 (preferably 20 to 40), or —O—(CF ₂ —CF(CF ₃ ) O) more preferably e6- and _e6 is from 25 to 55;

R ¹¹ , R ¹² and R ¹³ are each independently preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms.

Each of E ¹ , E ² , E ³ and E ⁴ is preferably a hydrogen atom, and E ⁵ is preferably a fluorine atom.

L ¹ and L ² each independently represent -{C(R ²⁵ )(R ²⁶ )}-unit (U _a1 ), -{C(Rf ^a26 )(Rf ^a27 )}-unit (U _a2 ), -{Si(R ²⁷ )(R ²⁸ )}-units (U _a3 ) or -M ⁷ -units (U _a5 ), one or more of which are aligned in any order and bonded to carbon containing a fluorine atom or an oxygen atom A divalent linking group of numbers 1 to 12 (preferably 1 to 10) is preferred. L ¹ is preferably -(CF ₂ ) _x1 - in which x1 is 1 to 5 (preferably 1 to 3) or a group represented by the following (L1-1) to (L1-5). Note that * in (L1-1) to (L1-5) below represents a bond. L ² is preferably -(CF ₂ ) _x2 - where x2 is 1 to 5 (preferably 1 to 3).

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

J ¹ , J ² and J ³ are each independently preferably methoxy, ethoxy or —(CH ₂ ) _e7 —Si(OR ¹⁴ ) ₃ , more preferably methoxy or ethoxy.

a10 is preferably 1, a11 is preferably 0, a12 is preferably 0 to 7, more preferably 0 to 5, a13 is preferably 0 to 3, a14 is preferably 1, a15 is preferably 0, a16 is preferably 0 to 6, more preferably 0 to 3, both a21 and a23 are preferably 0 or 1 (more preferably both are 0), d11 is preferably 1, d12 is preferably 1, e11, Both e21 and e31 are preferably 1-3. Each of e12, e22 and e32 is preferably 0 or 1, more preferably 0. These preferred ranges may be satisfied singly or in combination of two or more.

As the compound (A), Rf ^a1 in the above formula (a2) is O—(CF ₂ —CF(CF ₃ )O) _e6 — (e6 is 25 to 55), and R ¹² and R ¹³ are each independent is an alkyl group having 1 to 2 carbon atoms, L ¹ is a group represented by any one of the above (L1-1) to (L1-5), and L ² is a group having 1 to 5 carbon atoms (preferably 1 to 3), wherein a12 and a13 are 0, E ⁴ is a hydrogen atom, E ⁵ is a fluorine atom, and J ² and J ³ are both a methoxy group or an ethoxy group. (especially a methoxy group), a10 is 1, a11 is 0, a14 is 1, a15 is 0, a16 is 0 to 6 (especially 0), and a23 is 0 or 1 Yes (preferably 0), d11 is 1, d12 is 1, e21 and e31 are each independently 1 to 3, e22 and e32 are both 0 or 1 (especially 0) ( a21) is preferably used.

As the compound (A), Rf ^a1 in formula (a2) above is —O—(CF ₂ CF ₂ CF ₂ O) _e5 — and e5 is 15 to 80 (preferably 20 to 40). , e11, e21 and e31 are all 3, E ¹ to E ⁴ are all hydrogen atoms, E ⁵ is a fluorine atom, a11 and a15 are 0, L ¹ and L ² are is -(CF ₂ ) _x - in which x is 1 to 5 (preferably 1 to 3), a10 and a14 are 1, both J ¹ and J ² are methoxy groups, and a12 is 0 to 9, a21 is 0, a13 is 2, a16 is 0, and d11 and d12 are both 1. It is also preferred to use the compound (a22).

As the compound (A), Rf ^a1 in the above formula (a2) is —O—(CF ₂ CF ₂ CF ₂ O) _e5 —, e5 is 25 to 40, and L ¹ is a fluorine atom and an oxygen atom. a divalent linking group having 3 to 6 carbon atoms, L ² is a perfluoroalkylene group having 2 to 10 carbon atoms, both E ² and E ³ are hydrogen atoms, and E ⁵ is a fluorine atom. , J ² is —(CH ₂ ) _e7 —Si(OCH ₃ ) ₃ , e7 is 2 to 4, a10 is 1, a11 is 0, a12 is 0, a13 is 2 , a14 is 1, a15 is 0, a16 is 0, d11 is 1, d12 is 1 and e21 is 3 (a23) is also preferably used.

More specifically, the organosilicon compound (A) includes compounds of the following formula (a3).

In the above formula (a3), R ³⁰ is a perfluoroalkyl group having 1 to 6 carbon atoms, and R ³¹ is a perfluoropolyethylene group having 25 to 55 repeated perfluorooxyalkylene groups having 1 to 5 carbon atoms. It has an ether structure (both ends are oxygen atoms), R ³² is a group represented by any one of the above (L1-1) to (L1-5), and R ³³ is an alkyl group having 1 to 5 carbon atoms. , R ³⁴ is an alkoxy group, y11 is 1 to 3, y12 is 0 to 2, and y11+y12≦3. R ³⁰ is preferably a perfluoroalkyl group having 1 to 3 carbon atoms, and R ³¹ is a perfluoropolyether structure in which 25 to 55 branched perfluorooxyalkylene groups having 1 to 3 carbon atoms are repeated. (Both ends are oxygen atoms). y11+y12 is preferably three.

Examples of the organosilicon compound (A) include compounds represented by the following formula (a4).

In the above formula (a4), R ⁴⁰ is a C 2-5 perfluoroalkyl group, R ⁴¹ is a C 2-5 perfluoroalkylene group, and R ⁴² is a C 2-5 a fluoroalkylene group in which some of the hydrogen atoms of the alkylene 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; be. k1 is an integer of 1-5. k2 is an integer of 1 to 3, preferably 2 or more, and may be 3.

Furthermore, as the organosilicon compound (A), a compound represented by the following formula (a5) can also be mentioned.

In the above formula (a5), R ⁵⁰ is a perfluoroalkyl group having 2 to 6 carbon atoms, R ⁵¹ is a perfluoroalkylene group having 2 to 6 carbon atoms, and R ⁵² has 2 to 30 carbon atoms. is a perfluoroalkylene group, R ⁵³ is a trivalent saturated hydrocarbon group having 2 to 6 carbon atoms, and R ⁵⁴ is an alkyl group having 1 to 3 carbon atoms. The number of carbon atoms in R ⁵⁰ , R ⁵¹ and R ⁵³ is each independently preferably 2-4, more preferably 2-3. The carbon number of R ⁵² is preferably 2-16, more preferably 2-10. h1 is 5-50 and h2 is 1-10. h1 is preferably 10-40.

More specifically, the compound represented by the above formula (a5) includes a compound represented by the following formula (1), or a compound having a similar structure to the compound. OPTOOL (registered trademark) manufactured by Daikin Industries, Ltd. ) The organosilicon compound (A) in DSX is represented by the following formula (1).

In the above formula (1), r is 24, s is an integer of 1 to 10, and the number average molecular weight is about 5,000.

As the similar structure, a structure in which the number of carbon atoms in the hydrocarbon group of the above formula (1) or the number of carbon atoms in the hydrocarbon group substituted with a fluorine atom is different, a perfluoropolyether structure and a silicon atom without a linking group Other hydrocarbon groups (including hydrocarbon groups in which at least some of the hydrogen atoms are substituted with fluorine atoms) are present at arbitrary positions of the linking group between the bonding structure, the perfluoropolyether structure and the silicon atom Intervening structures, structures in which a silicon atom and a hydrolyzable group are bonded via a linking group, structures in which the values of r and s are different, and the like are included, but are not limited to these structures.

The number average molecular weight of the organosilicon compound (A) is preferably 2,000 or more, more preferably 4,000 or more, even more preferably 5,000 or more, still more preferably 5,300 or more, and 40 ,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less.

As the organosilicon compound (A), only one type may be used, or two or more types may be used.

The mass ratio (solid content) of the organosilicon compound (A) to 100% by mass of the mixed composition is more than 1% by mass. Formable. The mass ratio of the organosilicon compound (A) is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and even more preferably 13% by mass or more. . Moreover, the mass ratio of the organosilicon compound (A) is preferably 30% by mass or less, and by setting it in such a range, the appearance of the water-repellent layer (r) is improved. The mass ratio of the organosilicon compound (A) may be 25% by mass or less. The amounts of the organosilicon compound (A) and other compounds described later can be adjusted during preparation of the composition, or can be calculated from the analysis results of the composition. As a method of specifying from the analysis results of the composition, for example, the type of each compound contained in the composition is analyzed by gas chromatography mass spectrometry, liquid chromatography mass spectrometry, etc., and the obtained analysis The results can be identified by library searching, and the amount of each compound contained in the composition can be calculated from the above analytical results using the calibration curve method. Further, the mass ratio of the organosilicon compound (A) is preferably calculated as a ratio when the mixed composition of the organosilicon compound (A), the organosilicon compound (C) and the solvent is taken as 100% by mass, and the organic The same applies to the mass ratio of the silicon compound (C).

As described above, the mixed composition is obtained by mixing the organosilicon compound (A), the organosilicon compound (C), and preferably the solvent (especially the fluorine-based solvent (D1) and the non-fluorine-based solvent (D2)), Including those in which the reaction has progressed, examples in which the reaction has progressed include the mixed composition having a hydrolyzable hydrolyzable compound bonded to the silicon atom of the organosilicon compound (A) (which may be bonded via a linking group). Examples include compounds in which a group is hydrolyzed to a —SiOH group (Si and OH may be bonded via a linking group). Further, the mixed composition may contain a condensate of the organosilicon compound (A), and the condensate may be a —SiOH group possessed by the organosilicon compound (A) or an organosilicon compound produced by hydrolysis ( The -SiOH group (Si and OH may be bonded via a linking group) of A) is a -SiOH group derived from the organosilicon compound (A) (Si and OH are bonded via a linking group may be used), or condensates formed by dehydration condensation with —SiOH groups derived from other compounds.

2-2. Organosilicon compound (C)
The organosilicon compound (C) is a compound having an amino group or an amine skeleton, and may have both an amino group and an amine skeleton. The amine skeleton is represented by —NR ¹⁰⁰ —, where R ¹⁰⁰ is a hydrogen atom or an alkyl group. A hydrolyzable group or a hydroxy group is preferably bonded to the silicon atom of the organosilicon compound (C). The hydrolyzable groups bonded to the silicon atoms of the organosilicon compound (C) include alkoxy groups, halogen atoms, cyano groups, acetoxy groups, isocyanate groups and the like. The silicon atom of the organosilicon compound (C) is preferably bonded to an alkoxy group or a hydroxy group having 1 to 4 carbon atoms, more preferably an alkoxy group or a hydroxy group having 1 to 2 carbon atoms, and a methoxy group. is particularly preferred. The organosilicon compound (C) preferably has at least an amine skeleton, and more preferably has both an amine skeleton and an amino group. By using the organosilicon compound (C) in the mixed composition of the present invention, in a laminate in which a film obtained from the mixed composition is formed on a substrate, the film has good adhesion to the substrate. As a result, the wear resistance of the laminate can be improved.

Examples of the organosilicon compound (C) include compounds represented by the following formulas (c1) to (c3).

2-2-1. Organosilicon compound (C) represented by formula (c1) (hereinafter, organosilicon compound (C1))

In the above formula (c1),
R ^x11 , R ^x12 , R ^x13 , and R ^x14 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when multiple R ^x11 are present, the multiple R ^x11 are different may be different when there are a plurality of R ^x12 ; when there are a plurality of R ^x13 , a plurality of R ^x13 may be different ^; and when there are a plurality of R ^x14 may be different from each other in a plurality of R ^x14 ,
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 fluorine atoms or a fluorine atom, and a plurality of Rf ^x11 are present When there is a plurality of Rf ^x11 may be different, when there are a plurality of Rf ^x12 , a plurality of Rf ^x12 may be different, and when there are a plurality of Rf ^x13 , a plurality of Rf ^x13 may be different may be different, and if there are a plurality of Rf ^x14 , the plurality of Rf ^x14 may be different,
R ^x15 is an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^x15 are present, the plurality of R ^x15 may be different,
X ¹¹ is a hydrolyzable group, and when a plurality of X ¹¹ are present, the plurality of X ¹¹ may be different,
Y ¹¹ is -NH- or -S-, and when a plurality of Y ¹¹ are present, the 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 0 to 10,
p6 is an integer from 1 to 3,
having at least one Y ¹¹ which is —NH— if Z ¹¹ is not an amino group, and Z ¹¹ is an amino group if all Y ¹¹ are —S— or p5 is 0;
Z ¹¹ -, -Si(X ¹¹ ) _p6 (R ^x15 ) _3-p6 , p1 -{C(R ^x11 )(R ^x12 )}-units (U _c11 ), p2 -{C(Rf ^x11 ) (Rf ^x12 )}-unit (U _c12 ), p3-{Si(R ^x13 )(R ^x14 )}-unit (U _c13 ), p4-{Si(Rf ^x13 )(Rf ^x14 )} The _-unit (U c14 ) and p5 -Y ¹¹ -units (U _c15 ) ^form one end of the compound represented by the formula (c1), and -Si(X ¹¹ ) _p6 (R ^x15 ) Unless _3-p6 is the other end and —O— is not linked to —O—, each unit is linked in any order.

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

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

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

X ¹¹ is preferably an alkoxy group, a halogen atom, a cyano group, or an isocyanate group, more preferably an alkoxy group, even more preferably an alkoxy group having 1 to 4 carbon atoms, a methoxy group or an ethoxy is more preferred, and a methoxy group is particularly preferred.

Y ¹¹ is preferably -NH-.

Z ¹¹ is preferably a methacryloyl group, an acryloyl group, a mercapto group or an amino group, more preferably a mercapto group or an amino group, still more preferably an amino group.

p1 is preferably 1-15, more preferably 2-10. Each of p2, p3 and p4 is independently preferably 0-5, more preferably 0-2. p5 is preferably 0-5, more preferably 0-3. p6 is preferably 2 to 3, more preferably 3.

As the organosilicon compound (C), in the above formula (c1), both R ^x11 and R ^x12 are hydrogen atoms, Y ¹¹ is —NH—, and X ¹¹ is an alkoxy group (especially 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 0 to 5 ( In particular, it is preferable to use a compound of 1 to 3) and p6 of 3.

When KBM603 (manufactured by Shin-Etsu Chemical Co., Ltd.) used as compound (C) in the examples described later is represented by the above formula (c1), Z ¹¹ is an amino group, and both R ^x11 and R ^x12 are hydrogen atoms. , Y ¹¹ is —NH—, p1 is 5, p2 to p4 are all 0, p5 is 1, X ¹¹ are all methoxy groups, and p6 is 3.

In addition, p1 pieces of -{C(R ^x11 )(R ^x12 )}- do not need to be continuously bonded to -{C(R ^x11 )(R ^x12 )}-, and other units may be linked via , and p1 pieces in total may be used. The same applies to units enclosed by p2 to p5.

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

In the above formula (c1-2),
X ¹² is a hydrolyzable group, and when a plurality of X ¹² are present, the 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 a plurality of R ^x16 are present, the plurality of R ^x16 may be different,
p is an integer of 1 to 3, q is an integer of 2 to 5, r is an integer of 0 to 5, s is 0 or 1,
When s is 0, Z ¹² is an amino group.

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

Z ¹² is preferably an amino group.

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

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

When s is 1, q is preferably an integer of 2 to 3, r is preferably an integer of 2 to 4, and when s is 0, the sum of q and r is 1 to 5. Preferably. Preferably, s is 1.

2-2-2. Organosilicon compound (C) represented by formula (c2) (hereinafter referred to as organosilicon compound (C2))

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 ^; When a plurality of R x21 are present, the plurality of R ^x21 may be different,
Rf ^x20 and Rf ^x21 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom, and when there are multiple Rf ^x20 , multiple Rf ^x20 may be different, and when there are a plurality of Rf ^x21 , the plurality of Rf ^x21 may be different,
R ^x22 and R ^x23 are each independently an alkyl group having 1 to 20 carbon atoms, and when there are a plurality of R ^x22 and R ^x23 , a plurality of R ^x22 and R ^x23 may be different,
X ²⁰ and X ²¹ are each independently a hydrolyzable group, and when multiple X ²⁰ and X ²¹ are present, multiple X ²⁰ and X ²¹ may be different,
p20 is an integer of 1 to 30, p21 is an integer of 0 to 30, and at least one of the repeating units bracketed with p20 or p21 is replaced 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-{C( ^Rx20 )( ^Rx21 )}-units ( _Uc20 ), p21-{C( ^Rfx20 )( ^Rfx21 )}-units ( _Uc21 ) are p20 units ( U _c20 ) or p21 units (U _c21 ) need not be contiguous, and each unit (U _c21 ) and unit (U _c20 ) can be arranged in any order and combined to form the formula (c2). One end of the compound is -Si(X ²⁰ ) _p22 (R ^x22 ) _3-p22 , and the other end is -Si(X ²¹ ) _p23 (R ^x23 ) _3-p23 .

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

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

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

X ²⁰ and X ²¹ are preferably an alkoxy group, a halogen atom, a cyano group, or an isocyanate group, more preferably an alkoxy group, still more preferably an alkoxy group having 1 to 4 carbon atoms, a methoxy group or an ethoxy group. group is even more preferred, and a methoxy group is particularly preferred.

As described above, at least one amine skeleton —NR ¹⁰⁰ — may be present in the molecule, and the amine skeleton may be replaced by either a repeating unit bracketed with p20 or p21. , p20 are preferably part of a bracketed repeating unit. A plurality of the amine skeletons may be present, and in that case, the number of amine skeletons is preferably 1-10, more preferably 1-5, and even more preferably 2-5. In this case, it is preferable to have -{C(R ^x20 )(R ^x21 )} _p200 - between adjacent amine skeletons, and p200 is preferably 1 to 10, preferably 1 to 5. more preferred. p200 is included in the total number of p20s.

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

p20 is preferably 1-15, more preferably 1-10, excluding the number of repeating units replaced by the amine skeleton.

p21 is preferably 0 to 5, more preferably 0 to 2, excluding the number of repeating units replaced by the amine skeleton.

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

As the organosilicon compound (C2), in the above formula (c2), both R ^x20 and R ^x21 are hydrogen atoms, and X ²⁰ and X ²¹ are alkoxy groups (particularly preferably methoxy or ethoxy groups, particularly methoxy groups is preferred), at least one repeating unit bracketed with p20 is replaced with an amine skeleton —NR ¹⁰⁰ —, R ¹⁰⁰ is a hydrogen atom, p20 is 1 to 10 ( However, it is preferable to use a compound in which p21 is 0 and p22 and p23 are 3, except for the number of repeating units replaced by the amine skeleton.

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

In the above formula (c2-2),
X ²² and X ²³ are each independently a hydrolyzable group, and when a plurality of X ²² and X ²³ are present, the plurality of X ²² and X ²³ may be different,
R ^x24 and R ^x25 are each independently an alkyl group having 1 to 20 carbon atoms, and when there are a plurality of R ^x24 and R ^x25 , a plurality of R ^x24 and R ^x25 may be different,
—C _w H _2w — has at least one of its methylene groups replaced with an amine skeleton —NR ¹⁰⁰ —, and R ¹⁰⁰ is a hydrogen atom or an alkyl group;
w is an integer of 1 to 30 (excluding the number of methylene groups substituted for the amine skeleton),
p24 and p25 are each independently an integer of 1-3.

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

A plurality of amine skeletons —NR ¹⁰⁰ — may be present, and in that case, the number of amine skeletons is preferably 1 to 10, more preferably 1 to 5, and 2 to 5. More preferred. Moreover, in this case, it is preferable to have an alkylene group between adjacent amine skeletons. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. The number of carbon atoms in the alkylene groups between adjacent amine skeletons is included in the total number of w.

R ^x24 and R ^x25 are preferably alkyl groups having 1 to 10 carbon atoms, more preferably alkyl groups having 1 to 5 carbon atoms.

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

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

2-2-3. Organosilicon compound (C) represented by formula (c3) (hereinafter, organosilicon compound (C3))

In the above formula (c3),
Z ³¹ and Z ³² are each independently a reactive functional group other than a hydrolyzable group and a hydroxy group. Reactive functional groups include vinyl, α-methylvinyl, styryl, methacryloyl, acryloyl, amino, epoxy, ureido, or mercapto groups. Z ³¹ and Z ³² are preferably an amino group, a mercapto group, or a methacryloyl group, particularly preferably an amino group.

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

Rf ^x31 , Rf ^x32 , Rf ^x33 , and Rf ^x34 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom, and a plurality of Rf ^x31 are present When there are multiple Rf x31, the plurality of Rf ^x31 may be different, and when there are multiple Rf ^x32 , the plurality of Rf ^x32 may be different, and when there are multiple Rf ^x33 , the plurality of Rf ^x33 may be different. When there are multiple Rf ^x34 , each of the multiple Rf ^x34 may be different. Rf ^x31 , Rf ^x32 , Rf ^x33 and Rf ^x34 are preferably C 1-10 alkyl groups in which one or more hydrogen atoms are substituted with fluorine atoms or fluorine atoms.

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

X ³¹ , X ³² , X ³³ and X ³⁴ are each independently —OR ^c (R ^c is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or amino-C _1-3 alkyldi-C _1-3 alkoxysilyl is a group), and when a plurality of X ³¹ are present, the plurality of X ³¹ may be different, when a plurality of X ³² are present, the plurality of X ³² may be different, and X ³³ is When a plurality of X 33 are present, the plurality of X ³³ may be different, and when a plurality of X ³⁴ are present, the plurality of X ³⁴ may be different. 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, more preferably a hydrogen atom.

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

The organosilicon compound (C3) satisfies the condition that at least one of Z ³¹ and Z ³² is an amino group, or at least one of Y ³¹ is —NH— or —N(CH ₃ )—, and the formula ^p31 ^- {C(R ^x31 ) (R ^x32 )}-unit (U _c31 ), p32-{C(Rf ^x31 )(Rf ^x32 )}-unit (U _c32 ), p33-{Si(R ^x33 )(R ^x34 )} - unit (U _c33 ), p34 -{Si(Rf ^x33 )(Rf ^x34 )} - unit (U _c34 ), p35 -Y ³¹ - unit (U _c35 ), p36 -{Si(X ³¹ ) (X ³² )-O}-unit (U _c36 ) and p37 -{Si(X ³³ )(X ³⁴ )}-units (U _c37 ) arranged in arbitrary order and bonded together be done. p31 -{C(R ^x31 )(R ^x32 )}-units (U _c31 ) do not have to be continuously linked with -{C(R ^x31 )(R ^x32 )}- It may be bound via another unit, and the total number of p31 may be sufficient. The same applies to the units (U _c32 ) to (U _c37 ) enclosed by p32 to p37.

As the organosilicon compound (C3), Z ³¹ and Z ³² are amino groups, R ^x31 and R ^x32 are hydrogen atoms, p31 is 3 to 13 (preferably 5 to 10), R ^x33 and R Each of ^x34 is a hydrogen atom, each of Rf ^x31 to Rf ^x34 is 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, and each of p32 to p34 is 0 to 5, Y ³¹ is —NH—, p35 is 0 to 5 (preferably 0 to 3), X ³¹ to X ³⁴ are all —OH, and p36 is 1 to 5 (preferably is 1-3) and p37 is 1 is preferred.

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

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

In formula (c3-2), Z ³¹ and Z ³² are preferably an amino group, a mercapto group, or a methacryloyl group, 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, more preferably R ^c is a hydrogen atom. preferable. Y ³¹ is preferably -NH-. p41 to p44 are preferably 1 or more, preferably 5 or less, and more preferably 4 or less. Both p45 and p46 are preferably 0.

As described above, the mixed composition is prepared by mixing the organosilicon compound (A), the organosilicon compound (C), preferably the solvent (especially the fluorinated solvent (D1) and the non-fluorinated solvent (D2)), and then reacting As an example in which the reaction has progressed, the mixed composition includes a compound in which the hydrolyzable group bonded to the silicon atom of the organosilicon compound (C) is hydrolyzed to become a —SiOH group. Things are mentioned. Further, as an example of the progress of the reaction, the mixed composition may include a condensate of the organosilicon compound (C). As the condensate, the —SiOH group of the organosilicon compound (C) or the —SiOH group of the organosilicon compound (C) generated by hydrolysis is a —SiOH group derived from the organosilicon compound (C), or another A condensate formed by dehydration condensation with a -SiOH group derived from a compound is exemplified. Specifically, the condensate of the organosilicon compound (C) includes, for example, the organosilicon compound (C3') in which the organosilicon compound (C3) is condensed and bonded with at least one of the above X ³¹ to X ³⁴ . .

The organosilicon compound (C3′) has two or more structures (c31-1) represented by the following formula (c31-1), and the structures (c31-1) are represented by *3 or *4 below. A chain or ring-bonded compound, wherein the bond in *3 or *4 below is due to the condensation of two or more of the organosilicon compounds (C3) above X ³¹ or X ³² ,
*1 and *2 in the following formula (c31-1) are, respectively, at least the units enclosed by p31, p32, p33, p34, p35, (p36)-1, and p37 in the following formula (c31-2) One type is bonded in any order and a group having a terminal Z- is bonded, and the groups bonded to *1 and *2 may be different for each of the plurality of structures (c31-1),
When a plurality of structures (c31-1) are bonded in a chain, *3, which is the terminal, is a hydrogen atom, and *4 is a hydroxy group.

In the formula (c31-2),
Z is a reactive functional group other than a hydrolyzable group and a hydroxy group;
R ^x31 , R ^x32 , R ^x33 , R ^x34 , Rf ^x31 , Rf ^x32 , Rf ^x33 , Rf ^x34 , Y ³¹ , X ³¹ , X ³² , X ³³ , X ³⁴ , p31 to p37 are are synonymous with these signs of

When the organosilicon compound (C3) is a compound represented by the above formula (c3-2), the organosilicon compound (C3′) is, for example, a structure represented by the following formula (c31-3) *3 below. or *4 may be a chain or ring-bonded compound. When the structure represented by the following formula (c31-3) is linked in a chain, the terminal *3 is a hydrogen atom and the terminal *4 is a hydroxy group.

All the symbols in the above formula (c31-3) have the same meanings as the symbols in the above formula (c3-2).

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

As the organosilicon compound (C), only one type may be used, or two or more types may be used. As the organosilicon compound (C), the organosilicon compound (C1) is preferably used.

The mass ratio of the organosilicon compound (C) to 100% by mass of the mixed composition is preferably 0.1% by mass or more, more preferably 0.7% by mass or more, still more preferably 1% by mass or more, and still more preferably. is 1.5% by mass or more, particularly preferably 2% by mass or more, may be 10% by mass or less, may be 8% by mass or less, or may be 6% by mass or less good.

Further, the mass ratio (solid content) of the organosilicon compound (A) to the organosilicon compound (C) (hereinafter expressed as (A)/(C)) is preferably 0.2 or more, and is set within this range. Thus, the appearance of the water-repellent layer (r) is improved. (A)/(C) is more preferably 0.5 or more, still more preferably 1.0 or more, still more preferably 1.5 or more, and particularly preferably 2.0 or more. In addition, (A)/(C) is preferably 9.5 or less, and by setting it in such a range, the adhesion of the water-repellent layer (r) is improved. (A)/(C) is more preferably 8.0 or less, still more preferably 7.0 or less.

2-3. Solvent It is preferable that the mixed composition further contains a solvent. The amount (mass ratio) of the solvent is preferably 60% by mass or more, more preferably 65% by mass or more, based on 100% by mass of the mixed composition of the organosilicon compound (A), the organosilicon compound (C) and the solvent. more preferably 70 mass % or more, may be 98 mass % or less, may be 95 mass % or less, or may be 90 mass % or less. The solvent preferably contains a fluorinated solvent (D1) and a non-fluorinated solvent (D2). When the solvent contains the fluorine-based solvent (D1) and the non-fluorine-based solvent (D2), the amount of the solvent means the total amount of the fluorine-based solvent (D1) and the non-fluorine-based solvent (D2).

2-3-1. Fluorinated solvent (D1)
The organosilicon compound (A) is particularly easy to dissolve in fluorine-based solvents. As the fluorinated solvent (D1), for example, a fluorinated ether solvent, a fluorinated amine solvent, a fluorinated hydrocarbon solvent, a fluorinated alcohol solvent, or the like can be used. Solvents are preferably used.
Examples of fluorinated ether-based solvents include hydrofluoroethers having 3 to 8 carbon atoms, such as C ₃ F ₇ OCH ₃ (manufactured by 3M, Novec (registered trademark) 7000), C ₄ F ₉ OCH ₃ ( 3M Novec (registered trademark) 7100), C ₄ F ₉ OC ₂ H ₅ (3M Novec (registered trademark) 7200), C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ (3M , Novec (registered trademark) 7300) and the like can be used.
As the fluorinated amine-based solvent, an amine in which at least one hydrogen atom of ammonia is substituted with a fluoroalkyl group is preferable, and a third A class amine is preferred, specifically tris(heptafluoropropyl)amine, and Fluorinert (registered trademark) FC-3283 (manufactured by 3M) corresponds to this.
Fluorinated hydrocarbon solvents include fluorinated aliphatic hydrocarbon solvents such as 1,1,1,3,3-pentafluorobutane and perfluorohexane, and 1,3-bis(trifluoromethylbenzene). Examples include fluorinated aromatic hydrocarbon solvents. Examples of 1,1,1,3,3-pentafluorobutane include Solv 55 (manufactured by Solvex).
Fluorinated alcohol solvents include 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3-tetrafluoro-1-propanol, 2,2,3,3, 4,4,5,5-octafluoro-1-pentanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1-heptanol, perfluorooctyl ethanol, 1H,1H,2H,2H-tridecafluoro-1-n-octanol and the like.

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

As the fluorine-based solvent (D1), only one kind may be used, or two or more kinds may be used. As the fluorinated solvent (D1), it is preferable to use at least a fluorinated ether solvent or a fluorinated hydrocarbon solvent.

The amount (mass ratio) of the fluorine-based solvent (D1) with respect to 100% by mass of the mixed composition is preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more. Also, the mass ratio of the fluorinated solvent (D1) may be, for example, 90% by mass or less, 85% by mass or less, or 80% by mass or less. When using a plurality of types as the fluorine-based solvent (D1), the total amount should be within the above range.

2-3-2. Non-fluorinated solvent (D2)
Since the organosilicon compound (C) is easily dissolved in the non-fluorine-based solvent (D2), it is thought that the aggregation and condensation of the organosilicon compounds (C) can be suppressed. The effect of being superior can also be produced.

As the non-fluorine-based solvent, that is, the solvent (D2) containing no F atom, water, alcohol-based solvents, ketone-based solvents, ether-based solvents, hydrocarbon-based solvents, ester-based solvents, and the like can be used.

Examples of alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol (isopropyl alcohol), 1-butanol and the like.
Ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like.
Ether solvents include diethyl ether, dipropyl ether, tetrahydrofuran, 1,4-dioxane and the like.
Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents such as pentane and hexane, alicyclic hydrocarbon solvents such as cyclohexane, and aromatic hydrocarbon solvents such as benzene, toluene, and xylene.
Ester-based solvents include ethyl acetate, propyl acetate, butyl acetate, amyl acetate, and isoamyl acetate.

As the non-fluorine-based solvent (D2), only one type may be used, or two or more types may be used. The non-fluorine solvent (D2) preferably contains at least one of an alcohol solvent, a ketone solvent, and an ester solvent, and more preferably contains an alcohol solvent. Along with the alcohol solvent, the ester solvent and / Or it is more preferable to contain a ketone solvent. When the non-fluorine-based solvent (D2) contains an alcohol-based solvent, condensation between the organosilicon compounds (C) can be easily suppressed. In addition, when the non-fluorine-based solvent (D2) contains an alcohol-based solvent and an ester-based solvent, it is possible to obtain the effect of obtaining a uniform film with a good appearance or improving the abrasion resistance of the obtained film. . In addition, since the non-fluorine-based solvent (D2) contains an alcohol-based solvent and a ketone-based solvent, the abrasion resistance of the obtained film is improved. Further, by containing an alcohol solvent, an ester solvent and a ketone solvent in the non-fluorine solvent (D2), a uniform film with good appearance can be obtained.
When the non-fluorine-based solvent (D2) contains an alcohol solvent, the amount (mass ratio) of the alcohol-based solvent with respect to 100% by mass of the non-fluorine-based solvent (D2) is preferably 50% by mass or more, more preferably It is 60% by mass or more, more preferably 75% by mass or more, and may be 100% by mass or 90% by mass or less.
When the non-fluorine-based solvent (D2) contains an ester solvent, the amount (mass ratio) of the ester-based solvent with respect to 100% by mass of the non-fluorine-based solvent (D2) is preferably 3% by mass or more, more preferably It is 5% by mass or more, more preferably 8% by mass or more, and may be 15% by mass or less, or may be 13% by mass or less.
When the non-fluorine-based solvent (D2) contains a ketone-based solvent, the amount (mass ratio) of the ketone-based solvent with respect to 100% by mass of the non-fluorine-based solvent (D2) is preferably 3% by mass or more, more preferably It is 5% by mass or more, more preferably 8% by mass or more, and may be 15% by mass or less, or may be 13% by mass or less.

The amount (mass ratio) of the non-fluorinated solvent (D2) with respect to 100% by mass of the mixed composition is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 13% by mass or more, The upper limit may be, for example, 30% by mass or 25% by mass. When using a plurality of types as the non-fluorine-based solvent (D2), the total amount should be within the above range.

The distance Ra between the Hansen solubility parameter (HSP, hereinafter sometimes abbreviated as "HSP") of the fluorine-based solvent (D1) and the non-fluorine-based solvent (D2) obtained by the following formula (E.1) is preferably a predetermined value or more.

The Hansen solubility parameter divides the solubility parameter introduced by Hildebrand into three components: the dispersion term (δD), the polar term (δP), and the hydrogen bonding term (δH). It is represented. The dispersion term (δD) indicates the effect of the dispersion force, the polar term (δP) indicates the effect of the dipole force, and the hydrogen bond term (δH) indicates the effect of the hydrogen bond force.

The definition and calculation of the Hansen Solubility Parameters are described in Charles M. Hansen, Hansen Solubility Parameters: A Users Handbook (CRC Press, 2007). In addition, by using the computer software Hansen Solubility Parameters in Practice (HSPiP), the Hansen Solubility Parameters can be easily estimated from the chemical structure of compounds for which literature values are not known. Furthermore, for compounds for which literature values are unknown, it is possible to calculate the Hansen solubility parameter by using the melting sphere method described later. In the present invention, when determining the Hansen solubility parameters of fluorine-based solvents (D1) and non-fluorine-based solvents (D2), HSPiP version 5.2.05 was used for solvents registered in the database. Hansen Solubility Parameters were calculated using the values of Hansen Solubility Parameters, and for unregistered solvents, the dissolving ball method described later was used.

The dissolving sphere method is a method for calculating the Hansen solubility parameter of a target substance, in which the target substance is dissolved or dispersed in many different solvents whose Hansen solubility parameters A method for determining the Hansen Solubility Parameters by a solubility test that evaluates solubility or dispersibility. The type of solvent used in the solubility test is preferably selected so that the total value of the HSP dispersion term, polar term and hydrogen bonding term of each solvent varies widely between solvents, more specifically, preferably It is preferable to evaluate using 10 or more solvents, more preferably 15 or more solvents, and still more preferably 17 or more solvents. Specifically, among the solvents used in the solubility test, all the three-dimensional points of the solvent that dissolved or dispersed the target substance were included inside the sphere, and the points of the solvent that did not dissolve were outside the sphere. A sphere (solubility sphere) that is a sphere with a minimum radius is searched for, and the central coordinates of the sphere are used as the Hansen solubility parameter of the object. Evaluation of solubility and dispersibility is carried out by visually determining whether or not the target substance is dissolved in the solvent and whether or not it is dispersed. If the mixture of the target substance and the solvent becomes cloudy, the target substance precipitates, or the target substance and the solvent separate into layers, it can be determined that the target substance is not dissolved or dispersed in the solvent. A specific method for the solubility test will be described in detail in the Examples section.

For example, if the Hansen Solubility Parameters of some other solvent that was not used to determine the Hansen Solubility Parameters of the object was (δd, δp, δh), then the point indicated by the coordinates would be inside the solubility sphere of the object. , the solvent is believed to dissolve or disperse the object. On the other hand, if the coordinate point is outside the solubility sphere of the target, the solvent is considered incapable of dissolving and dispersing the target.

The distance Ra1 between the fluorinated solvent (D1) and the non-fluorinated solvent (D2) in the Hansen solubility parameter obtained by the following formula (E.1) is preferably 5.2 (J/cm ³ ) ^0.5 or more. , more preferably 5.5 (J/cm ³ ) ^0.5 or more, still more preferably 7 (J/cm ³ ) ^0.5 or more, and the distance Ra1 is, for example, 25 (J/cm ³ ). ^0.5 or less.

[In the formula,
δD1: dispersion term (J/cm ³ ) of Hansen solubility parameter of fluorine-based solvent (D1) ^0.5 ,
δD2: dispersion term (J/cm ³ ) of Hansen solubility parameter of non-fluorine solvent (D2) ^0.5 ,
δP1: the polar term of the Hansen solubility parameter (J/cm ³ ) of the fluorine-based solvent (D1) ^0.5 ,
δP2: the polar term of the Hansen solubility parameter (J/cm ³ ) of the non-fluorinated solvent (D2) ^0.5 ,
δH1: Hydrogen bond term (J/cm ³ ) of Hansen solubility parameter of fluorine-based solvent (D1) ^0.5 ,
δH2: Hydrogen bond term (J/cm ³ ) of Hansen solubility parameter of non-fluorinated solvent (D2) is ^0.5 ]

In the present invention, when a plurality of types of fluorine-based solvents (D1) are used, or when a plurality of types of non-fluorine-based solvents (D2) are used, the distance Ra1 of the Hansen solubility parameter described above is the fluorine-based solvent (D1) and the non-fluorine-based solvent (D1). Any of the combinations selected one by one from the fluorinated solvent (D2) may satisfy the above range.

Further, when a plurality of types of fluorine-based solvents (D1) are used, δD1, δP1, and δH1 of each fluorine-based solvent and the volume fraction of each fluorine-based solvent with respect to the total fluorine-based solvent are used to determine δD1total and δP1total of the entire fluorine-based solvent. and δH1total can be determined. δD1total can be obtained based on the following formula (E.2), and δP1total and δH1total can also be obtained in the same manner.

In the above formula, δD1 _i is the value of δD1 for each fluorine-based solvent when there are multiple types of fluorine-based solvents (D1), n is the number of types of fluorine-based solvents (D1), and X _i is the volume fraction of each fluorinated solvent to the total fluorinated solvent.

Further, even when a plurality of types of non-fluorine-based solvents (D2) are used, δD2total, δP2total, and δH2total of the entire non-fluorine-based solvent can be obtained in the same manner. Then, from δD1total, δP1total, δH1total, δD2total, δP2total, and δH2total, the distance Ra′ between the HSP of the entire fluorine-based solvent and the HSP of the entire non-fluorine-based solvent can be obtained. The distance Ra' is preferably 15 (J/cm ³ ) ^0.5 or less, and may be 11 (J/cm ³ ) ^0.5 or more.

In addition, the distance Ra2 of the Hansen solubility parameter between the organosilicon compound (C) and the non-fluorine solvent (D2) obtained by the following formula (E.3) is 0.5 (J/cm ³ ) ^0.5 or more. is preferably 1.0 (J/cm ³ ) ^0.5 or more, more preferably 2.0 (J/cm ³ ) ^0.5 or more, and for example 10 (J/cm ³ ) ^{0 0.5} or less, preferably 8 (J/cm ³ ) ^0.5 or less, more preferably 7 (J/cm ³ ) ^0.5 or less.

[In the formula,
δDC: dispersion term (J/cm ³ ) of the Hansen solubility parameter of the organosilicon compound (C) ^0.5 ,
δD2: dispersion term (J/cm ³ ) of Hansen solubility parameter of non-fluorine solvent (D2) ^0.5 ,
δPC: the polar term of the Hansen solubility parameter of the organosilicon compound (C) (J/cm ³ ) ^0.5 ,
δP2: the polar term of the Hansen solubility parameter (J/cm ³ ) of the non-fluorinated solvent (D2) ^0.5 ,
δHC: hydrogen bond term of Hansen solubility parameter of organosilicon compound (C) (J/cm ³ ) ^0.5 ,
δH2: Hydrogen bonding term of Hansen solubility parameter of non-fluorinated solvent (D2) ((J/cm ³ ) is ^0.5 )

The Hansen solubility parameter of the organosilicon compound (C) can be determined by the same method as the method for determining the Hansen solubility parameter of the fluorine-based solvent (D1) and the non-fluorine-based solvent (D2) described above. In the present invention, the Hansen solubility parameter of the organosilicon compound (C) is calculated by using the above-described dissolving ball method.

When a single compound is used as the organosilicon compound (C), the HSP values (δDC, δPC, δHC) of the organosilicon compound (C) calculated by the melting ball method are used as they are, but the organosilicon compound (C ), it is calculated from the HSP values (δDC, δPC, δHC) of each organosilicon compound (C) and the volume fraction of each organosilicon compound (C) with respect to all the organosilicon compounds (C). In addition, .delta.DC, .delta.PC and .delta.HC of the entire organosilicon compound (C) are used. δDC when multiple types of organosilicon compounds (C) are used can be determined based on the following formula (E.4), and δPC and δHC when multiple types of organosilicon compounds (C) are used are similarly determined. be able to.

In the above formula, δDCi is the value of the dispersion term (δD) of each organosilicon compound (C) when there are multiple types of organosilicon compounds (C), and n is the type of the organosilicon compound (C). and XCi is the volume fraction of each organosilicon compound (C) to all organosilicon compounds (C).

When using multiple types of non-fluorine-based solvents (D2), δD2total, δP2total, and δH2total are used as δD2, δP2, and δH2 in formula (E.3).

The mass ratio of the fluorine-based solvent (D1) to the non-fluorine-based solvent (D2) is preferably 1% by mass or more, more preferably 50% by mass or more, still more preferably 100% by mass or more, and 200% by mass or more. , 240% by mass or more, 280% by mass or more, or 300% by mass or more. Further, the mass ratio of the fluorine-based solvent (D1) to the non-fluorine-based solvent (D2) is, for example, 3000% by mass or less, 2000% by mass or less, 1000% by mass or less, 800% by mass or less, 700% by mass or less, 600% by mass. % or less, or 500% by mass or less. The mass ratio of the fluorine-based solvent (D1) to the non-fluorine-based solvent (D2) is particularly preferably 240% by mass or more and 800% by mass or less, 280% by mass or more and 700% by mass or less, or 300% by mass or more and 600% by mass or less. . If the mass ratio of the fluorine-based solvent (D1) to the non-fluorine-based solvent (D2) is too small, the wear resistance may decrease, whereas if it is too large, the appearance may be impaired.

2-4. Organosilicon compound (B)
The mixed composition may further contain an organosilicon compound (B) represented by the following formula (b1). When the organic silicon compound (B) is mixed in the mixed composition, the mixed composition contains the organic silicon compound (A), the organic silicon compound (B), the organic silicon compound (C), and preferably a solvent. It includes those obtained by mixing them and undergoing reaction during storage, for example. The organosilicon compound (B) is present between the organosilicon compounds (A) in the film and has the effect of improving the slideability of water droplets and the like. The organosilicon compound (B) has a hydrolyzable group or a hydroxy group represented by ^A2 , as described later. Examples of the hydrolyzable group include an alkoxy group, a halogen atom, a cyano group, an acetoxy group and an isocyanate group.

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 fluorine atoms or a fluorine atom,
R ^b11 , R ^b12 , R ^b13 , and R ^b14 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when a plurality of R ^b11 are present, the plurality of R ^b11 are different from each other. When there are a plurality of R ^b12 , the plurality of R ^b12 may be different, when there are a plurality of R ^b13 , a plurality of R ^b13 may be different, and when there is a plurality of R ^b14 a plurality of R ^b14 may be different,
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 fluorine atoms or a fluorine atom, and a plurality of Rf ^b11 are present When there is a plurality of Rf b11, the plurality of Rf ^b11 may be different, when there are a plurality of Rf ^b12 , the plurality of Rf ^b12 may be different, and when there is a plurality of Rf ^b13 , the plurality of Rf ^b13 may be different. may be present, and if there are multiple Rf ^b14 , the plurality of Rf ^b14 may be different,
R ^b15 is an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^b15 are present, the plurality of R ^b15 may be different,
A ¹ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR- wherein R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms, and when there are a plurality of A ¹ , the plurality of A ¹ may be different,
A ² is a hydrolyzable group or a hydroxy group, and when a plurality of A ² are present, the plurality of A ² may be different,
b11, b12, b13, b14, and b15 are each independently an integer of 0 to 100,
c is an integer from 1 to 3,
Rf ^b10 -, -Si(A ² ) _c (R ^b15 ) _3-c , b11 -{C(R ^b11 )(R ^b12 )}-unit (U _b1 ), b12 -{C(Rf ^b11 ) (Rf ^b12 )}-unit (U _b2 ), b13-{Si(R ^b13 )(R ^b14 )}-unit (U _b3 ), b14-{Si(Rf ^b13 )(Rf ^b14 )} -unit (U _b4 ), b15 -A ¹ -units (U _b5 ), Rf ^b10 - is one terminal in formula (b1), and -Si(A ² ) _c (R ^b15 ) _3-c becomes the other end, and are linked in any order as long as they do not form a fluoropolyether structure and -O- is not linked to -O- to -F.

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

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

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

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

^A2 is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom, more preferably a methoxy group, an ethoxy group or a chlorine atom.

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

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

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

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

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

c is preferably 2 to 3, more preferably 3.

The total value of b11, b12, b13, b14, and b15 is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 80 or less, more preferably 50 or less, and still more preferably 20. It is below.

In particular, Rf ^b10 is a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, both R ^b11 and R ^b12 are hydrogen atoms, ^A2 is a methoxy group or an ethoxy group, and b11 is 1 to 5, b12 is 0 to 5, b13, b14, and b15 are all 0, and c is 3.

Specific examples of the compounds represented by the above formula (b1) include C _j F _2j+1 -Si-(OCH ₃ ) ₃ and C _j F _2j+1 -Si-(OC ₂ H ₅ ) ₃ (where j is 1 to 12). integers), 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 _2H5 ) ₃ , _C8F17 _- Si- ₍ _OC2H5 ) ₃ _are preferred. Also, _CF3CH2O ( _CH2 ) _kSiCl3 , _CF3CH2O ₍ _CH2 ) _kSi ₍ _OCH3 ) ₃ _, _CF3CH2O ₍ _CH2 ) _kSi ₍ _OC2H5 ) ₃ , _CF3 ( _CH2 )2Si( _CH3 ) ₂ ( _CH2 ) _kSiCl3 , _CF3 ( _CH2 ) _2Si(CH3)2 ₍ _CH2 ₎ _kSi ₍ OCH3) ₃ _, _CF3 ₍ _CH2 )2Si( _CH3 ) ₂ ( _CH2 ) _kSi ( _OC2H5 ) ₃ , _CF3 ( _CH2 ) _6Si ( _CH3 ) ₂ ₍ _CH2 ) _kSiCl3 _, _CF3 ₍ _CH2 ) _6Si ( _CH3 ) ₂ ( _CH2 ) _kSi (OCH3) ₃ , _CF3 ₍ _CH2 ) _6Si ( _CH3 ) ₂ ( _CH2 ) _kSi ( _OC2H5 ) ₃ _, _CF3COO (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 5 to 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 may also be mentioned (where m is 0 to 10, preferably 0 to 7, n is 1 to 5, preferably 2 to 4). ). CF ₃ (CF ₂ ) _p —(CH ₂ ) _q —Si—(CH ₂ CH=CH ₂ ) ₃ may also be mentioned, where p is 2 to 10, preferably 2 to 8, q are all 1 to 5, preferably 2 to 4). Furthermore, CF ₃ (CF ₂ ) _p —(CH ₂ ) _q SiCH ₃ Cl ₂ , CF ₃ (CF ₂ ) _p —(CH ₂ ) _q SiCH ₃ (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) _p —( CH ₂ ) _q SiCH ₃ (OC ₂ H ₅ ) ₂ (where p is 2 to 10, preferably 3 to 7, q is 1 to 5, preferably 2 to 4 is).

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

In the above formula (b2), R ⁶⁰ is a perfluoroalkyl group having 1 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. .

As the organosilicon compound (B), only one type may be used, or two or more types may be used. The amount (mass ratio) of the organosilicon compound (B) with respect to 100% by mass of the mixed composition is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, and 15% by mass or less. It is preferably 10% by mass or less, more preferably 10% by mass or less.

As described above, the mixed composition of the present invention comprises an organosilicon compound (A), an organosilicon compound (C), preferably a solvent (fluorinated solvent (D1) and non-fluorinated solvent (D2)), and optionally After mixing the organosilicon compound (B) used in the above, the reaction may have progressed. For example, it includes a compound whose degradable group is a —SiOH group by hydrolysis. Further, the mixed composition may contain a condensate of the organosilicon compound (B), and the condensate may be a —SiOH group possessed by the organosilicon compound (B) or an organosilicon compound produced by hydrolysis ( Condensates formed by dehydration condensation of —SiOH groups of B) with —SiOH groups derived from the organosilicon compound (B) or —SiOH groups derived from other compounds are exemplified.

The total amount of the organosilicon compound (A) and the organosilicon compound (C) is preferably 2% by mass or more, more preferably 5% by mass or more, and still more preferably 7% by mass with respect to 100% by mass of the mixed composition. or more, and may be 40% by mass or less, or may be 30% by mass or less.

The mixed composition contains the organosilicon compound (A), the organosilicon compound (C), a preferably used solvent, and additives other than the organosilicon compound (B) within a range that does not impair the effects of the present invention. For example, silanol condensation catalysts, antioxidants, rust inhibitors, UV absorbers, light stabilizers, anti-mold agents, antibacterial agents, antiviral agents, anti-biofouling agents, deodorants, pigments, flame retardants, Various additives such as antistatic agents and resins may be mixed. The amount (mass ratio) of the additive is preferably 5% by mass or less, more preferably 1% by mass or less, relative to 100% by mass of the mixed composition. Among the additives, the amount (mass ratio) of the resin is preferably less than 1% by mass, more preferably 0% with respect to 100% by mass of the mixed composition (including the solvent). .5% by mass or less, and may be 0% by mass. The amount of the additive (mass ratio) is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass with respect to 100% by mass of the total solid content in the mixed composition. % by mass or less, particularly preferably 4% by mass or less. In addition, among the additives, the amount (mass ratio) of the resin in particular is 30% by mass or less, 20% by mass or less, 10% by mass or less, or 4% by mass with respect to 100% by mass of the total solid content in the mixed composition. % or less, preferably less than 4% by mass or 2% by mass or less, and may be 0% by mass. The ratios of the additives and the resin to the total amount of solids mentioned above are equal to those ratios in the water-repellent layer.

When preparing the mixed composition, the mixing order of each compound is not limited. It is preferable to prepare each solution (p1) in which the system solvent (D2) is mixed, and to mix the solutions (r1) and (p1).

3. base material (s)
The present invention is a laminate comprising the water-repellent layer (r) and the base material (s), and the material of the base material (s) of the present invention is not particularly limited, and may be either an organic material or an inorganic material. Also, the shape of the substrate may be flat, curved, or a combination of these. Examples of organic materials include acrylic resins, acrylonitrile resins, polycarbonate resins, polyester resins (such as polyethylene terephthalate), styrene resins, cellulose resins, polyolefin resins, vinyl resins (such as polyethylene, polyvinyl chloride (that is, vinyl chloride resin), vinylbenzyl chloride resin, polyvinyl alcohol, etc.), polyvinylidene chloride resin, polyamide resin, polyimide resin, polyamideimide resin, polyetherimide resin, polyethersulfone resin, polysulfone resin, polyvinyl alcohol resin, polyvinyl acetal resin and thermoplastic resins such as these copolymers; resins such as thermosetting resins such as phenolic resins, urea resins, melamine resins, epoxy resins, unsaturated polyesters, silicone resins and urethane resins. Examples of inorganic materials include metals such as iron, silicon, copper, zinc, and aluminum, alloys containing these metals, ceramics, and glass. Among these, inorganic materials are particularly preferable, and glass is more preferable.

It is also preferable to disperse inorganic particles, organic particles, rubber particles in the substrate (s), and also colorants such as pigments and dyes, fluorescent brighteners, dispersants, plasticizers, heat stabilizers, light stabilizers. Ingredients such as agents, infrared absorbers, ultraviolet absorbers, antistatic agents, antioxidants, lubricants and solvents may also be incorporated.

The thickness of the substrate (s) is, for example, 5 μm or more, preferably 10 μm or more, more preferably 20 μm or more, still more preferably 30 μm or more, and may be 8 mm or less, preferably 7 mm or less, It is more preferably 6.5 mm or less, still more preferably 6 mm or less.

4. Layer (X)
In the laminate of the present invention, it is preferable that the substrate (s) and the water-repellent layer (r) are laminated via a layer (X) different from the substrate (s) and the water-repellent layer (r). . Examples of the layer (X) include layers formed from at least one selected from the group (X1) consisting of active energy ray-curable resins and thermosetting resins. The active energy ray is defined as an energy ray capable of decomposing a compound that generates active species to generate active species. Active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, γ rays, electron beams, and the like. The active energy curable resins include acrylic resins, epoxy resins, oxetane resins, urethane resins, polyamide resins, vinylbenzyl chloride resins, vinyl resins (polyethylene, vinyl chloride resins, etc.), and styrene resins. UV-curable resins such as resins, phenolic resins, vinyl ether-based resins, silicone-based resins, or mixed resins thereof, and electron beam-curable resins are included, and UV-curable resins are particularly preferred. In addition, as the layer (X), at least one selected from the group (X2) consisting of titanium oxide, zirconium oxide, aluminum oxide, niobium oxide, tantalum oxide, lanthanum oxide, and _SiO2 Layers that are formed can also be mentioned. As group (X1), acrylic resins, silicone resins, styrene resins, vinyl chloride resins, polyamide resins, phenol resins, and epoxy resins are particularly preferred. SiO ₂ is preferred for group (X2). The thickness of the layer (X) is, for example, 0.1 nm or more and 100 μm or less, preferably 1 nm or more and 60 μm or less, more preferably 1 nm or more and 10 μm or less.

4-1. Hard coat layer (hc)
When the layer (X) is formed from at least one selected from the group (X1), the layer (X) can function as a hard coat layer (hc) having surface hardness, and the substrate (s ) can be imparted with scratch resistance. The hard coat layer (hc) generally has a pencil hardness of B or higher, preferably HB or higher, more preferably H or higher, and even more preferably 2H or higher. When the layer (X) contains the hard coat layer (hc), that is, when the layer (X) has the function of a hard coat layer, the hard coat layer (hc) may have a single layer structure or a multilayer structure. may The hard coat layer (hc) preferably contains, for example, the above-described UV-curable resin, and particularly preferably contains an acrylic resin or a silicone resin. is preferred. It is also preferable to contain an epoxy-based resin, since there is a tendency that the adhesion between the substrate (s) and the film (r) is improved. A specific method for forming the active energy ray-curable resin and the thermosetting resin constituting the group (X1) will be described later in the column of the display device.

When the layer (X) contains the hard coat layer (hc), the hard coat layer (hc) may contain additives. Additives are not limited and include inorganic microparticles, organic microparticles, or mixtures thereof. Examples of additives include ultraviolet absorbers, silica, metal oxides such as alumina, and inorganic fillers such as polyorganosiloxane. By including the inorganic filler, the adhesion between the substrate (s) and the film (r) can be improved. The thickness of the hard coat layer (hc) is, for example, 1 μm or more and 100 μm or less, preferably 2 μm or more and 100 μm or less. When the thickness of the hard coat layer (hc) is 1 μm or more, sufficient scratch resistance can be ensured, and when it is 100 μm or less, flex resistance can be ensured, and as a result, curling due to curing shrinkage can be suppressed. becomes.

4-2. Antireflection layer (ar)
When the layer (X) is formed from at least one selected from the group (X2), the layer (X) can function as an antireflection layer (ar) that prevents reflection of incident light. When the layer (X) contains an antireflection layer (ar), the antireflection layer (ar) is a layer exhibiting reflection characteristics in which the reflectance is reduced to about 5.0% or less in the visible light region of 380 to 780 nm. is preferably Layer (X) preferably comprises a layer formed from _SiO2 .

The structure of the antireflection layer (ar) is not particularly limited, and may be a single layer structure or a multilayer structure. In the case of a multilayer structure, a structure in which low refractive index layers and high refractive index layers are alternately laminated is preferable, and the number of laminated layers is preferably 2 to 20 in total. Materials constituting the high refractive index layer include titanium oxide, zirconium oxide, aluminum oxide, niobium oxide, tantalum oxide and lanthanum oxide, and silica is a material constituting the low refractive index layer. mentioned. The multi-layered antireflection layer has a structure in which SiO ₂ (silica) and ZrO ₂ or SiO ₂ and Nb ₂ O ₅ are alternately laminated, and the outermost layer on the side opposite to the substrate (s) is SiO ₂ . is preferred. The antireflection layer (ar) can be formed by vapor deposition, for example. The thickness of the antireflection layer (ar) is, for example, 0.1 nm to 5 μm.

The layer (X) may contain both the hard coat layer (hc) and the antireflection layer (ar). In this case, the laminate of the present invention comprises the substrate (s), the hard It is preferable that the coat layer (hc), the antireflection layer (ar), and the film (r) are laminated in this order.

When the layer (X) is formed from at least one selected from the group (X1), for example, the mixture composition constituting the layer (X) is applied to the substrate (s), and heat, ultraviolet rays, etc. The layer (X) can be formed by curing with an active energy ray of . Moreover, when the layer (X) is formed from at least one selected from the group (X2), the layer (X) can be formed, for example, by a vapor deposition method.

5. Method for manufacturing a laminate The laminate of the present invention is produced by forming the above-described layer (X) on the substrate (s) as necessary, and then vapor-depositing and curing the mixed composition after heating. can be formed.

Known conditions can be adopted as the conditions for vapor-depositing the mixed composition on the substrate (s) or the layer (X) provided on the substrate (s). The degree of vacuum is, for example, about 2.0×10 ⁻³ Pa or less. As a heating method for vapor deposition, either a resistance heating method or an electron beam heating method may be used, and the heating temperature is, for example, 100 to 400.degree. The film formation time is, for example, about 1 to 90 seconds.

After vacuum deposition, by standing in air at room temperature or heating (for example, 35 to 150° C., preferably 40 to 90° C., 5 to 90 minutes, preferably 30 to 80 minutes), In a preferred embodiment, the hydrolyzable group possessed by the organosilicon compound (A) is hydrolyzed by taking in moisture in the air, followed by dehydration condensation, or in a preferred embodiment, the —SiOH group possessed by the organosilicon compound (A). By dehydration condensation, siloxane bonds are formed and a cured film can be obtained. In addition, the humidity condition during standing at room temperature or during heating may be 50 to 90% RH.

After forming the water-repellent layer (r), it may be left vapor-deposited, or it may be subjected to a predetermined post-treatment, and the abrasion resistance of the film can be further improved by the post-treatment. Post-treatments include heating and holding, standing in a humidified atmosphere, ultrasonic cleaning, and wiping the surface with a cloth containing a solvent or a dry cloth. These post-treatments are performed alone. may be used, or two or more may be used in combination. Among these, heating and holding, ultrasonic cleaning, and wiping the surface with a dry cloth are particularly preferred. Heating may be maintained at, for example, 100 to 200° C. for 10 to 60 minutes. Ultrasonic cleaning may be performed using, for example, water, a fluorinated solvent, or alcohol as a cleaning liquid for about 1 to 5 minutes. Wiping the surface can be done several times. From the viewpoint of further increasing wear resistance, it is preferable to wipe the surface with a dry cloth or perform ultrasonic cleaning after heating and holding. By heating and holding, the interaction between any of the organosilicon compound (A), the organosilicon compound (C), the substrate (s), or the layer (X) changes to a state with higher durability. expected to do so. Wiping the surface also removes the excess, resulting in a smoother, cleaner film. On such films, lower resistance during abrasion testing is expected and higher abrasion resistance is expected.

It is preferable to subject the substrate (s) or the layer (X) provided on the substrate (s) to an easy-adhesion treatment before vapor-depositing the mixed composition. Hydrophilic treatment such as corona treatment, plasma treatment, ultraviolet treatment, etc., can be mentioned as the easy-adhesion treatment. Formation of functional groups such as OH groups (especially when the base material is an epoxy resin) or COOH groups (especially when the base material is an acrylic resin) on the surface of the base material by performing adhesion treatment such as plasma treatment. can be formed, and the adhesion between the substrate (s) or the layer (X) and the water-repellent layer (r) is further improved. In particular, it is preferable to subject the substrate (s) or the layer (X) formed from the group (X1) to an easy-adhesion treatment.

7. Display Device The laminate of the present invention is suitably used for a display device. The laminate of the present invention can preferably be used as a front panel in a display device, and the front panel is sometimes called a window film.

The display device preferably comprises a display device laminate containing a window film (that is, the laminate of the present invention) and an organic EL display panel. body is placed. In the flexible display device, it is preferable that the laminate for a flexible display device including a window film having flexible properties and an organic EL display panel are provided. A laminate is arranged and configured to be foldable. The laminate for a display device (preferably a laminate for a flexible display device) may further contain a polarizing plate (preferably a circularly polarizing plate), a touch sensor, etc. to constitute a touch panel display, and the order of lamination thereof is arbitrary. However, it is preferable that the layers are laminated in the order of the window film, the polarizing plate and the touch sensor, or in the order of the window film, the touch sensor and the polarizing plate from the viewing side. When the polarizing plate is present on the viewing side of the touch sensor, the pattern of the touch sensor becomes less visible and the visibility of the displayed image is improved, which is preferable. Each member can be laminated using an adhesive, a pressure-sensitive adhesive, or the like. Also, the flexible display device may include a light shielding pattern formed on at least one surface of any one of the window film, the polarizing plate, and the touch sensor.

(window film)
The window film is arranged on the viewing side of the display device (preferably the flexible image display device) and plays a role of protecting other components from external shocks or environmental changes such as temperature and humidity. Glass may be used as such a protective layer, and in a flexible image display device, a material having flexible properties may be used for the window film instead of being rigid and hard like glass. Therefore, when the laminate of the present invention is used as a window film in a flexible display device, the substrate (s) preferably has a layer made of a flexible transparent substrate, and the substrate (s) is at least one of It may have a multi-layer structure in which a hard coat layer is laminated on the surface.

The transparent substrate has a visible light transmittance of, for example, 70% or more, preferably 80% or more. Any transparent polymer film can be used as the transparent substrate. Specifically, polyolefins such as polyethylene, polypropylene, polymethylpentene, norbornene, or cycloolefin derivatives having a monomer unit containing cycloolefin, (modified) cellulose such as diacetyl cellulose, triacetyl cellulose, and propionyl cellulose acrylics such as methyl methacrylate (co)polymers, polystyrenes such as styrene (co)polymers, acrylonitrile-butadiene-styrene copolymers, acrylonitrile-styrene copolymers, ethylene-vinyl acetate copolymers Polyvinyl chlorides, polyvinylidene chlorides, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyesters such as polycarbonate and polyarylate, polyamides such as nylon, polyimides, polyamideimides, polyetherimides, Films formed of polymers such as polyethersulfones, polysulfones, polyvinyl alcohols, polyvinyl acetals, polyurethanes, and epoxy resins may be used, and unstretched uniaxially or biaxially stretched films may be used. can be done. These polymers can be used alone or in combination of two or more. Among the transparent substrates described above, preferred are polyamide films, polyamideimide films, polyimide films, polyester films, olefin films, acrylic films, and cellulose films, which are excellent in transparency and heat resistance. It is also preferable to disperse inorganic particles such as silica, organic fine particles, rubber particles, etc. in the polymer film. In addition, colorants such as pigments and dyes, optical brighteners, dispersants, plasticizers, heat stabilizers, light stabilizers, infrared absorbers, ultraviolet absorbers, antistatic agents, antioxidants, lubricants, solvents, etc. may contain a compounding agent. The thickness of the transparent substrate is 5 μm or more and 200 μm or less, preferably 20 μm or more and 100 μm or less. Particularly when used in a flexible image display device, the thickness of the transparent substrate is preferably 5 μm or more and 60 μm or less.

The hard coat layer when the laminate of the present invention is used as a window film is also the same as the hard coat layer (hc) described above. As described above, the hard coat layer (hc) is preferably formed from an active energy ray-curable resin and a thermosetting resin. It can be formed by curing a hardcoat composition containing the forming reactive material. The hard coat composition contains at least one polymer of a radically polymerizable compound and a cationic polymerizable compound.

The radically polymerizable compound is a compound having a radically polymerizable group. The radically polymerizable group possessed by the radically polymerizable compound may be any functional group capable of causing a radical polymerization reaction, and examples thereof include a group containing a carbon-carbon unsaturated double bond. Specific examples include a vinyl group and a (meth)acryloyl group. When the radically polymerizable compound has two or more radically polymerizable groups, these radically polymerizable groups may be the same or different. The number of radically polymerizable groups in one molecule of the radically polymerizable compound is preferably two or more from the viewpoint of improving the hardness of the hard coat layer. The radically polymerizable compound is preferably a compound having a (meth)acryloyl group from the viewpoint of high reactivity, and a polyfunctional acrylate monomer having 2 to 6 (meth)acryloyl groups in one molecule. Compounds called epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate and oligomers having several (meth) acryloyl groups in the molecule and having a molecular weight of several hundred to several thousand are preferred. Available. It preferably contains one or more selected from epoxy (meth)acrylate, urethane (meth)acrylate and polyester (meth)acrylate.

The cationically polymerizable compound is a compound having a cationically polymerizable group such as an epoxy group, an oxetanyl group, or a vinyl ether group. The number of cationically polymerizable groups in one molecule of the cationically polymerizable compound is preferably 2 or more, more preferably 3 or more, from the viewpoint of improving the hardness of the hard coat layer. As the cationically polymerizable compound, among others, a compound having at least one of an epoxy group and an oxetanyl group as a cationically polymerizable group is preferable. A cyclic ether group such as an epoxy group or an oxetanyl group is preferable from the viewpoint that shrinkage accompanying a polymerization reaction is small. In addition, among the cyclic ether groups, compounds having epoxy groups are readily available in various structures, do not adversely affect the durability of the resulting hard coat layer, and are easy to control compatibility with radically polymerizable compounds. There is an advantage. In addition, among the cyclic ether groups, the oxetanyl group tends to have a higher degree of polymerization than the epoxy group, is less toxic, accelerates the network formation rate obtained from the cationically polymerizable compound in the resulting hard coat layer, and radicals It has the advantage of forming an independent network without leaving unreacted monomers in the film even in a region where the polymerizable compound is mixed.

Examples of cationic polymerizable compounds having an epoxy group include polyglycidyl ethers of polyhydric alcohols having an alicyclic ring, or compounds containing cyclohexene rings or cyclopentene rings, which are treated with a suitable oxidizing agent such as hydrogen peroxide or peracid. Alicyclic epoxy resin obtained by epoxidation; polyglycidyl ether of aliphatic polyhydric alcohol or its alkylene oxide adduct, polyglycidyl ester of aliphatic long-chain polybasic acid, homopolymer of glycidyl (meth)acrylate, Aliphatic epoxy resins such as copolymers; bisphenols such as bisphenol A, bisphenol F and hydrogenated bisphenol A, or derivatives such as alkylene oxide adducts and caprolactone adducts thereof, and glycidyl ethers produced by reaction with epichlorohydrin, and glycidyl ether type epoxy resins derived from bisphenols such as novolak epoxy resins.
The hard coat composition may further include a polymerization initiator. Examples of the polymerization initiator include radical polymerization initiators, cationic polymerization initiators, radical and cationic polymerization initiators, etc., and can be appropriately selected and used. These polymerization initiators are decomposed by at least one of active energy ray irradiation and heating to generate radicals or cations to promote radical polymerization and cationic polymerization.

Any radical polymerization initiator may be used as long as it can release a substance that initiates radical polymerization by at least one of active energy ray irradiation and heating. Examples of thermal radical polymerization initiators include organic peroxides such as hydrogen peroxide and perbenzoic acid, and azo compounds such as azobisbutyronitrile.
As active energy ray radical polymerization initiators, Type 1 type radical polymerization initiators that generate radicals by decomposition of molecules and Type 2 type radical polymerization initiators that generate radicals by hydrogen abstraction type reaction in coexistence with tertiary amines are used. Yes, they can be used alone or in combination.

The cationic polymerization initiator should be capable of releasing a substance that initiates cationic polymerization by at least one of active energy ray irradiation and heating. As cationic polymerization initiators, aromatic iodonium salts, aromatic sulfonium salts, cyclopentadienyl iron (II) complexes and the like can be used. These can initiate cationic polymerization by either or both of active energy ray irradiation and heating depending on the difference in structure.

The polymerization initiator can be included in an amount of 0.1 to 10% by weight with respect to 100% by weight of the hard coat composition as a whole. If the content of the polymerization initiator is less than 0.1% by weight, curing may not proceed sufficiently, and it may be difficult to realize the mechanical properties and adhesion of the finally obtained coating film. If the content is more than % by weight, adhesion failure, cracking, and curling may occur due to cure shrinkage.

The hard coat composition may further contain one or more selected from the group consisting of solvents and additives. The solvent is capable of dissolving or dispersing the polymerizable compound and the polymerization initiator, and any solvent known as a solvent for hard coat compositions in this technical field can be used without limitation. The additives may further include inorganic particles, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, antifouling agents, and the like.

(Circularly polarizing plate)
As described above, the display device (preferably flexible display device) of the present invention preferably includes a polarizing plate, especially a circularly polarizing plate. A circularly polarizing plate is a functional layer having a function of transmitting only a right-handed or left-handed circularly polarized light component by laminating a λ/4 retardation plate on a linearly polarizing plate. For example, by converting external light into right-handed circularly polarized light and blocking the left-handed circularly polarized light reflected by the organic EL panel, and allowing only the luminescent component of the organic EL to pass through, the effect of the reflected light is suppressed to create an image. used to make it easier to see. In order to achieve the circular polarization function, the absorption axis of the linear polarizer and the slow axis of the λ/4 retardation plate should theoretically be 45 degrees, but in practice they are 45±10 degrees. The linear polarizing plate and the λ/4 retardation plate do not necessarily have to be laminated adjacent to each other as long as the relationship between the absorption axis and the slow axis satisfies the above range. Although it is preferable to achieve perfect circular polarization at all wavelengths, it is not always necessary in practice, 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 visible side of the linear polarizing plate to circularly polarize the emitted light, thereby improving the visibility when wearing polarized sunglasses.

A linear polarizer is a functional layer that passes light oscillating in the direction of the transmission axis, but blocks the polarization of the oscillating component perpendicular to it. The linear polarizing plate may have a configuration including a linear polarizer alone or a linear polarizer and a protective film attached to at least one surface of the linear polarizer. The thickness of the linear polarizing plate may be 200 μm or less, preferably 0.5 μm or more and 100 μm or less. 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.

The linear polarizer may be a film-type polarizer manufactured by dyeing and stretching a polyvinyl alcohol (hereinafter sometimes abbreviated as PVA) film. A dichroic dye such as iodine is adsorbed on a PVA-based film that has been oriented by stretching, or the film is stretched while adsorbed to PVA, thereby aligning the dichroic dye and exhibiting polarizing performance. The production of the film-type polarizer may include other steps such as swelling, cross-linking with boric acid, washing with an aqueous solution, and drying. The stretching and dyeing processes may be carried out on the PVA-based film alone, or may be carried out while it is laminated with another film (stretching resin base material) such as polyethylene terephthalate. The thickness of the PVA-based film used is preferably 3 to 100 μm, and the draw ratio is preferably 2 to 10 times. As a method for producing a laminate of a stretchable resin base material and a PVA-based resin layer, a method of applying a coating liquid containing a PVA-based resin to the surface of the stretchable resin base material and drying it is preferable.

In particular, if the manufacturing method includes the step of stretching and dyeing the PVA-based resin layer and the resin substrate for stretching in the state of a laminate, even if the PVA-based resin layer is thin, it is supported by the resin substrate for stretching. Thus, the film can be stretched without problems such as breakage due to stretching.

The thickness of the polarizer is 20 μm or less, preferably 12 μm or less, more preferably 9 μm or less, even more preferably 1 to 8 μm, particularly preferably 3 to 6 μm. If it is within the above range, it becomes a preferred embodiment without inhibiting bending.

Further, another example of the polarizer is a liquid crystal coated polarizer formed by applying a liquid crystal polarizing composition. The liquid crystal polarizing composition may contain a liquid crystal compound and a dichroic dye compound. The liquid crystalline compound only needs to have a property of exhibiting a liquid crystal state, and it is particularly preferable to have a high-order alignment state such as a smectic phase because high polarizing performance can be exhibited. Moreover, the liquid crystalline compound preferably has a polymerizable functional group.
The dichroic dye compound is a dye that exhibits dichroism by aligning with the liquid crystalline compound, and may have a polymerizable functional group, and the dichroic dye itself has liquid crystallinity. You may have
Any one of the compounds contained in the liquid crystal polarizing composition has 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 cross-linking agent, a silane coupling agent, and the like.
The liquid crystal polarizing layer is manufactured by coating a liquid crystal polarizing composition on an alignment film to form a liquid crystal polarizing layer. The liquid crystal polarizing layer can be formed thinner than the film-type polarizer, and the thickness is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less.

The alignment film is produced, for example, by coating an alignment film-forming composition on a substrate and imparting alignment properties by rubbing, polarized light irradiation, or the like. The alignment film-forming composition contains an alignment agent, and may further contain a solvent, a cross-linking agent, an initiator, a dispersant, a leveling agent, a silane coupling agent, and the like. Examples of the alignment agent include polyvinyl alcohols, polyacrylates, polyamic acids, and polyimides. When using an alignment agent that imparts alignment properties by polarized light irradiation, it is preferable to use an alignment 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 alignment film is preferably 5 nm or more and 10,000 nm or less, and more preferably 10 nm or more and 500 nm or less in terms of sufficiently expressing the alignment control force.
The liquid crystal polarizing layer can be laminated by peeling from the base material and transferring, or the base material can be laminated as it is. It is also preferable that the base material plays a role as a protective film, a retardation plate, or a transparent base material for a window film.

As the protective film, any transparent polymer film can be used, and the same materials and additives as those used for the transparent base material of the window film can be used. Cellulose-based films, olefin-based films, acrylic films, and polyester-based films are preferred. It may also be a coating-type protective film obtained by applying and curing a cationic curable composition such as an epoxy resin or a radical curable composition such as an acrylate. The protective film may optionally contain plasticizers, ultraviolet absorbers, infrared absorbers, colorants such as pigments and dyes, fluorescent brighteners, dispersants, heat stabilizers, light stabilizers, antistatic agents, and antioxidants. , a lubricant, a solvent, and the like. The thickness of the protective film is preferably 200 μm or less, more preferably 1 μm or more and 100 μm or less. When the thickness of the protective film is within the above range, the flexibility of the film tends to be less likely to decrease. The protective film can also serve as the transparent base material of the window film.

The λ/4 retardation plate is a film that provides a λ/4 retardation in a direction (in-plane direction of the film) perpendicular to the traveling direction of incident light. 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, if necessary, retardation modifiers, plasticizers, ultraviolet absorbers, infrared absorbers, colorants such as pigments and dyes, fluorescent brighteners, dispersants, heat stabilizers, light stabilizers agents, antistatic agents, antioxidants, lubricants, solvents, and the like.
The thickness of the stretched retardation plate is preferably 200 μm or less, more preferably 1 μm or more and 100 μm or less. 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.

Another example of the λ/4 retardation plate is a liquid crystal coated retardation plate formed by coating a liquid crystal composition.
The liquid crystal composition includes a liquid crystal compound exhibiting a liquid crystal state such as nematic, cholesteric, or smectic. The 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 cross-linking agent, a silane coupling agent, and the like.
The liquid crystal-coated retardation plate can be produced by applying a liquid crystal composition on a base and curing to form a liquid crystal retardation layer in the same manner as the liquid crystal polarizing layer. The liquid crystal coating type retardation plate can be formed thinner than the stretching type retardation plate. The thickness of the liquid crystal polarizing layer is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less.
The liquid crystal-coated retardation plate can be laminated by peeling from the base material and transferred, or the base material can be laminated as it is. It is also preferable that the base material plays a role as a protective film, a retardation plate, or a transparent base material for a window film.

In general, many materials exhibit larger birefringence at shorter wavelengths and smaller birefringence at longer wavelengths. In this case, it is not possible to achieve a retardation of λ/4 in the entire visible light region, so that the in-plane retardation is preferably 100 nm or more so that it is λ/4 around 560 nm where visibility is high. It is designed to be 180 nm or less, more preferably 130 nm or more and 150 nm or less. A reverse-dispersion λ/4 retardation plate using a material having a birefringence wavelength dispersion characteristic opposite to that of a normal one is preferable in terms of good visibility. As such materials, for example, those described in JP-A-2007-232873 and the like for the stretched retardation plate, and those described in JP-A-2010-30979 and the like for the liquid crystal-coated retardation plate can be used. .
As another method, a technique of obtaining a broadband λ/4 retardation plate by combining with a λ/2 retardation plate is also known (for example, JP-A-10-90521). The λ/2 retardation plate is also manufactured by a material method similar to that of the λ/4 retardation plate. The combination of the stretched retardation plate and the liquid crystal-coated retardation plate is arbitrary, but the thickness of both can be reduced by using the liquid crystal-coated retardation plate.
A method is known in which a positive C plate is laminated on the circularly polarizing plate in order to improve the visibility in the oblique direction (for example, Japanese Patent Application Laid-Open No. 2014-224837). The positive C-plate may be either a liquid crystal-coated retardation plate or a stretched retardation plate. The retardation in the thickness direction of the retardation plate is preferably −200 nm or more and −20 nm or less, more preferably −140 nm or more and −40 nm or less.

(touch sensor)
A display device (preferably a flexible display device) including the laminate of the present invention preferably includes a touch sensor as described above. A touch sensor is used as an input means. As the touch sensor, there are various types such as a resistive film type, a surface acoustic wave type, an infrared type, an electromagnetic induction type, and an electrostatic capacity type, and the capacitive type is preferred.
A capacitive touch sensor is divided into an active area and a non-active area located outside the active area. The active area is an area corresponding to the area (display part) where the screen is displayed on the display panel, and is an area where a user's touch is sensed. display area). The touch sensor preferably includes a flexible substrate, a sensing pattern formed in an active region of the substrate, and an external driving circuit formed in a non-active region of the substrate through the sensing pattern and a pad portion. each sensing line for connecting to a As the flexible substrate, the same material as the transparent substrate of the window film can be used. The substrate of the touch sensor preferably has a toughness of 2,000 MPa % or more from the viewpoint of suppressing cracks in the touch sensor. More preferably, the toughness is 2,000 MPa% or more and 30,000 MPa% or less. Here, the toughness is defined as the lower area of the stress-strain curve (Stress-strain curve) obtained through a tensile test of a polymer material up to the breaking point.

The sensing patterns may include first patterns formed in a first direction and second patterns 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 in the same layer, and each pattern must be electrically connected to sense a touched point. The first pattern has a form in which a plurality of unit patterns are connected to each other through joints, while the second pattern has a structure in which a plurality of unit patterns are separated from each other in an island form. A separate bridge electrode is required for direct connection. A well-known transparent electrode can be applied to the electrode for connection of the second pattern. Materials for the transparent electrode include, for example, indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), indium zinc tin oxide (IZTO), and indium gallium zinc oxide (IGZO). , cadmium tin oxide (CTO), PEDOT (poly(3,4-ethylenedioxythiophene)), carbon nanotube (CNT), graphene, metal wire, etc., preferably ITO. These can be used alone or in combination of two or more. The metal used for the metal wire is not particularly limited, and examples thereof include silver, gold, aluminum, copper, iron, nickel, titanium, terenium, chromium, etc. These may be used alone or in combination of two or more. can be done.
A bridge electrode may be formed on the insulating layer above the sensing pattern with an insulating layer interposed therebetween, and the bridge electrode may be formed on the substrate, and the insulating layer and the sensing pattern may be formed thereon. The bridge electrode may be made of the same material as the sensing pattern, and may be made of molybdenum, silver, aluminum, copper, palladium, gold, platinum, zinc, tin, titanium, or an alloy of two or more of these. can.
Since the first pattern and the second pattern should be electrically insulated, an insulating layer is formed between the sensing pattern and the bridge electrode. The insulating layer can be formed only between the joints and bridge electrodes of the first pattern, or can be formed as a layer covering the entire sensing pattern. In the case of a layer covering the entire sensing pattern, the bridge electrode can connect the second pattern through contact holes formed in the insulating layer.

The touch sensor is induced by a difference in transmittance between a patterned area where a sensing pattern is formed and a non-patterned area where no sensing pattern is formed, specifically by a difference in refractive index in these areas. An optical adjustment layer may further be included between the substrate and the electrode as a means for properly compensating for differences in optical transmittance. The optical modulating layer can comprise an inorganic insulating material or an organic insulating material. The optical control layer may be formed by coating a photocurable composition containing a photocurable organic binder and a solvent on a substrate. The photocurable composition may further include inorganic particles. The inorganic particles can increase the refractive index of the optical adjustment layer.
The photocurable organic binder includes a copolymer of each monomer such as an acrylate-based monomer, a styrene-based monomer, and a carboxylic acid-based monomer within a range that does not impair the effects of the present invention. be able to. The photocurable organic binder may be, for example, a copolymer containing different repeating units such as epoxy group-containing repeating units, acrylate repeating units, and carboxylic acid repeating units.
Examples of the inorganic particles include zirconia particles, titania particles, and alumina particles.
The photocurable composition may further include additives such as a photopolymerization initiator, a polymerizable monomer, and a curing aid.

(adhesion layer)
Each layer (window film, circularly polarizing plate, touch sensor) forming the laminate for the display device (preferably a flexible image display device) and film members (linear polarizing plate, λ/4 retardation plate, etc.) constituting each layer are It can be joined with an adhesive. Examples of the adhesive include water-based adhesives, organic solvent-based adhesives, solvent-free adhesives, solid adhesives, solvent volatile adhesives, moisture-curable adhesives, heat-curable adhesives, anaerobic-curable adhesives, and active energy ray-curable adhesives. Commonly used adhesives such as adhesives, curing agent-mixed adhesives, hot-melt adhesives, pressure-sensitive adhesives (adhesives), and rewetting adhesives can be used, preferably water-based solvent volatilization. A type adhesive, an active energy ray-curable adhesive, and a pressure-sensitive adhesive can be used. The thickness of the adhesive layer can be appropriately adjusted according to the desired adhesive strength and the like, and is preferably 0.01 to 500 μm, more preferably 0.1 to 300 μm. A plurality of adhesive layers are present in the laminate for a display device (preferably a flexible image display device), and the respective thicknesses and types may be the same or different.

As the water-based solvent volatilization adhesive, water-soluble polymers such as polyvinyl alcohol-based polymers and starch, and polymers in a water-dispersed state such as ethylene-vinyl acetate-based emulsions and styrene-butadiene-based emulsions can be used as main polymers. In addition to the main polymer and water, crosslinking agents, silane compounds, ionic compounds, crosslinking catalysts, antioxidants, dyes, pigments, inorganic fillers, organic solvents, and the like may be added. When bonding with the water-based solvent volatilization type adhesive, adhesion can be imparted by injecting the water-based solvent volatilization type adhesive between the layers to be adhered, laminating the layers to be adhered, and then drying. When the water-based solvent volatilization type adhesive is used, the thickness of the adhesive layer is preferably 0.01 to 10 μm, more preferably 0.1 to 1 μm. When the water-based solvent volatilization type adhesive is used for multiple layers, the thickness and type of each layer may be the same or different.

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 upon irradiation with an active energy ray. The active energy ray-curable composition can contain at least one polymer of the same radically polymerizable compound and cationic polymerizable compound as those contained in the hard coat composition. As the radically polymerizable compound, the same compound as the radically polymerizable compound in the hard coat composition can be used.
As the cationic polymerizable compound, the same compound as the cationic polymerizable compound in the hard coat composition can be used.
Epoxy compounds are particularly preferred as the cationic polymerizable compound used in the active energy ray-curable composition. It is also preferred to contain a monofunctional compound as a reactive diluent in order to reduce the viscosity of the adhesive composition.

The active energy ray composition can contain a monofunctional compound to reduce viscosity. Examples of the monofunctional compound include acrylate-based monomers having one (meth)acryloyl group in one molecule, compounds having one epoxy group or oxetanyl group in one molecule, such as glycidyl (meth) ) acrylates and the like.
The active energy ray composition can further contain a polymerization initiator. Examples of the polymerization initiator include radical polymerization initiators, cationic polymerization initiators, radical and cationic polymerization initiators, and these are appropriately selected and used. These polymerization initiators are decomposed by at least one of active energy ray irradiation and heating to generate radicals or cations to promote radical polymerization and cationic polymerization. In the description of the hard coat composition, an initiator capable of initiating at least one of radical polymerization and cationic polymerization upon exposure to active energy rays can be used.
The active energy ray-curable composition further includes an ion scavenger, an antioxidant, a chain transfer agent, an adhesion imparting agent, a thermoplastic resin, a filler, a flow viscosity modifier, a plasticizer, an antifoaming agent solvent, an additive, and a solvent. can include When bonding two layers to be adhered with the active energy ray-curable adhesive, the active energy ray-curable composition is applied to one or both of the layers to be adhered, and then laminated, and any adherend layer is adhered. Alternatively, both layers to be adhered can be adhered by irradiating them with active energy rays for curing. When the active energy ray-curable adhesive is used, the adhesive layer preferably has a thickness of 0.01 to 20 μm, more preferably 0.1 to 10 μm. When the active energy ray-curable adhesive is used to form a plurality of adhesive layers, the thickness and type of each layer may be the same or different.

The adhesives are classified into acrylic adhesives, urethane adhesives, rubber adhesives, silicone adhesives, etc., depending on the main polymer, and any of them can be used. In addition to the base polymer, the adhesive may contain a cross-linking agent, a silane compound, an ionic compound, a cross-linking catalyst, an antioxidant, a tackifier, a plasticizer, a dye, a pigment, an inorganic filler, and the like. An adhesive layer is formed by dissolving and dispersing each component constituting the adhesive in a solvent to obtain an adhesive composition, applying the adhesive composition on a substrate and then drying it. be. The adhesive layer may be formed directly, or may be transferred after being separately formed on the substrate. It is also preferable to use a release film to cover the adhesive surface before adhesion. When the active energy ray-curable adhesive is used, the adhesive layer preferably has a thickness of 0.1 to 500 μm, more preferably 1 to 300 μm. When using a plurality of layers of the pressure-sensitive adhesive, the thickness and type of each layer may be the same or different.

(Shading pattern)
The light shielding pattern can be applied as at least part of a bezel or housing of the display device (preferably a flexible image display device). The visibility of the image is improved by hiding the wiring arranged at the peripheral portion of the display device (preferably the flexible image display device) by the light-shielding pattern and making it difficult to see. The light shielding pattern may be in the form of a single layer or multiple layers. The color of the light-shielding pattern is not particularly limited, and various colors such as black, white, and metallic color may be used. The light-shielding pattern may be formed of pigments for realizing colors and polymers such as acryl-based resin, ester-based resin, epoxy-based resin, polyurethane, and silicone. These may be used singly or as a mixture of two or more. The light-shielding pattern can be formed by various methods such as printing, lithography, and inkjet. The thickness of the light-shielding pattern is preferably 1-100 μm, more preferably 2-50 μm. It is also preferable to impart a shape such as an inclination in the thickness direction of the light shielding pattern.

Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited by the following examples, and it is of course possible to make appropriate modifications within the scope that can be adapted to the gist of the above and below. Included in scope.

Example 1
A compound (a1) satisfying the above formula (a3) including the preferred range as the organosilicon compound (A) and Novec (registered trademark) 7200 as the fluorinated solvent (D1) are mixed and stirred at room temperature for a predetermined time. to obtain a mixture (a). Further, KBM603 (N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) as the organosilicon compound (C) and isopropyl alcohol as the non-fluorine solvent (D2) were mixed. , and shaken for a predetermined time at room temperature to obtain a mixture (c). Further, the mixed solution (a) and the mixed solution (c) were mixed and mixed using a vortex mixer to obtain a film-forming solution. Table 1 shows the mixing ratio of the organosilicon compound (A), the fluorine-based solvent (D1), the organosilicon compound (C), and the non-fluorine-based solvent (D2). The compound (a1) is a compound that also satisfies the requirements of the compounds (a11) and (a21).

Next, a glass having a thickness of 0.7 mm was used as the substrate (s), and SiO ₂ and metal oxides other than SiO ₂ were alternately laminated on the substrate (s) by a vacuum deposition method. A layer (X) (antireflection layer) having SiO ₂ on the side opposite to the substrate (s) was laminated. The surface of the layer (X) on which the film was formed was activated using an atmospheric pressure plasma device (manufactured by Fuji Machine Manufacturing Co., Ltd.).

Furthermore, after dropping 1 mL of the film-forming solution into a Mo boat for vapor deposition, the solvent was evaporated to prepare a sample to be used for vapor deposition. Using VPC-410A manufactured by ULVAC KIKO Co., Ltd., a layer obtained by activating the above sample by a vacuum deposition method (resistance heating method, pressure 1 × 10 ^-3 Pa, applied current 50 A, deposition processing time 90 seconds) ( X) to obtain a laminate in which the substrate (s), the layer (X), and the film (r) are laminated in this order. After film formation, the film was heated and held at a temperature of 40° C. and a relative humidity of 90% for 60 minutes. After that, the membrane surface was wiped with a dry cloth.

Example 2
In place of the compound (a1) and Novec7200 as the fluorine-based solvent (D1), Optool (registered trademark) DSX (manufactured by Daikin Industries, Ltd.) (20% by mass of the organosilicon compound (A) and perfluorohexane as the solvent 80% by mass) was used in the same manner as in Example 1 to obtain a laminate in which the substrate (s), the layer (X), and the film (r) were laminated in this order.

Example 3
In the same manner as in Example 1, except that the mixing ratio of compound (a1), KBM603, Novec7200, and isopropyl alcohol was changed as shown in Table 1, the substrate (s), layer (X), and film (r) were prepared in this order. A laminated body was obtained.

Comparative example 1
As the film-forming solution, 20% by mass of the compound (a1) and 80% by mass of Novec (registered trademark) 7200 were mixed, and the mixture was stirred at room temperature for a predetermined time. Thus, a laminate was obtained in which the substrate (s), the layer (X), and the film (r) were laminated in this order.

Comparative example 2
The substrate (s), the layer A laminate was obtained in which (X) and film (r) were laminated in this order.

Comparative example 3
In the same manner as in Example 1, except that the mixing ratio of compound (a1), KBM603, Novec7200, and isopropyl alcohol was changed as shown in Table 1, the substrate (s), layer (X), and film (r) were prepared in this order. A laminated body was obtained.

The laminates obtained in Examples and Comparative Examples were evaluated in the following manner.

(1) Initial contact angle A water droplet of 1 μL is dropped on the film (r) side surface of the obtained laminate, and a contact angle measurement device (manufactured by Kyowa Interface Science Co., Ltd., DM700) is used to measure the droplet method (analysis method: θ/2 method) was used to measure the contact angle of water.

(2) Initial sliding angle Using DM700 manufactured by Kyowa Interface Science Co., Ltd., sliding method (analysis method: tangent method, water droplet amount: 20.0 μL, tilt method: continuous tilt, sliding detection: after sliding, movement determination: forward angle, The slide angle of the film (r) side surface of the laminate was measured by the slide determination distance: 5 dots). In this embodiment, 1 dot is 0.01 mm.

(3) N amount measurement by XPS Using JFS-9010 type manufactured by JEOL Ltd., excitation X-ray: MgKα, X-ray output of 110 W, photoelectron escape angle of 45 °, pass energy of 50 eV, carbon (C1s) : 260 to 300 eV, nitrogen (N1s: 390 to 410 eV), oxygen (O1s): 525 to 545 eV, fluorine (F1s): 680 to 698 eV, silicon (2p): 92 to 112 eV. Regarding the N content on the surface of the water-repellent layer (r), the atomic ratio of the N (nitrogen) amount to the total amount of carbon, nitrogen, oxygen, fluorine and silicon was determined.

(4) Film thickness measurement Using VG Theta Probe analysis software manufactured by Thermo Fisher Scientific, based on the spectrum of each element obtained in the XPS measurement in (3) above, a depth profile is constructed by film thickness calculation and simulation calculation. gone.
Specifically, in the angle-resolved lens mode, measurements were made from detection angles of 81.13° to 24.88°, and the information depth was set to 6 to 7 nm, and the depth from the surface was calculated for each detection angle. The film thickness was calculated from the slope of the straight line obtained by plotting the values calculated from the peak area ratio of the signal derived from the base material for each detection angle.

(5) Abrasion resistance test On the surface of the film (r) of the laminate, 16 sheets of Kimwipe wiper S-200 manufactured by Nippon Paper Crecia Co., Ltd. are applied to a 15 mm square elastic body (Maped (France) plastic eraser model number 1156SMTR00). After mounting, a load of 200 g was applied, and an abrasion resistance test was performed by rubbing 20,000 times at a stroke of 30 mm and 70 r/min (90 reciprocations per minute). After the wear resistance test, the contact angle and sliding angle were measured in the same manner as in (1) and (2) above.

Table 1 shows the results. Note that dD, dP and dH in the Hansen solubility parameters of isopropyl alcohol are values registered in the database, dD = 15.8 (J/cm ³ ) ^0.5 , dP = 6.1 (J/cm ³ ) ^{0 .5} , dH = 16.4 (J/cm ³ ) ^0.5 , and dD, dP and dH in the Hansen solubility parameters of Novec 7200 are the values registered in the database and dD = 13.1 (J/cm ³ ) ^0.5 , dP=2.8 (J/cm ³ ) ^0.5 , dH=2.1 (J/cm ³ ) ^0.5 . dD, dP and dH in the Hansen solubility parameters of perfluorohexane are the values registered in the database, dD = 12.1 (J/cm ³ ) ^0.5 , dP = 0 (J/cm ³ ) ^0.5 , dH = 0 (J/cm ³ ) ^0.5 , and dD, dP, and dH in the Hansen solubility parameter of KBM603 are values measured and calculated by the solubility sphere method, and dD = 16.6 (J/cm ³ ). ^0.5 , dP=7.2 (J/cm ³ ) ^0.5 , dH=12.45 (J/cm ³ ) ^0.5 .

In the measurement of the Hansen solubility parameter by the solubility sphere method, 1 mL of a solvent (source: Polymer Handbook 4th edition) with a known solubility parameter shown below and 1 mL of the target compound were added to a transparent container to prepare a mixed solution. The obtained mixture was shaken, the appearance of the liquid was visually observed, and the solubility of the target compound in the solvent was evaluated based on the following evaluation criteria based on the obtained observation results. When the evaluation criterion was 1 or 2, it was determined that the solvent dissolved the measurement sample, and when the evaluation criterion was 0, it was determined that the solvent did not dissolve the measurement sample. The numbers shown in parentheses after the names of the solvents described below are the evaluation results of the solubility of KBM603 in each solvent.
(Evaluation Criteria) 2: Appearance of mixed liquid is translucent.
1: Appearance of mixed liquid is colorless and transparent.
0: The appearance of the mixed liquid is cloudy.
(Solvent) Hexane (1), HFC-365mfc (1), 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane (0), HFE7000 (1), hexadecane (0), p-xylene (2), isoamyl acetate (1), 2-propanol (1), diacetone alcohol (1), diethylene glycol (2), propylene carbonate (1), ethylene glycol (2), dimethyl sulfoxide (2), ethanol (1)

According to the mixed composition of the present invention, a laminate including the substrate (s) and the water-repellent layer (r) can be formed in one step (one-liquid) by vapor deposition. It was found that the nitrogen content was 0.30 atomic % or more and 10 atomic % or less. It was also found that the laminate has excellent abrasion resistance on the surface of the water-repellent layer (r).

The laminate of the present invention can be used for display devices such as touch panel displays, optical elements, semiconductor elements, building materials, nanoimprint technology, solar cells, window glass for automobiles and buildings, metal products such as cookware, ceramic products such as tableware, and plastics. It is industrially useful because it can be suitably formed into a film on automotive parts and the like. It is also preferably used for items such as kitchens, bathrooms, washbasins, mirrors, and members around toilets.

Claims

A laminate comprising a substrate (s) and a water-repellent layer (r),
A laminate in which the water-repellent layer (r) has a nitrogen content of 0.30 atomic % or more and 10 atomic % or less.
After rubbing the surface of the water-repellent layer (r) 20,000 times with a load of 200 g per area of 1.5 cm × 1.5 cm, (i) the water contact angle is 105 ° or more, and 2. The laminate according to claim 1, which satisfies at least one of (ii) a water sliding angle of less than 45[deg.].
The water-repellent layer (r) is
an organosilicon compound (A) having a fluoropolyether structure represented by the following formula (a1);
3. The laminate according to claim 1, which is a cured product of a mixed composition of an organosilicon compound (C) having an amino group or amine skeleton represented by any one of the following formulas (c1) to (c3).

In the above formula (a1),
Rf a26 , Rf a27 , Rf a28 , and Rf a29 are each independently a fluorinated alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom ; When a plurality of Rf a26 are present, a plurality of Rf a26 may be different, when a plurality of Rf a27 are present, a plurality of Rf a27 may be different, and when a plurality of Rf a28 are present, a plurality of Rf a28 may be different from each other, and when a plurality of Rf a29 are present, the plurality of Rf a29 may be different,
R 25 and R 26 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogenated alkyl group having 1 to 4 carbon atoms in which one or more hydrogen atoms are substituted with halogen atoms group, at least one of R 25 and R 26 bonded to one carbon atom is a hydrogen atom ; When doing, multiple R 26 may be different,
R 27 and R 28 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a single bond ; When a plurality of R 28 are present, the plurality of R 28 may be different,
R 29 and R 30 are each independently an alkyl group having 1 to 20 carbon atoms, and when a plurality of R 29 are present, the plurality of R 29 may be different, and when a plurality of R 30 are present may have different R 30s ,
M 7 is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, -C(=O)NR-, - CH═CH— or —C 6 H 4 — (phenylene group), 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 M 7 is When a plurality of M7 are present, the plurality of M7 may be different,
M 5 is a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and when multiple M 5 are present, the multiple M 5 may be different,
M 10 is a hydrogen atom or a halogen atom,
M 8 and M 9 are each independently a hydrolyzable group, a hydroxy group, or —(CH 2 ) e7 —Si(OR 14 ) 3 , e7 is 1 to 5, and R 14 is a methyl group or an ethyl group, and when there are a plurality of M 8 , the plurality of M 8 may be different, and when there is a plurality of M 9 , the plurality of M 9 may be different,
f21, f22, f23, f24, and f25 are each independently an integer of 0 to 600, and the total value of f21, f22, f23, f24, and f25 is 13 or more,
f26 is an integer from 0 to 20,
f27 is each independently an integer of 0 to 2,
g21 is an integer of 1 to 3, g22 is an integer of 0 to 2, g21 + g22 ≤ 3,
g31 is an integer of 1 to 3, g32 is an integer of 0 to 2, g31 + g32 ≤ 3,
M 10 -, -Si (M 9 ) g31 (H) g32 (R 30 ) 3-g31-g32 , f21 -{C(R 25 )(R 26 )}-units (U a1 ), f22 -{C(Rf a26 )(Rf a27 )}-unit (U a2 ), f23 -{Si(R 27 )(R 28 )}-unit (U a3 ), f24-{Si(Rf a28 )(Rf a29 )}-units (U a4 ), f25 -M 7 -units (U a5 ), and f26 -[C(M 5 ){(CH 2 ) f27 -Si(M 8 ) g21 (H) g22 (R 29 ) 3-g21-g22 }]-unit (U a6 ) has M 10 - at one end in formula (a1), and -Si(M 9 ) g31 (H) g32 ( R 30 ) 3-g31-g32 are the other ends, and are arranged in an order that forms a fluoropolyether structure at least in part, and each unit can be in any order as long as —O— is not continuous with —O— Join side by side.

In the above formula (c1),
R x11 , R x12 , R x13 , and R x14 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when multiple R x11 are present, the multiple R x11 are different. may be different when there are a plurality of R x12 , and when there are a plurality of R x13 , a plurality of R x13 may be different, and when there are a plurality of R x14 may be different from each other in a plurality of R x14 ,
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 fluorine atoms or a fluorine atom, and a plurality of Rf x11 are present When there is a plurality of Rf x11 may be different, when there are a plurality of Rf x12 , a plurality of Rf x12 may be different, and when there are a plurality of Rf x13 , a plurality of Rf x13 may be different may be different, and if there are multiple Rf x14 , the multiple Rf x14 may be different,
R x15 is an alkyl group having 1 to 20 carbon atoms, and when a plurality of R x15 are present, the plurality of R x15 may be different,
X 11 is a hydrolyzable group, and when a plurality of X 11 are present, the plurality of X 11 may be different,
Y 11 is -NH- or -S-, and when a plurality of Y 11 are present, the 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 0 to 10,
p6 is an integer from 1 to 3,
having at least one Y 11 which is —NH— if Z 11 is not an amino group, and Z 11 is an amino group if all Y 11 are —S— or p5 is 0;
Z 11 -, -Si(X 11 ) p6 (R x15 ) 3-p6 , p1 -{C(R x11 )(R x12 )}-units (U c11 ), p2 -{C(Rf x11 ) (Rf x12 )}-unit (U c12 ), p3-{Si(R x13 )(R x14 )}-unit (U c13 ), p4-{Si(Rf x13 )(Rf x14 )} - unit (U c14 ), p5 -Y 11 - units (U c15 ), Z 11 - becomes one end of the compound represented by formula (c1), and -Si(X 11 ) p6 (R x15 ) Unless 3-p6 is the other end and —O— is not linked to —O—, each unit is linked in any order.

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 ; When a plurality of R x21 are present, the plurality of R x21 may be different,
Rf x20 and Rf x21 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom, and when there are multiple Rf x20 , multiple Rf x20 may be different, and when there are a plurality of Rf x21 , a plurality of Rf x21 may be different,
R x22 and R x23 are each independently an alkyl group having 1 to 20 carbon atoms, and when there are a plurality of R x22 and R x23 , a plurality of R x22 and R x23 may be different,
X 20 and X 21 are each independently a hydrolyzable group, and when multiple X 20 and X 21 are present, multiple X 20 and X 21 may be different,
p20 is an integer of 1 to 30, p21 is an integer of 0 to 30, and at least one of the repeating units bracketed with p20 or p21 is replaced 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-{C( Rx20 )( Rx21 )}-units ( Uc20 ), p21-{C( Rfx20 )( Rfx21 )}-units ( Uc21 ) are p20 units ( U c20 ) or p21 units (U c21 ) need not be contiguous, and each unit (U c21 ) and unit (U c20 ) can be arranged in any order and combined to form the formula (c2). One end of the compound is -Si(X 20 ) p22 (R x22 ) 3-p22 , and the other end is -Si(X 21 ) p23 (R x23 ) 3-p23 .

In the above formula (c3),
Z 31 and Z 32 are each independently a reactive functional group other than a hydrolyzable group and a hydroxy group. The reactive functional group is a vinyl group, α-methylvinyl group, styryl group, methacryloyl group, acryloyl group, amino group, epoxy group, ureido group, or mercapto group,
R x31 , R x32 , R x33 and R x34 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when there are multiple R x31 , the multiple R x31 may be different. may be different when there are a plurality of R x32 , and when there are a plurality of R x33, a plurality of R x33 may be different, and when there are a plurality of R x34 may be different from each other in a plurality of R x34 ,
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 fluorine atoms or a fluorine atom, and a plurality of Rf x31 are present When there are multiple Rf x31, the plurality of Rf x31 may be different, and when there are multiple Rf x32 , the plurality of Rf x32 may be different, and when there are multiple Rf x33 , the plurality of Rf x33 may be different. may be different, and if there are multiple Rf x34 , the multiple Rf x34 may be different,
Y 31 is —NH—, —N(CH 3 )— or —O—, and when there are a plurality of Y 31 , the plurality of Y 31 may be different,
X 31 , X 32 , X 33 and X 34 are each independently —OR c (R c is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or amino-C 1-3 alkyldi-C 1-3 alkoxysilyl is a group), and when a plurality of X 31 are present, the plurality of X 31 may be different, when a plurality of X 32 are present, the plurality of X 32 may be different, and X 33 is When a plurality of X 33 are present, the plurality of X 33 may be different, and when a plurality of X 34 are present, the plurality of X 34 may be different,
p31 is an integer of 0 to 20, p32, p33, and p34 are each independently an integer of 0 to 10, p35 is an integer of 0 to 5, and p36 is an integer of 1 to 10 and 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 is -NH- or -N(CH 3 )-, and a compound represented by formula (c3) p31 -{C(R x31 )(R x32 )}-units, unless one end of is Z 31 - and the other end is Z 32 -, and -O- is not linked to -O- (U c31 ), p32-{C(Rf x31 )(Rf x32 )}-units (U c32 ), p33-{Si(R x33 )(R x34 )}-units (U c33 ), p34 -{Si(Rf x33 )(Rf x34 )}-units (U c34 ), p35 -Y 31 -units (U c35 ), p36 -{Si(X 31 )(X 32 )-O }-unit (U c36 ) and p37 -{Si(X 33 )(X 34 )}-units (U c37 ) are arranged and bonded in any order.
A window film or touch panel display comprising the laminate according to any one of claims 1 to 3.
A method for producing a laminate having a substrate (s) and a water-repellent layer (r),
A mixed composition of an organosilicon compound (A) having a fluoropolyether structure, an organosilicon compound (C) having an amino group or an amine skeleton, and a solvent, wherein the organosilicon compound ( a step of heating a mixed composition in which the mass ratio of A) is more than 1% by mass and the mass ratio of the organosilicon compound (C) is 0.1% by mass or more; A method for producing a laminate, comprising a step of forming a water-repellent layer (r) by vacuum deposition on a substrate (s).
Furthermore, a step of forming a layer (X) different from the substrate (s) and the water-repellent layer (r) on the substrate (s),
6. The manufacturing method according to claim 5, wherein the mixed composition after heating is vacuum-deposited on the layer (X) provided on the substrate (s) to form the water-repellent layer (r).
Furthermore, a step of hydrophilizing the surface of the substrate (s) or the surface of the layer (X) provided on the substrate (s),
7. The manufacturing method according to claim 5 or 6, wherein the mixed composition after heating is vacuum-deposited onto the hydrophilized surface of the substrate (s) or the hydrophilized surface of the layer (X).