TW202405053A - Curable composition - Google Patents

Abstract

The present invention provides a curable composition comprising: component (A): a fluoropolyether group-containing acrylic compound containing a acrylic group, a hydrolyzable silane group, and a fluoropolyether group; component (B): a fluoropolyether group-containing silane compound containing a fluoropolyether group and a hydrolyzable silyl group; component (C): a cross-linking agent; component (D): a catalyst; component (E): a radical polymerization initiator; and component (F): a fluoropolyether group-containing alcohol.

Description

Hardening composition

This disclosure relates to curable compositions containing fluorine-containing compounds.

It is known that a composition containing a certain fluorine-containing compound can impart excellent water repellency, oil repellency, antifouling properties, etc. to a cured product (Patent Documents 1 and 2).

[Prior technical literature]

[Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2019-6843

[Patent Document 2] International Publication No. 2019/088126

The fluorine-containing polyether group-containing acrylic compound described in Patent Document 1 is cured by ultraviolet irradiation. However, in areas where ultraviolet irradiation is difficult, it cannot be sufficiently cured and uncured portions are generated. In addition, the obtained hardened material has a low elastic modulus and poor elongation. Patent document 2 The contained fluoropolyether-based silane compound can be hardened by moisture (moisture), but the hardening speed is slow and the liquid may spread and drip during coating.

An object of this disclosure is to provide a curable composition excellent in curability.

This disclosure contains the following aspects.

[1] A hardening composition containing:

Component (A): A fluoropolyether-based acrylic compound containing an acrylic group, a hydrolyzable silane group, and a fluoropolyether group,

Component (B): a fluoropolyether-based silane compound containing a fluoropolyether group and a hydrolyzable silica group,

Ingredient (C): cross-linking agent,

Ingredients (D): Catalyst,

Ingredient (E): free radical polymerization initiator, and

Ingredient (F): Fluorine-containing polyether alcohol.

[2] The curable composition according to the above [1], wherein the content of component (F) is 0.5 to 30 mass % with respect to the total amount of component (A) to component (F).

[3] The curable composition according to the above [1] or [2], wherein the content of component (F) is 0.5 to 5% by mass relative to the total amount of component (A) to component (F).

[4] The curable composition according to any one of the above [1] to [3], wherein the fluorine-containing polyether alcohol is a fluorine-containing polyether alcohol represented by the following formula (F1) or (F2) Ether-based carboxylic acid compounds,

R ^F5 -X ^L -OH (F1)

HO-X ^L -R ^F6 -X ^L -OH (F2)

In the formula:

R ^F5 are independently Rf ⁵ -R ^FF -O _q5 -;

R ^F6 - is Rf ⁶ _p5 -R ^FF -O _q5 -;

Rf ⁵ are each independently a C _1-16 alkyl group that may be substituted by 1 or more than 1 fluorine atom;

Rf ⁶ is a C _1-6 alkylene group which may be substituted by 1 or more than 1 fluorine atom;

R ^FF are independently divalent fluoropolyether groups;

p5 is 0 or 1;

q5 are independently 0 or 1;

X ^L is independently a single bond or a divalent base.

[5] The curable composition according to the above [4], wherein R ^FF are each independently a group represented by the following formula:

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ R ^Fa ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f -

In the formula, R ^Fa are independently a hydrogen atom, a fluorine atom or a chlorine atom,

a, b, c, d, e and f are each independently an integer from 0 to 200. The sum of a, b, c, d, e and f is more than 1. Mark a, b, c, d, e or f The order in which the repeating units enclosed in parentheses are present in the formula is arbitrary. However, when all R ^Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1. above.

[6] The curable composition according to the above [4] or [5], wherein X ^L is independently a single bond, C _1-6 alkylene group, -(CH ₂ ) _z21 -O-(CH ₂ ) _z22 - (in the formula, z21 is an integer from 0 to 6, z22 is an integer from 0 to 6), or -(CH ₂ ) _z23 -phenylene-(CH ₂ ) _z24 - (in the formula, z23 is 0 to 6, z24 is an integer from 0 to 6).

[7] The curable composition according to any one of the above [1] to [6], wherein the fluorine-containing polyether group-containing acrylic compound contains the following formula (A1), (A2) or (A3) The compound shown is

R ^F1 -X ^A -X ^B R ^Ac _m (A1)

R ^Ac _m X ^B -X ^A -R ^F2 -X ^A -X ^B R ^Ac _m (A2)

R ^Ac _m X ^B -X ^A -(R ^F2 -R ^g -R ^a (R ^Ac ) _m3 -R ^g ) _x -R ^F2 -X ^A -X ^B R ^Ac _m (A3)

In the formula:

R ^F1 is Rf ¹ -R ^F -O _q -,

R ^F2 are independently -Rf ² _p -R ^F -O _q -,

Rf ¹ is a C _1-16 alkyl group which may be substituted by 1 or more than 1 fluorine atom,

Rf ² is a C _1-6 alkylene group which may be substituted by 1 or more than 1 fluorine atom,

R ^F are independently divalent fluoropolyether groups,

p is 0 or 1,

q is independently 0 or 1,

X ^A is independently a single bond or a divalent organic group,

X ^B are independently the basis of (m+1) valence,

However, in each formula, at least one X ^B is a (m+1) valent group containing a hydrolyzable silicon group,

R ^Ac are each independently -X ^D -X ^E (-X ^F -OCO-CR ⁵ =CH ₂ ) _m' ,

X ^D is a single bond or a divalent base,

X ^E is the basis of a single bond or (m'+1) valence,

X ^F are independently single bonds or divalent bases,

R ⁵ is a hydrogen atom, a halogen atom, or an organic group with one valence from 1 to 8 carbon atoms,

m’ is an integer from 1 to 10,

m are independently integers from 0 to 10,

R ^a are independently organic radicals with (m3+2) valence,

m3 is an integer from 0 to 4,

However, at least one of m and m3 is 1 or more,

R ^g is independently -NR ^c CO-R ^e -, -NR ^c COO-R ^e -, or -NR ^c CONR ^c -R ^e -, where the left side of these groups is bonded to R ^a ,

R ^c is each independently a hydrogen atom, C _1-6 alkyl group, or C _6-16 aryl group,

R ^e are each independently a single bond or a divalent organic group,

x is an integer above 1.

[8] The curable composition according to the above [7], wherein R ^F are each independently a group represented by the following formula:

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ R ^Fa ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f -

In the formula, R ^Fa are independently a hydrogen atom, a fluorine atom or a chlorine atom,

a, b, c, d, e and f are each independently an integer from 0 to 200. The sum of a, b, c, d, e and f is more than 1. Mark a, b, c, d, e or f The order in which the repeating units enclosed in parentheses are present in the formula is arbitrary. However, when all R ^Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1. above.

[9] The curable composition according to the above [7] or [8], wherein R ^F are each independently the following formula (f1), (f2), (f3), (f4), (f5) , or the basis shown in (f6):

-(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1)

In the formula, d is an integer from 1 to 200, and e is 0 or 1;

-(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f2)

In the formula, c and d are independently integers from 0 to 30;

e and f are independently integers from 1 to 200;

The sum of c, d, e and f is an integer from 10 to 200;

The order of the repeating units marked c, d, e or f and enclosed in parentheses in the formula is arbitrary;

-(R ⁶ -R ⁷ ) _g - (f3)

In the formula, R ⁶ is OCF ₂ or OC ₂ F ₄ ;

R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of 2 or 3 groups selected from these groups;

g is an integer from 2 to 100;

-(R ⁶ -R ⁷ ) _g -R ^r -(R ^7' -R ^6' ) _g' - (f4)

In the formula, R ⁶ is OCF ₂ or OC ₂ F ₄ ,

R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of 2 or 3 groups independently selected from these groups,

R ^6' is OCF ₂ or OC ₂ F ₄ ,

R ^7' is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of 2 or 3 groups independently selected from these groups. ,

g is an integer from 2 to 100,

g’ is an integer from 2 to 100,

R ^r is

In the formula, * shows the bonding position;

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f5)

In the formula, e is an integer from 1 to 200, a, b, c, d and f are each independently an integer from 0 to 200, and the sum of a, b, c, d, e and f is at least 1. In addition , the order of the repeating units marked a, b, c, d, e or f and enclosed in brackets in the formula is arbitrary;

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f6)

In the formula, f is an integer from 1 to 200, a, b, c, d and e are each independently an integer from 0 to 200, and the sum of a, b, c, d, e and f is at least 1. In addition , the order of the repeating units marked a, b, c, d, e or f and enclosed in brackets in the formula is arbitrary.

[10] The curable composition according to any one of [7] to [9] above, wherein X ^E is a single bond.

[11] The curable composition according to any one of [7] to [10] above, wherein X ^E is -X ^G -X ^H ;

X ^G is a single key,

C _1-6 alkylene group,

-(CH ₂ ) _z9 -O-(CH ₂ ) _z10 -(in the formula, z9 is an integer from 0 to 6, z10 is an integer from 0 to 6), or -(CH ₂ ) _z11 -phenylene-(CH ₂ ) _z12 - (in the formula, z11 is an integer from 0 to 6, z12 is an integer from 0 to 6);

X ^H is as follows

R ⁸ is a hydrogen atom or a C _1-6 alkyl group.

[12] The curable composition according to any one of the above [7] to [11], wherein X ^D is -O-, -CO-, -COO-, -OCO-, -CONH-, - NHCO-, -OCONH-, -NHCOO-, -NH-CO-NH-, -CH ₂ CH(OH)CH ₂ -, -CH(CH ₂ OH)CH ₂ --(OSiR ¹⁴ ₂ ) _d5 -;

In the formula, * and ** show the bonding position, * is bonded to X ^B , and ** is bonded to X ^E ;

R ¹⁴ is C _1-6 alkyl or C _6-16 aryl;

d5 is an integer from 1 to 10.

[13] The curable composition according to any one of [7] to [12] above, wherein X ^F is a single bond,

C _1-6 alkylene group,

-(CH ₂ ) _z5 -O-(CH ₂ ) _z6 -(in the formula, z5 is an integer from 0 to 6, z6 is an integer from 0 to 6), or -(CH ₂ ) _z7 -phenylene-(CH ₂ ) _z8 -(In the formula, z7 is an integer from 0 to 6, z8 is an integer from 0 to 6).

[14] The curable composition according to any one of [7] to [13] above, wherein R ⁵ is a hydrogen atom or a methyl group.

[15] The curable composition according to any one of the above [7] to [14], wherein X ^A is each independently a single bond or a group represented by the following formula;

-(C _α R ¹¹ _{2 α} ) _s1 -R ¹² _t1 -

In the formula:

R ¹¹ is independently a hydrogen atom or a fluorine atom,

α is independently an integer from 1 to 10,

R ¹² is independently -O-, -CO-, -NR ¹⁰ -, -CONR ¹⁰ -, -NR ¹⁰ CO-, -COO-, -OCO-, or -OCONH-,

R ¹⁰ is a hydrogen atom or C _1-6 alkyl group,

s1 is an integer from 0 to 3,

t1 is an integer from 0 to 3,

The total of s1 and t1 is more than 1,

The order in which the repeating units marked s1 or t1 and enclosed in parentheses in the formula are arbitrary.

[16] The curable composition according to any one of the above [7] to [15], wherein X ^A is -CONR ¹⁰ -C _{α 1} H _{2 α 1} -, -(C _{α 2} H _{2 α 2} )-OCONR ¹⁰ -, -(C _{α 3} H _{2 α 3} )-, or -(C _{α 4} H _{2 α 4} )-O-(C _{α 5} H _{2 α 5} ),

R ¹⁰ is a hydrogen atom or C _1-6 alkyl group,

α 1 is an integer from 1 to 10,

α 2 is an integer from 1 to 10,

α 3 is an integer from 1 to 10,

α 4 is an integer from 0 to 6,

α 5 is an integer from 0 to 6.

[17] The curable composition according to any one of the above [7] to [16], wherein X ^B is each independently a group including a group represented by the following formula;

SiR ¹ _nb R ^sb _4-nb

In the formula:

R ¹ is a hydroxyl group or a hydrolyzable group,

R ^sb is a single bond,

nb is 1 or 2.

[18] The curable composition according to any one of the above [7] to [17], wherein X ^B is each independently a group represented by X ^Ba (R ^Si ) _na ;

In the formula:

X ^Ba are independently the basis of (m+na+1) valence,

R ^Si are independently -X ^C -SiR ¹ _n' R ² _3-n' ,

X ^C is a divalent organic radical with carbon number from 1 to 10,

R ¹ are each independently a hydroxyl group or a hydrolyzable group,

R ² are each independently a hydrogen atom or a monovalent organic group,

n’ is an integer from 1 to 3,

na is an integer from 1 to 10.

[19] The curable composition according to the above [18], wherein X ^C is a C _1-6 alkylene group,

-(CH ₂ ) _z1 -O-(CH ₂ ) _z2 -(in the formula, z1 is an integer from 0 to 6, z2 is an integer from 0 to 6), or -(CH ₂ ) _z3 -phenylene-(CH ₂ ) _z4 -(In the formula, z3 is an integer from 0 to 6, z4 is an integer from 0 to 6).

[20] The curable composition according to the above [18] or [19], wherein n' is 3.

[21] The curable composition according to any one of [18] to [20] above, wherein X ^Ba is a trivalent group, n is 1, and m is 1.

[22] The curable composition according to any one of the above [18] to [21], wherein X ^Ba is N or -C(-O-)-, n is 1, and m is 1.

[23] The curable composition according to any one of the above [7] to [22], wherein the formula (A3) is

R ^b ₂ NR ^d -CO-(R ^F2 -CO-NR ^c -R ^a (R ^Ac ) _m3 -NR ^c -CO) _x -R ^F2 -CO-R ^d -NR ^b ₂ (A3-b)

In the formula,

R ^b is independently R ^Si , R ^Ac , or R ^c ,

However, at least one of R ^b is R ^Si ,

R ^Si are independently -X ^C -SiR ¹ _n' R ² _3-n' ,

X ^C is a divalent organic radical with carbon number from 1 to 10,

R ¹ are each independently a hydroxyl group or a hydrolyzable group,

R ² are each independently a hydrogen atom or a monovalent organic group,

n’ is an integer from 1 to 3,

R ^d are each independently a single bond or a divalent organic group,

R ^F2 , R ^a , R ^c , R ^Ac , m3, and x are synonymous with the description in claim 4.

[24] The curable composition according to the above [23], wherein one of the R ^b 's bonded to the N atoms at each terminal in the formula (A3) is R ^Si and the others are R ^c or R ^Ac .

[25] The curable composition according to the above [23] or [24], wherein R ^d is each independently a single bond, or -(CH ₂ ) _z17 -NR ¹⁰ -(CH ₂ ) _z18 -(Formula , R ¹⁰ is a hydrogen atom or a C _1-6 alkyl group, z17 is an integer from 0 to 6, and z18 is an integer from 0 to 6).

[26] The curable composition according to any one of the above [7] to [25], wherein R ^a is each independently a group represented by the following formula:

-R ⁹ -(R ^a' -R ⁹ ) _k -

In the formula:

R ⁹ are each independently C _1-6 alkylene group,

R ^a' are independently 3-valent bases,

k is an integer from 1 to 4.

[27] The curable composition as described in the above [26], wherein R ^a' is independently N, -C(-O-)-, and carbon-carbon atoms, and may include amine bonds or amide bonds. A trivalent group of bonding, urethane bonding, urea bonding, ether bonding, or ester bonding.

[28] The curable composition according to the above [26] or [27], wherein k is 1 or 2.

[29] The curable composition according to any one of the above [7] to [28], wherein R ^c is each independently a hydrogen atom or a C _1-6 alkyl group.

[30] The curable composition according to any one of [7] to [29] above, wherein x is an integer from 1 to 5.

[31] The curable composition according to any one of [7] to [30] above, wherein the fluorine-containing polyether group-containing acrylic compound contains a compound represented by formula (A1) or (A2).

[32] The curable composition according to any one of the above [7] to [31], wherein the fluorine-containing polyether group-containing acrylic compound contains a compound represented by formula (A3).

[33] The curable composition according to any one of the above [1] to [32], wherein the fluorine-containing polyether group-containing silane compound is represented by the following formula (B1) or (B2). Fluoropolyether-based silane compound,

R ^F3 _α -X ^Z -R ^Si _β (B1)

R ^Si _γ -X ^Z -R ^F4 -X ^Z -R ^Si _γ (B2)

In the formula:

R ^F3 are independently Rf ³ -R ^FB -O _q3 -;

R ^F4 is -Rf ⁴ _p3 -R ^FB -O _q3 -;

Rf ³ are each independently a C _1-16 alkyl group that may be substituted by 1 or more than 1 fluorine atom;

Rf ⁴ is a C _1-6 alkylene group which may be substituted by 1 or more than 1 fluorine atom;

R ^FB are independently divalent fluoropolyether groups;

p3 is 0 or 1;

q3 is independently 0 or 1;

R ^Si is independently a monovalent group including a Si atom bonded to a hydroxyl group, a hydrolyzable group, a hydrogen atom or a monovalent organic group;

At least one R ^Si is a univalent group containing a Si atom bonded to a hydroxyl group or a hydrolyzable group;

X and ^Z are each independently a single bond or an organic group with a valence of 2 to 10;

α is an integer from 1 to 9;

β is an integer from 1 to 9;

γ is independently an integer from 1 to 9.

[34] The curable composition according to the above [33], wherein R ^Si is a group represented by the following formula (S1), (S2), (S3), (S4) or (S5):

-SiR ²⁵ _n1 R ²⁶ _3-n1 (S2)

-SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 (S3)

-CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 (S4)

-NR ^g1 R ^h1 (S5)

In the formula:

R ²⁵ is independently a hydroxyl group or a hydrolyzable group;

R ²⁶ are each independently a hydrogen atom or a monovalent organic group;

n1 is an integer from 0 to 3 in each (SiR ²⁵ _n1 R ²⁶ _3-n1 ) unit independently;

X ¹¹ is independently a single bond or a divalent organic group;

R ²⁷ are each independently a hydrogen atom or a monovalent organic group;

t is independently an integer above 2;

R ²⁸ is independently a hydrogen atom, a halogen atom or -X ¹¹ -SiR ²⁵ _n1 R ²⁶ _3-n1 ;

R ²⁹ are each independently a single bond, an oxygen atom, an alkylene group with 1 to 6 carbon atoms, or an alkyleneoxy group with 1 to 6 carbon atoms;

R ^a1 are independently -Z ¹ -SiR ²¹ _p1 R ²² _q1 R ²³ _r1 ;

Z ¹ is independently an oxygen atom or a divalent organic group;

R ²¹ are independently -Z ^1' -SiR ^21' _p1' R ^22' _q1' R ^23' _r1' ;

R ²² are each independently a hydroxyl group or a hydrolyzable group;

R ²³ are each independently a hydrogen atom or a monovalent organic group;

p1 are independently integers from 0 to 3;

q1 are independently integers from 0 to 3;

r1 are independently integers from 0 to 3;

Z ^1' are each independently an oxygen atom or a divalent organic group;

R ^21' are independently -Z ^1” -SiR ^22” _q1” R ^23” _r1” ;

R ^22' is independently a hydroxyl group or a hydrolyzable group;

R ^23' are each independently a hydrogen atom or a monovalent organic group;

p1’ are independently integers from 0 to 3;

q1’ are independently integers from 0 to 3;

r1’ are independently integers from 0 to 3;

Z ^1″ are independently oxygen atoms or divalent organic groups;

R ^22″ are each independently a hydroxyl group or a hydrolyzable group;

R ^23″ are each independently a hydrogen atom or a monovalent organic group;

q1” are independently integers from 0 to 3;

r1” are independently integers from 0 to 3;

R ^b1 are each independently a hydroxyl group or a hydrolyzable group;

R ^c1 are each independently a hydrogen atom or a monovalent organic group;

k1 are independently integers from 0 to 3;

l1 are independently integers from 0 to 3;

m1 are independently integers from 0 to 3;

R ^d1 are independently -Z ² -CR ³¹ _p2 R ³² _q2 R ³³ _r2 ;

Z ² are independently a single bond, an oxygen atom or a divalent organic group;

R ³¹ are independently -Z ^2' -CR ^32' _q2' R ^33' _r2' ;

R ³² are independently -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 ;

R ³³ are each independently a hydrogen atom, a hydroxyl group or a monovalent organic group;

p2 are independently integers from 0 to 3;

q2 are independently integers from 0 to 3;

r2 are independently integers from 0 to 3;

Z ^2' are independently a single bond, an oxygen atom or a divalent organic group;

R ^32' are independently -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 ;

R ^33' are independently a hydrogen atom, a hydroxyl group or a monovalent organic group;

q2’ are independently integers from 0 to 3;

r2’ are independently integers from 0 to 3;

Z ³ are independently a single bond, an oxygen atom or a divalent organic group;

R ³⁴ is independently a hydroxyl group or a hydrolyzable group;

R ³⁵ are each independently a hydrogen atom or a monovalent organic group;

n2 are independently integers from 0 to 3;

R ^e1 are independently -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 ;

R ^f1 are each independently a hydrogen atom, a hydroxyl group or a monovalent organic group;

k2 are independently integers from 0 to 3;

l2 are independently integers from 0 to 3;

m2 are independently integers from 0 to 3;

R ^g1 and R ^h1 are independently -Z ⁴ -SiR ²⁵ _n1 R ²⁶ _3-n1 , -Z ⁴ -SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 , -Z ⁴ -CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 ;

Z ⁴ are independently a single bond, an oxygen atom or a divalent organic group;

However, in the formulas (S1), (S2), (S3), (S4) and (S5), there is at least one Si atom bonded to a hydroxyl group or a hydrolyzable group.

[35] The curable composition according to any one of the above [1] to [32], wherein the fluorine-containing polyether group silane compound is a fluorine-containing polyether group represented by the following formula (B3) of silane compounds,

R ³⁹ _j -R ³⁸ -NR ³⁷ CO-(R ^F4 -CONR ³⁷ -R ³⁶ -NR ³⁷ CO) _r -R ^F4 -CONR ³⁷ -R ³⁸ -R ³⁹ _j (B3)

In the formula:

R ^F4 is -Rf ⁴ _p3 -R ^FB -O _q3 -;

Rf ⁴ is a C _1-6 alkylene group which may be substituted by 1 or more than 1 fluorine atom;

R ^FB are independently divalent fluoropolyether groups;

p3 is 0 or 1;

q3 is 0 or 1;

R ³⁶ are each independently a divalent organic group,

R ³⁷ is each independently a hydrogen atom or an organic group with one valence of carbon atoms from 1 to 8,

R ³⁸ are each independently an organic radical with (j+1) valence,

R ³⁹ are each independently -SiR ²⁵ _n1 R ²⁶ _3-n1 ,

R ²⁵ is independently a hydroxyl group or a hydrolyzable group;

R ²⁶ are each independently a hydrogen atom or a monovalent organic group;

n1 is an integer from 0 to 3 in each (SiR ²⁵ _n1 R ²⁶ _3-n1 ) unit independently;

j are independently integers from 1 to 9,

r is an integer above 1.

[36] The curable composition according to any one of the above [33] to [35], wherein R ^FB is each independently a group represented by the following formula:

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ R ^Fa ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f -

In the formula, R ^Fa are independently a hydrogen atom, a fluorine atom or a chlorine atom,

a, b, c, d, e and f are each independently an integer from 0 to 200. The sum of a, b, c, d, e and f is more than 1. Mark a, b, c, d, e or f The order of the repeating units enclosed in brackets in the formula is arbitrary. However, when all R ^Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1. above.

[37] The curable composition according to any one of the above [1] to [36], wherein the cross-linking agent is a compound represented by formula (C1),

(R ^g1 -O) _δ -Si-R ^g2 _4-δ (C1)

in the formula;

Each time R ^g1 appears, it is independently a hydrogen atom or a 1-valent organic group;

R ^g2 are independently univalent organic groups;

δ is an integer from 2 to 4.

[38] The curable composition according to any one of the above [1] to [37], wherein the cross-linking agent is tetraethoxysilane, tetramethoxysilane, or methyltriethoxysilane , methyl trimethyl Oxysilane, dimethyldimethoxysilane, dimethyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, tridecafluoro-n-octyltriethoxysilane Silane, or tridecafluoro-n-octyltrimethoxysilane.

[39] The curable composition according to any one of the above [1] to [38], wherein the catalyst is an acid, an alkali, a transition metal, or is selected from a tin-based catalyst and a titanium-based catalyst. , zirconia-based catalysts, bismuth-based catalysts, and metal complexes of organic amine-based catalysts.

[40] The curable composition according to any one of the above [1] to [39], wherein the catalyst is acetic acid, trifluoroacetic acid, ammonia, triethylamine, diethylamine, Ti, Ni, Sn, di-n-butyltin(IV) dilaurate, diisopropoxybis(acetylethylacetate)titanium, tetra-n-butoxytitanium, tetrakis-2-ethylhexyloxytitanium, tetraacetylacetyltitanium , Zirconium tetraacetyl acetonate, zirconium tetra-n-butoxide, zirconium dibutoxybis (ethyl acetate acetate), or bismuth (ethyl 2-hexanoate).

[41] The curable composition according to any one of the above [1] to [40], wherein the radical polymerization initiator is a diketone, a gallioin, a gallioin ether, or a thiophene ether. Oxonones, benzophenones, acetophenones, quinones, aminobenzoic acids, halogen compounds, acylphosphine oxides, or peroxides.

啉基-1-丙酮、2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁-1-酮、蒽醌、1,4-萘醌、2-二甲 基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸(正丁氧基)乙酯、4-二甲基胺基苯甲酸異戊酯、4-二甲基胺基苯甲酸2-乙基己酯、苯甲醯氯、三鹵甲基苯基碸、醯基氧化膦、或二-三級丁基過氧化物、苯甲醯甲酸甲酯、1-羥基-環己基-苯基-酮、1-〔4-(2-羥基乙氧基)-苯基〕-2-羥基-2-甲基-1-丙-1-酮、2-羥基-1-{4-〔4-(2-羥基-2-甲基-丙醯基)-苄基〕苯基}-2-甲基-丙-1-酮、2-甲基-1-(4-甲基硫基苯基)-2-

啉基丙-1-酮、2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-1-丁酮、2-(二甲基胺基)-2-〔(4-甲基苯基)甲基〕-1-〔4-(4-

啉基)苯基〕-1-丁酮、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、雙(η 5-2,4-環戊二烯-1-基)-雙(2,6-二氟-3-(1H-吡咯-1-基)-苯基)鈦、1,2-辛二酮，1-〔4-(苯基硫基)-,2-(O-苯甲醯基肟)〕、乙酮，1-〔9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基〕-,1-(0-乙醯肟)、2-羥基-2-甲基-1-苯基-丙-1-酮、2,4,6-三甲基苯甲醯基-二苯基-氧化膦、三級丁基氫過氧化物、氫過氧化異丙苯、二異丙苯氫過氧化物、對薄荷烷氫過氧化物、或三級甲基丁基氫過氧化物。 [42] The curable composition according to any one of the above [1] to [41], wherein the radical polymerization initiator is benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl Ether, thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4 ,4'-bis(diethylamino)benzophenone, acetophenone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone , 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl[4-(methylthio)phenyl]-2-

Phino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-

Phinylphenyl)-butan-1-one, anthraquinone, 1,4-naphthoquinone, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethyl (n-butoxy)ethyl aminobenzoate, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, benzoyl chloride, trihalogen Methylphenyl trisulfide, hydroxyl phosphine oxide, or di-tertiary butyl peroxide, methyl benzoate, 1-hydroxy-cyclohexyl-phenyl-one, 1-[4-(2-hydroxy Ethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propanol) methyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-

Oxylinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-

Phylinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-

Phylyl)phenyl]-1-butanone, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, bis( eta 5-2,4-cyclopentadiene-1- base)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyl oxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl oxime)-9H-carbazol-3-yl]-,1- (0-acetyl oxime), 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, tris Grade butyl hydroperoxide, cumene hydroperoxide, dicumyl hydroperoxide, p-menthane hydroperoxide, or tertiary methyl butyl hydroperoxide.

[43] The curable composition according to any one of [1] to [42] above, further containing a solvent.

[44] A hardened product obtained from the curable composition according to any one of the above [1] to [43].

[45] An article including a base material and a layer formed on the surface of the base material of the curable composition according to any one of the above [1] to [43].

According to the present disclosure, a curable composition excellent in curability can be provided.

As used in this specification, "monovalent organic group" means a monovalent group containing carbon. The monovalent organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. Derivatives of hydrocarbon groups refer to groups with one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the end of the hydrocarbon group or in the molecular chain. . In addition, when "organic group" is shown alone, it means a monovalent organic group. In addition, "divalent organic group" means a divalent group containing carbon. Examples of the bivalent organic group include a bivalent group in which one hydrogen atom is detached from the organic group. The same applies to an organic group having a valence of 3 or more, and means a group in which a predetermined number of hydrogen atoms are detached from the organic group.

When used in this specification, "hydrocarbon group" means a group containing carbon and hydrogen, and means a group in which a hydrogen atom is detached from a hydrocarbon. The hydrocarbon group is not particularly limited, but the series includes C _1-20 hydrocarbon groups, such as aliphatic hydrocarbon groups, aromatic hydrocarbon groups, etc. The above-mentioned "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. In addition, the hydrocarbon group may contain one or more than one ring structure. The hydrocarbyl group may be substituted by 1 or more than 1 substituent.

When used in this specification, the substituent of the "hydrocarbyl group" is not particularly limited, but the series includes, for example: halogen atoms, C _1-6 alkane that can be substituted by 1 or more than 1 halogen atoms. Base, C _2-6 alkenyl, C _2-6 alkynyl, C _3-10 cycloalkyl, C _3-10 unsaturated cycloalkyl, 5 to 10 membered heterocyclyl, 5 to 10 membered unsaturated One or more than one radical of a heterocyclic group, a C _6-10 aryl group and a 5 to 10-membered heteroaryl group.

When used in this specification, a "hydrolyzable group" means a group that can undergo a hydrolysis reaction, that is, a group that can be separated from the main skeleton of the compound through a hydrolysis reaction. Examples of hydrolyzable groups include -OR ^j , -OCOR ^j , -ON=CR ^j ₂ , -NR ^j ₂ , -NHR ^j , -NCO, -NCO, or halogen (in this equation, R ^j represents Substituted or unsubstituted C _1-4 alkyl), etc.

The hardening composition of the present disclosure includes:

Component (A): A fluoropolyether-based acrylic compound containing (meth)acrylic acid group, hydrolyzable silane group, and fluoropolyether group,

Component (B): a fluoropolyether-based silane compound containing a fluoropolyether group and a hydrolyzable silica group,

Ingredient (C): cross-linking agent,

Ingredients (D): Catalyst,

Ingredient (E): free radical polymerization initiator, and

Ingredient (F): Fluorine-containing polyether alcohol.

Component (A): An acrylic compound containing a (meth)acrylic acid group, a hydrolyzable silane group, and a fluoropolyether group containing a fluoropolyether group.

The curable composition of the present disclosure includes a fluorine-containing polyether group acrylic compound containing (meth)acrylic acid group, hydrolyzable silane group, and fluoropolyether group. The curable composition of the present disclosure has UV curability by virtue of the acrylic compound containing the above-mentioned fluorine-containing polyether group. Here, the (meth)acrylic acid group includes an acrylic acid group and a methacrylic acid group.

The above-mentioned fluoropolyether group-containing acrylic compound contains a (meth)acrylic acid group, a hydrolyzable silane group, and a fluoropolyether group in the molecule.

In a preferred embodiment, the above-mentioned fluorine-containing polyether group acrylic compound includes a compound represented by the following formula (A1), (A2) or (A3),

R ^F1 -X ^A -X ^B R ^Ac _m (A1)

R ^Ac _m X ^B -X ^A -R ^F2 -X ^A -X ^B R ^Ac _m (A2)

R ^Ac _m X ^B -X ^A -(R ^F2 -R ^g -R ^a (R ^Ac ) _m3 -R ^g ) _x -R ^F2 -X ^A -X ^B R ^Ac _m (A3)

In the formula:

R ^F1 is Rf ¹ -R ^F -O _q -,

R ^F2 are independently Rf ² _p -R ^F -O _q -,

Rf ¹ is a C _1-16 alkyl group which may be substituted by 1 or more than 1 fluorine atom,

Rf ² is a C _1-6 alkylene group which may be substituted by 1 or more than 1 fluorine atom,

R ^F are independently divalent fluoropolyether groups,

p is 0 or 1,

q is independently 0 or 1,

X ^A is independently a single bond or a divalent organic group,

X ^B are independently the basis of (m+1) valence,

However, in each formula, at least one X ^B is a (m+1) valent group containing a hydrolyzable silicon group,

R ^Ac are each independently -X ^D -X ^E (-X ^F -OCO-CR ⁵ =CH ₂ ) _m' ,

X ^D is a single bond or a divalent base,

X ^E is the basis of a single bond or (m'+1) valence,

X ^F are independently single bonds or divalent bases,

R ⁵ is a hydrogen atom, a halogen atom, or an organic group with one valence from 1 to 8 carbon atoms,

m’ is an integer from 1 to 10,

m are independently integers from 0 to 10,

R ^a are independently organic radicals with (m3+2) valence,

m3 is an integer from 0 to 4,

However, at least one of m and m3 is 1 or more,

R ^g is independently -NR ^c CO-R ^e -, -NR ^c COO-R ^e -, or -NR ^c CONR ^c -R ^e -, where the left side of these groups is bonded to R ^a ,

R ^c is each independently a hydrogen atom, C _1-6 alkyl group, or C _6-16 aryl group,

R ^e are each independently a single bond or a divalent organic group.

x is an integer above 1.

In one aspect, the above-mentioned fluorine-containing polyether group acrylic compound includes a compound represented by formula (A1) or (A2). For example, the above-mentioned fluorine-containing polyether group acrylic compound is a compound represented by formula (A1) or (A2).

In one aspect, the above-mentioned fluorine-containing polyether group-containing acrylic compound includes a compound represented by formula (A1). For example, the above-mentioned fluorine-containing polyether group acrylic compound is a compound represented by formula (A1).

In one aspect, the above-mentioned fluorine-containing polyether group acrylic compound includes a compound represented by formula (A2). For example, the above-mentioned fluorine-containing polyether group acrylic compound is a compound represented by formula (A2).

In one aspect, the above-mentioned fluorine-containing polyether group acrylic compound includes a compound represented by formula (A3). For example, the above-mentioned fluorine-containing polyether group acrylic compound is a compound represented by formula (A3).

In a preferred embodiment, the above-mentioned fluorine-containing polyether group acrylic compound includes a compound represented by formula (A2) and/or a compound represented by formula (A3). For example, the above-mentioned fluorine-containing polyether group acrylic compound is a compound represented by formula (A2) and/or a compound represented by formula (A3).

In another preferred embodiment, the above-mentioned fluorine-containing polyether group acrylic compound includes a compound represented by formula (A2) and a compound represented by formula (A3). For example, the above-mentioned fluorine-containing polyether group acrylic compound is a compound represented by formula (A2) and a compound represented by formula (A3).

Compounds having (meth)acrylic acid groups at both ends (for example, compounds represented by formula (A2) and compounds represented by formula (A3)) and compounds having (meth)acrylic acid groups at one end (for example, compounds represented by formula The molar ratio (two-terminal compound/single-terminal compound) of the compound represented by (A1) is preferably 50/50 to 100/0, more preferably 60/40 to 100/0, and still more preferably 90/10 to 100/0.

In the above formula (A1), R ^F1 is Rf ^{1 -RF} -O _q -.

In the above formulas (A2) and (A3), R ^F2 is -Rf ² _p -R ^F -O _q -.

In the above formula, Rf ¹ is a C _1-16 alkyl group which may be substituted by 1 or more than 1 fluorine atom.

The "C _1-16 alkyl group" in the above-mentioned C _1-16 alkyl group that can be substituted by one or more fluorine atoms can be a straight chain or a branched chain, preferably a straight chain or a branched chain of C _1-6 alkyl, especially C _1-3 alkyl, more preferably straight-chain C _1-6 alkyl, especially C _1-3 alkyl.

The above-mentioned Rf ¹ is preferably a C _1-16 alkyl group that can be substituted by one or more fluorine atoms, more preferably a CF ₂ HC _1-15 perfluoroalkylene group, and even more preferably a C _1-16 perfluoroalkyl group. Fluoroalkyl.

The above-mentioned C _1-16 perfluoroalkyl group can be a straight chain or branched chain, preferably a straight chain or branched chain C _1-6 perfluoroalkyl group, especially a C _1-3 perfluoroalkyl group, more preferably It is a linear C _1-6 perfluoroalkyl group, especially a C _1-3 perfluoroalkyl group, specifically -CF ₃ , -CF ₂ CF ₃ , or -CF ₂ CF ₂ CF ₃ .

In the above formula, Rf ² is independently a C _1-6 alkylene group which may be substituted by one or more than one fluorine atom.

The "C _1-6 alkylene group" in the above-mentioned C _1-6 alkylene group that can be substituted by one or more fluorine atoms can be a straight chain or a branched chain, preferably a straight chain or a branched chain. The C _1-3 alkylene group is more preferably a straight-chain C _1-3 alkylene group.

The above-mentioned Rf ² is preferably a C _1-6 alkylene group which may be substituted by one or more fluorine atoms, more preferably a C _1-6 perfluoroalkylene group, and even more preferably a C _1-3 perfluoro group. Alkylene.

The above-mentioned C _1-6 perfluoroalkylene group can be a straight chain or a branched chain, preferably a straight chain or branched chain C _1-3 perfluoroalkylene group, and more preferably a straight chain C _1-3 perfluoroalkylene group. Fluoroalkyl, specifically -CF ₂ -, -CF ₂ CF ₂ -, or -CF ₂ CF ₂ CF ₂ -.

In the above formula, p is 0 or 1. In one aspect, p is 0. In other aspects, p is 1.

In the above formula, q is independently 0 or 1. In one aspect, q is 0. In other aspects, q is 1.

In the above formulas (A1) to (A3), R ^F is each independently a divalent fluoropolyether group.

^RF is preferably a linear divalent fluoropolyether group. By using a linear divalent fluoropolyether group, the viscosity becomes relatively low, and the coating properties and operability are improved.

R ^F is preferably a base represented by the following formula:

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ R ^Fa ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f -

In the formula:

R ^Fa are each independently a hydrogen atom, a fluorine atom or a chlorine atom,

a, b, c, d, e and f are each independently an integer from 0 to 200, and the sum of a, b, c, d, e and f is 1 or more. The order of presence of each repeating unit marked a, b, c, d, e or f and enclosed in parentheses in the formula is arbitrary. However, when all R ^Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1 or more.

R ^Fa is preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom. However, when all R ^Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1 or more.

Preferably, a, b, c, d, e and f can each independently be an integer from 0 to 100.

The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. The sum of a, b, c, d, e and f is preferably 200 or less, more preferably 100 or less, still more preferably 60 or less, and may be, for example, 50 or less or 30 or less.

These repeating units may be linear or branched, and may include cyclic structures. For example, -(OC ₆ F ₁₂ )- can be -(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF ₂ CF(CF ₃ )CF ₂ CF ₂ CF ₂ )-, -(OCF ₂ CF ₂ CF(CF ₃ )CF ₂ CF ₂ )-, -(OCF ₂ CF ₂ CF ₂ CF(CF ₃ )CF ₂ )- , -(OCF ₂ CF ₂ CF ₂ CF ₂ CF(CF ₃ ))-etc. -(OC ₅ F ₁₀ )- can be -(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ CF ₂ )-, -(OCF ₂ CF(CF ₃ ) CF ₂ CF ₂ )-, -(OCF ₂ CF ₂ CF(CF ₃ )CF ₂ )-, -(OCF ₂ CF ₂ CF ₂ CF(CF ₃ ))-, etc. -(OC ₄ F ₈ )- can be -(OCF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ )-, -(OCF ₂ CF(CF ₃ )CF ₂ )- ,-(OCF ₂ CF ₂ CF(CF ₃ ))-,-(OC(CF ₃ ) ₂ CF ₂ )-,-(OCF ₂ C(CF ₃ ) ₂ )-,-(OCF(CF ₃ )CF( Any one of CF ₃ ))-, -(OCF(C ₂ F ₅ )CF ₂ )- and -(OCF ₂ CF(C ₂ F ₅ ))-. -(OC ₃ F ₆ )- (that is, in the above formula, R ^Fa is a fluorine atom) can be -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )- and -(OCF ₂ CF (CF ₃ )) - any one. -(OC ₂ F ₄ )- can be any one of -(OCF ₂ CF ₂ )- and -(OCF(CF ₃ ))-.

The above-mentioned ring structure may be a three-member ring, a four-member ring, a five-member ring, or a six-member ring as described below.

[In the formula, * shows the bonding position]

The above-mentioned ring structure can preferably be a four-member ring, a five-member ring, or a six-member ring, and more preferably, it can be a four-member ring or a six-member ring.

The repeating unit having a ring structure is preferably the following unit.

[In the formula, * shows the bonding position]

In one aspect, the repeating units are linear. By forming the repeating unit into a linear chain, the durability of the hardened material layer can be improved.

In one aspect, the repeating units are in the form of branched chains.

In one aspect, R ^F is each independently a base represented by any one of the following formulas (f1) to (f6).

-(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1)

[In the formula, d is an integer from 1 to 200, e is 0 or 1, preferably 1];

-(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f2)

[In the formula, c and d are each independently an integer from 0 to 30, e and f are each independently an integer from 1 to 200,

The sum of c, d, e and f is 2 or more,

The order of the repeating units marked c, d, e or f and enclosed in parentheses in the formula is arbitrary];

-(R ⁶ -R ⁷ ) _g - (f3)

[In the formula, R ⁶ is OCF ₂ or OC ₂ F ₄ ,

R ⁷ can be a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of 2 or 3 groups independently selected from these groups. ,

g is an integer from 2 to 100];

-(R ⁶ -R ⁷ ) _g -R ^r -(R ^7' -R ^6' ) _g' - (f4)

[In the formula, R ⁶ is OCF ₂ or OC ₂ F ₄ ,

R ⁷ can be a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of 2 or 3 groups independently selected from these groups. ,

R ^6' is OCF ₂ or OC ₂ F ₄ ,

R ^7' may be a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or 2 or 3 groups independently selected from these groups. combination,

g is an integer from 2 to 100,

g’ is an integer from 2 to 100,

R ^r is

(In the formula, * shows the bonding position)];

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f5)

[In the formula, e is an integer from 1 to 200, a, b, c, d and f are each independently an integer from 0 to 200. In addition, a, b, c, d, e or f are marked with brackets The order of the repeated units enclosed in the formula is arbitrary]

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f6)

[In the formula, f is an integer from 1 to 200, a, b, c, d and e are each independently an integer from 0 to 200. In addition, a, b, c, d, e or f are marked with brackets The order of the repeated units enclosed in the formula is arbitrary]

In the above formula (f1), d is preferably an integer from 5 to 200, more preferably from 10 to 100, and still more preferably from 15 to 50, such as 25 to 35. In one aspect, e is 1. In other aspects, e is 0. (OC ₃ F ₆ ) in the above formula (f1) is preferably a base represented by (OCF ₂ CF ₂ CF ₂ ), (OCF ₂ CF (CF ₃ )) or (OCF (CF ₃ )CF ₂ ), more preferably Preferably, it is the basis represented by -(OCF ₂ CF ₂ CF ₂ ) _d -. (OC ₂ F ₄ ) in the above formula (f1) is preferably a group represented by (OCF ₂ CF ₂ ) or (OCF (CF ₃ )), more preferably a group represented by (OCF ₂ CF ₂ ).

In the above formula (f2), e and f are each independently preferably an integer from 5 to 200, more preferably an integer from 10 to 200. In addition, the sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. In one aspect, the above formula (f2) is preferably -(OCF ₂ CF ₂ CF ₂ CF ₂ ) _c -(OCF ₂ CF ₂ CF ₂ ) _d -(OCF ₂ CF ₂ ) _e -(OCF ₂ ) _f -The basis shown. In other aspects, formula (f2) may be a basis represented by -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f -.

In the above formula (f3), R ⁶ is preferably OC ₂ F ₄ . In the above (f3), R ⁷ is preferably a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ , or a combination of 2 or 3 groups independently selected from these groups, more preferably It is a base selected from OC ₃ F ₆ and OC ₄ F ₈ . As a combination of 2 or 3 groups independently selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ , there is no particular limitation, but the series is for example: -OC ₂ F ₄ OC ₃ F ₆ -, -OC ₂ F ₄ OC ₄ F ₈ -, -OC ₃ F ₆ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₃ F ₆ -, -OC ₃ F ₆ OC ₄ F ₈ -, -OC ₄ F ₈ OC ₄ F ₈ -, -OC ₄ F ₈ OC ₃ F ₆ -, -OC ₄ F ₈ OC ₂ F ₄ -, -OC ₂ F ₄ OC ₂ F ₄ OC ₃ F ₆ -, -OC ₂ F ₄ OC ₂ F ₄ OC ₄ F ₈ -, -OC ₂ F ₄ OC ₃ F ₆ OC ₂ F ₄ -, -OC ₂ F ₄ OC ₃ F ₆ OC ₃ F ₆ -, -OC ₂ F ₄ OC ₄ F ₈ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₂ F ₄ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₂ F ₄ OC ₃ F ₆ -, -OC ₃ F ₆ OC ₃ F ₆ OC ₂ F ₄ -, and -OC ₄ F ₈ OC ₂ F ₄ OC ₂ F ₄ -etc. In the above formula (f3), g is preferably an integer of 3 or more, more preferably 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ may be either linear or branched chains, and linear chains are preferred. In this aspect, the above formula (f3) is preferably -(OC ₂ F ₄ -OC ₃ F ₆ ) _g - or -(OC ₂ F ₄ -OC ₄ F ₈ ) _g -.

In the above formula (f4), R ⁶ , R ⁷ and g are synonymous with the description in the above formula (f3) and have the same aspect. R ^6' , R ^7' and g' are respectively synonymous with R ⁶ , R ⁷ and g described in the above formula (f3) and have the same aspect. R ^r is preferably

[In the formula, * shows the bonding position]

Better for

[In the formula, * shows the bonding position]

In the above formula (f5), e is preferably an integer from 1 to 100, more preferably from 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.

In the above formula (f6), f is preferably an integer from 1 to 100, more preferably from 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.

In one aspect, the above-mentioned R ^F is a base represented by the above-mentioned formula (f1) or (f2).

In one aspect, the above-mentioned R ^F is a base represented by the above-mentioned formula (f1).

In one aspect, the above-mentioned R ^F is a base represented by the above-mentioned formula (f2).

In one aspect, the above-mentioned R ^F is a base represented by the above-mentioned formula (f3) or (f4).

In one aspect, the above-mentioned R ^F is the base represented by the above-mentioned formula (f3).

In one aspect, the above-mentioned R ^F is the base represented by the above-mentioned formula (f4).

In one aspect, the above-mentioned R ^F is the base represented by the above-mentioned formula (f5).

In one aspect, the above-mentioned R ^F is the base represented by the above-mentioned formula (f6).

In the above R ^F , the ratio of e to f (hereinafter referred to as "e/f ratio") is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, still more preferably 0.2 to 1.5, and more preferably The optimal range is 0.2 to 0.85. By setting the e/f ratio to 10 or less, the durability and chemical resistance (for example, durability against artificial sweat) of the hardened material layer obtained from this compound are further improved. A smaller e/f ratio improves the durability and chemical resistance of the hardened material layer. On the other hand, by setting the e/f ratio to 0.1 or more, the stability of the compound can be further improved. A larger e/f ratio improves the stability of the compound.

In one aspect, the above e/f ratio is preferably 0.2 to 0.95, more preferably 0.2 to 0.9.

In one aspect, from the viewpoint of heat resistance, the e/f ratio is preferably 1.0 or more, more preferably 1.0 to 2.0.

In the above-mentioned fluorine-containing polyether group acrylic compound, the number average molecular weight of the ^RF1 and ^RF2 parts is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. In this specification, the number average molecular weight of ^RF1 and ^RF2 is the value measured by ¹⁹ F-NMR.

In the above formulas (A1) to (A3), R ^Ac is each independently -X ^D -X ^E (-X ^F -OCO-CR ⁵ =CH ₂ ) _m' .

The above-mentioned X ^D is a single bond or a divalent group, such as a divalent organic group.

X ^D is preferably -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -OCONH-, -NHCOO-, -NH-CO-NH-, -CH ₂ CH( OH)CH ₂ -, -CH(CH ₂ OH)CH ₂ -, -(OSiR ¹⁴ ₂ ) _d5 -,

[In the formula, * and ** show the bonding position, * is bonded with X ^B , ** is bonded with X ^E ],

R ¹⁴ is C _1-6 alkyl or C _6-16 aryl,

d5 is an integer from 1 to 10. The left side of these bases is bonded to X ^B .

X ^D is more preferably -CONH-, -CH ₂ CH(OH)CH ₂ -, or -CH(CH ₂ OH)CH ₂ -, more preferably -CONH-.

The above X ^E is a single bond or a base of (m'+1) valence.

In one aspect, X ^E is a single bond.

In one aspect, X ^E is a trivalent or tetravalent base as shown below.

-X ^G -X ^H

[In the formula:

X ^G is a single key,

C _1-6 alkylene group,

-(CH ₂ ) _z9 -O-(CH ₂ ) _z10 -(In the formula, z9 is an integer from 0 to 6, such as an integer from 1 to 6, z10 is an integer from 0 to 6, such as an integer from 1 to 6), Or -(CH ₂ ) _z11 -phenylene-(CH ₂ ) _z12 -(in the formula, z11 is an integer from 0 to 6, such as 1 to 6, z12 is an integer from 0 to 6, such as 1 to 6 integer),

X ^H is the following

R ⁸ is a hydrogen atom or C _1-6 alkyl group]

The above-mentioned C _1-6 alkylene group can be a straight chain or a branched chain, preferably a straight chain.

In a preferred embodiment, the above-mentioned C _1-6 alkylene group is a C _2-4 alkylene group.

The above-mentioned C _1-6 alkyl group is preferably a C _1-3 alkyl group, and more preferably is a methyl group.

The above-mentioned X ^F are each independently a single bond or a divalent group, such as a divalent organic group (preferably a divalent organic group having 1 to 10 carbon atoms).

In one aspect, X ^F is a single bond,

C _1-6 alkylene group,

-(CH ₂ ) _z5 -O-(CH ₂ ) _z6 -(In the formula, z5 is an integer from 0 to 6, such as an integer from 1 to 6, z6 is an integer from 0 to 6, such as an integer from 1 to 6), Or -(CH ₂ ) _z7 -phenylene-(CH ₂ ) _z8 -(in the formula, z7 is an integer from 0 to 6, such as an integer from 1 to 6, z8 is an integer from 0 to 6, such as 1 to 6 integer). These groups, for example, can be substituted with one or more substituents selected from the group consisting of fluorine atom, C _1-6 alkyl group, C _2-6 alkenyl group, and C _2-6 alkynyl group, but preferably Not superseded. The left side of these bases is bonded to X ^B .

The above-mentioned C _1-6 alkylene group can be a straight chain or a branched chain, preferably a straight chain.

In a preferred embodiment, X ^F is a C _1-6 alkylene group, preferably a C _2-4 alkylene group.

In one aspect, ^XD , ^XE , and ^XF are single bonds.

The above-mentioned R ⁵ is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 8 carbon atoms.

The above-mentioned monovalent organic group is preferably C _1-8 alkyl, C _3-8 cycloalkyl, or C _5-8 aryl, more preferably C _1-6 alkyl or phenyl, and even more preferably C _1-3 alkyl, particularly preferably methyl.

In one aspect, ^R5 is a hydrogen atom.

In one aspect, ^R5 is methyl.

The above m' is an integer from 1 to 10, preferably an integer from 1 to 3, and more preferably 1.

In the above formulas (A1) to (A3), X ^A is each independently a single bond or a divalent organic group.

In one aspect, X ^A is independently a single bond, or a divalent organic group without urethane bond.

In a preferred embodiment, X ^{and A} are independently single bonds, or the groups shown below.

-(C _α R ¹¹ _2α ) _s1 -R ¹² _t1 -

[In the formula:

R ¹¹ is independently a hydrogen atom or a fluorine atom,

α is independently an integer from 1 to 10,

R ¹² is independently -O-, -CO-, -CONH-, -NHCO-, -COO-, -OCO-, or -OCONH-,

s1 is an integer from 0 to 3,

t1 is an integer from 0 to 3,

The total of s1 and t1 is more than 1,

The order of the repeating units marked s1 or t1 and enclosed in parentheses in the formula is arbitrary]

Also, in the formula, the left side is bonded to ^RF1 or ^RF2 .

In one aspect, X ^A is a single bond.

In one aspect, X ^A is each independently the above-(C _α R ¹¹ _2α ) _s1 -R ¹² _t1 -.

The above-mentioned R ¹¹ is preferably a hydrogen atom.

The above α is independently preferably an integer from 1 to 6, more preferably an integer from 1 to 4, and still more preferably an integer from 2 to 4.

The above R ¹² is each independently preferably -O-, -CO-, -NR ¹⁰ -, -CONH-, or -COO-, more preferably -CONH-.

The above R ¹⁰ is a hydrogen atom or a C _1-6 alkyl group, preferably a hydrogen atom.

The above-mentioned s1 is preferably an integer from 1 to 3, more preferably 1 or 2, and even more preferably 1.

The above t1 is preferably an integer from 0 to 2, more preferably 1 or 2, and even more preferably 1.

in a better state,

R ¹¹ is a hydrogen atom,

α is an integer from 2 to 4,

R ¹² is -O-, -CO-, -NR ¹⁰ -, -CONH-, or -COO-,

R ¹⁰ is a hydrogen atom or C _1-6 alkyl group,

s1 is 1 or 2,

t1 is 0 or 1.

_{In a more} ^{preferred embodiment} _, ^_ _{_ _ _ _} -(C _α5 H _2α5 ),

R ¹⁰ is a hydrogen atom or C _1-6 alkyl group,

α1 is an integer from 1 to 10,

α2 is an integer from 1 to 10,

α3 is an integer from 1 to 10,

α4 is an integer from 0 to 6,

α5 is an integer from 0 to 6. The left side of these groups is bonded to ^RF1 or ^RF2 .

X ^A is preferably -CONH-C _α H _2α -. The left side of these groups is bonded to ^RF1 or ^RF2 .

The above-mentioned C _α1 H _2α1 is preferably (CH ₂ ) _α1 .

The above-mentioned C _α2 H _2α2 is preferably (CH ₂ ) _α2 .

The above-mentioned C _α3 H _2α3 is preferably (CH ₂ ) _α3 .

The above-mentioned C _α4 H _2α4 is preferably (CH ₂ ) _α4 .

The above C _α5 H _2α5 is preferably (CH ₂ ) _α5 .

In the above formulas (A1) to (A3), X ^B is each independently a base of (m+1) valence. However, in each formula, at least one X ^B is a (m+1)-valent group containing a hydrolyzable silicon group.

In one aspect, X ^B are each independently a (m+1)-valent group containing a hydrolyzable silicon group.

In one aspect, X ^B each independently contains the basis of the basis shown below,

SiR ¹ _nb R ^sb _4-nb

[In the formula:

R ¹ is a hydroxyl group or a hydrolyzable group,

R ^sb is a single bond,

nb is 1 or 2],

Or, it is the base shown below.

X ^Ba (R ^Si ) _na

[In the formula:

X ^Ba are independently the basis of (m+na+1) valence,

R ^Si are independently -X ^C -SiR ¹ _n' R ² _3-n' ,

X ^C is a divalent organic radical with carbon number from 1 to 10,

R ¹ are each independently a hydroxyl group or a hydrolyzable group,

R ² are each independently a hydrogen atom or a monovalent organic group,

n’ is an integer from 1 to 3,

na is an integer from 1 to 10]

In one aspect, X ^B are each independently a basis represented by X ^Ba (R ^Si ) _na .

[In the formula:

X ^Ba are independently the basis of (m+na+1) valence,

R ^Si are independently -X ^C -SiR ¹ _n' R ² _3-n' ,

X ^C is a divalent organic radical with carbon number from 1 to 10,

R ¹ are each independently a hydroxyl group or a hydrolyzable group,

R ² are each independently a hydrogen atom or a monovalent organic group,

n’ is an integer from 1 to 3,

na is an integer from 1 to 10]

Among these aspects, formulas (A1) and (A2) are represented by the following formulas (A1-a) and (A2-a) respectively:

R ^F1 -X ^A -X ^Ba R ^Si _na R ^Ac _m (A1-a)

R ^Ac _m R ^Si _na X ^Ba -X ^A -R ^F2 -X ^A -X ^Ba R ^Si _na R ^Ac _m (A2-a)

[In the formula, each symbol is the same as above]

In the above formulas (A1) to (A3), R ^Si is each independently -X ^C -SiR ¹ _n' R ² _3-n' .

The above-mentioned X ^C is a divalent organic group having 1 to 10 carbon atoms.

In one aspect, X ^C is C _1-6 alkylene,

-(CH ₂ ) _z1 -O-(CH ₂ ) _z2 -(In the formula, z1 is an integer from 0 to 6, such as an integer from 1 to 6, z2 is an integer from 0 to 6, such as an integer from 1 to 6),

-(CH ₂ ) _z3 -phenylene-(CH ₂ ) _z4 -(In the formula, z3 is an integer from 0 to 6, such as an integer from 1 to 6, z4 is an integer from 0 to 6, such as an integer from 1 to 6 ), or -(CH ₂ ) _z13 -OCONH-(CH ₂ ) _z14 -(in the formula, z13 is an integer from 0 to 6, and z14 is an integer from 0 to 6). These groups, for example, can be substituted with one or more substituents selected from the group consisting of fluorine atom, C _1-6 alkyl group, C _2-6 alkenyl group, and C _2-6 alkynyl group, but preferably Not superseded. The left side of these bases is bonded to X ^B .

The above-mentioned C _1-6 alkylene group can be a straight chain or a branched chain, preferably a straight chain.

In a preferred embodiment, X ^C is a C _1-6 alkylene group, preferably a C _2-4 alkylene group.

The above R ¹ is each independently a hydroxyl group or a hydrolyzable group.

R ¹ is preferably each independently a hydrolyzable group.

R ¹ is preferably independently -OR ^h , -OCOR ^h , -ON=CR ^h ₂ , -NR ^h ₂ , -NHR ^h , -NCO, or halogen (in these formulas, R ^h represents substituted or unsubstituted Substituted C _1-4 alkyl), more preferably -OR ^h (ie, alkoxy). As R ^h , the series includes unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, etc.; and substituted alkyl groups such as chloromethyl. Among these, an alkyl group is preferable, especially an unsubstituted alkyl group, and a methyl group or an ethyl group is more preferable. In one aspect, R ^h is methyl, in another aspect, R ^h is ethyl.

The above-mentioned R ² are each independently a hydrogen atom or a monovalent organic group. These monovalent organic groups are monovalent organic groups other than the above-mentioned hydrolyzable groups.

In R ² , the monovalent organic group is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group, and still more preferably a methyl group.

In the above formula, n' in each (SiR ¹ _n' R ² _3-n' ) unit is independently an integer from 1 to 3, preferably 2 or 3, more preferably 3.

The above na is preferably an integer from 1 to 6, more preferably an integer from 1 to 3, and particularly preferably 1.

In one aspect, the above X ^Ba is a trivalent base, preferably

，

。於一態樣中，上述-C(-O-)-為O與R^Si鍵結。於其他態樣中，-C(-O-)-為O與R^Ac鍵結。

,

. In one aspect, -C(-O-)- mentioned above is O and R ^Si bonded. In other aspects, -C(-O-)- is O bonded to R ^Ac .

In a preferred embodiment, X ^Ba is N. At this time, in the formula, m is 1 and n is 1.

In other aspects, X ^B are each independently a group including a group represented by SiR ¹ _nb R ^sb _4-nb ,

[In the formula:

R ¹ is a hydroxyl group or a hydrolyzable group,

R ^sb is a single bond,

nb is 1 or 2]

Preferably, it is a group represented by -X ^Bb -SiR ¹ _nb R ^sb _4-nb .

[In the formula:

X ^Bb is a single bond or a 2-valent base,

R ¹ is a hydroxyl group or a hydrolyzable group,

R ^sb is a single bond,

nb is 1 or 2]

Among these aspects, formulas (A1) and (A2) are represented by the following formulas (A1-b) and (A2-b) respectively:

R ^F1 -X ^A -X ^Bb -SiR ^a _nb R ^Ac _m (A1-b)

R ^Ac _m R ^a _nb Si-X ^Bb -X ^A -R ^F2 -X ^A -X ^Bb -SiR ^a _nb R ^Ac _m (A2-b)

[In the formula, each symbol has the same meaning as above]

In one aspect, nb is 1.

In other aspects, nb is 2.

In one aspect, X ^Bb is a single bond.

In other aspects, X ^Bb is a divalent group, C _1-6 alkylene group.

In the above formulas (A1) and (A2), m is each independently an integer from 0 to 10, and n is each independently an integer from 1 to 10.

m is preferably an integer from 1 to 10, more preferably an integer from 1 to 6, still more preferably an integer from 1 to 3, and still more preferably 1.

n is preferably an integer from 1 to 6, more preferably an integer from 1 to 3, and particularly preferably 1.

In a preferred embodiment, m is 1 and n is 1.

In the above (A3), R ^a is each independently an organic group with a valence of (m3+2).

In one aspect, R ^a is a basis represented by:

-R ⁹ -(R ^a' -R ⁹ ) _k -

[In the formula:

R ⁹ are each independently C _1-6 alkylene group,

R ^a' are each independently a trivalent radical, such as a trivalent organic radical,

k is an integer from 1 to 4]

Among these groups, -C(-O-)- mentioned above is O bonded to R ^Ac .

R ⁹ is preferably a C _1-4 alkylene group, more preferably a C _2-4 alkylene group.

In one aspect, k is 0.

In other aspects, k is an integer from 1 to 4.

In a preferred embodiment, k is an integer between 1 and 2.

In one aspect, k is 1.

In one aspect, k is 2.

In one aspect, R ^a' is each independently a trivalent group including an N atom or an O atom.

In a preferred embodiment, R ^a' may independently include amine bonding, amide bonding, urethane bonding, and urea bonding between N, -C(-O-)-, and carbon-carbon atoms. trivalent base for bonding, ether bonding, or ester bonding

In one aspect, R ^a' is independently the basis of:

In one aspect, R ^a' is N.

In one aspect, R ^a' is -C(-O-)-.

In the above formula (A3), m3 is an integer from 0 to 4.

m3 is preferably an integer from 1 to 4, more preferably 1 or 2.

In one aspect, m3 is 1.

In one aspect, m3 is 2.

In the above formula (A3), R ^g is each independently -NR ^c CO-R ^e -, -NR ^c COO-R ^e -, or -NR ^c CONR ^c -R ^e -. Here, the left side of these bases is bonded to R ^a .

The above-mentioned R ^g is preferably -NR ^c CO-R ^e .

The above-mentioned R ^c are each independently a hydrogen atom, a C _1-6 alkyl group, or a C _6-16 aryl group.

The above-mentioned C _1-6 alkyl group is preferably a C _1-3 alkyl group, and particularly preferably a methyl group. The C _1-6 alkyl group may be straight chain or branched chain.

The above-mentioned C _6-16 aryl group is preferably a C _6-10 aryl group, and more preferably a phenyl group.

In one aspect, R ^c is a hydrogen atom.

In one aspect, R ^c is methyl.

In the above formula, R ^e are each independently a single bond or a divalent organic group.

In one aspect, R ^e is a single bond.

In one aspect, R ^e are each independently a divalent organic group.

The above-mentioned divalent organic group is preferably -R ⁴³ -O _x2 -R ⁴⁴ - (in the formula, R ⁴³ and R ⁴⁴ are independently a single bond or a C _1-20 alkylene group, and x2 is 0 or 1). These C _1-20 alkylene groups may be straight chain or branched chain, but are preferably straight chain. These C _1-20 alkylene groups are preferably C _1-10 alkylene groups, more preferably C _1-6 alkylene groups, and still more preferably C _1-3 alkylene groups.

In the above formula (A3), x is an integer of 1 or more.

In one aspect, x is preferably an integer from 1 to 100, more preferably an integer from 1 to 10, and more preferably an integer from 1 to 5, for example, an integer from 2 to 10, and more preferably An integer from 2 to 5.

In a preferred embodiment, formula (A3) is the following formula (A3-a):

R ^b ₂ NR ^j -(R ^F2 -R ^g -R ^a (R ^Ac ) _m3 -R ^g ) _x -R ^F2 -R ^j -NR ^b ₂ (A3-a)

[In the formula,

R ^b is independently R ^Si , R ^Ac , or R ^c ,

However, at least one of R ^b is R ^Si ,

R ^j is independently -CO-R ^d -, -OR ^d -, or -NR ^c -R ^d -, where the left side of these groups is bonded to ^RF2 ,

R ^d are each independently a single bond or a divalent organic group,

R ^F2 , R ^a , R ^c , R ^Ac , m3, and x are synonymous with the above]

In the above formula (A3-a), R ^b is each independently R ^Si , R ^Ac , or R ^c .

In the above formula (A3-a), at least one R ^b is R ^Si .

In a preferred embodiment, at least one of the R ^b bonded to the N atoms located at each terminal of the formula (A3-a) is R ^Si .

In one aspect, one of the R ^b's bonded to the N atoms located at each terminal of the formula (A3-a) is R ^Si and the others are R ^c .

In other aspects, one of the R ^b's bonded to the N atom at each end of the formula (A3-a) is R ^Si , and the others are R ^Ac .

In a preferred embodiment, R ^Ac is -CONH-X ^F -OCO-CR ⁵ =CH ₂ .

The above R ^j are each independently -CO-R ^d -, -OR ^d -, or -NR ^c -R ^d -. Here, the left side of these bases is bonded to ^RF2 .

In one aspect, R ^j are each independently -CO-R ^d -.

The above R ^d are each independently a single bond or a divalent organic group.

In one aspect, R ^d is a single bond.

In other aspects, R ^d is a divalent organic radical.

The divalent organic group in ^Rd is C _1-10 alkylene group, preferably C _2-6 alkylene group,

-(CH ₂ ) _z13 -O-(CH ₂ ) _z14 -(In the formula, z13 is an integer from 0 to 6, such as an integer from 1 to 6, z14 is an integer from 0 to 6, such as an integer from 1 to 6), -(CH ₂ ) _z15 -phenylene-(CH ₂ ) _z16 -(In the formula, z15 is an integer from 0 to 6, such as an integer from 1 to 6, z16 is an integer from 0 to 6, such as an integer from 1 to 6 ), or -(CH ₂ ) _z17 -NR ¹⁰ -(CH ₂ ) _z18 -(in the formula, R ¹⁰ is a hydrogen atom or a C _1-6 alkyl group, z17 is an integer from 0 to 6, z18 is an integer from 0 to 6 integer). These groups, for example, can be substituted with one or more substituents selected from the group consisting of fluorine atom, C _1-6 alkyl group, C _2-6 alkenyl group, and C _2-6 alkynyl group, but preferably Not superseded. The left side of these groups is bonded to CO.

The divalent organic group in R ^d is preferably -(CH ₂ ) _z17 -NR ¹⁰ -(CH ₂ ) _z18 -(in the formula, R ¹⁰ is a hydrogen atom or a C _1-6 alkyl group, and z17 is 0 to 6 an integer, z18 is an integer from 0 to 6), more preferably -NR ¹⁰ -(CH ₂ ) _z18 -(in the formula, R ¹⁰ is a hydrogen atom or a C _1-6 alkyl group, z18 is an integer from 1 to 6) .

The above-mentioned C _1-10 alkylene group may be a straight chain or a branched chain, preferably a straight chain.

In a preferred form, formula (A3) is formula (A3-b):

R ^b ₂ NR ^d -CO-(R ^F2 -CO-NR ^c -R ^a (R ^Ac ) _m3 -NR ^c -CO) _x -R ^F2 -CO-R ^d -NR ^b ₂ (A3-b)

[In the formula, R ^F2 , R ^a , R ^b , R ^c , R ^d , R ^Ac , m3, and x are synonymous with the above]

The fluorine-containing polyether group-containing acrylic compound represented by the above formulas (A1) to (A3) is not particularly limited, but may have a number average molecular weight of 5×10 ² to 2×10 ⁵ . Among these ranges, from the viewpoint of abrasion durability, it is preferable to have a number average molecular weight of 2×10 ³ to 1×10 ⁵ , and more preferably to have a number average molecular weight of 3×10 ³ to 2×10 ⁴ . In addition, these "number average molecular weights" are values measured by ¹⁹ F-NMR.

The fluorine-containing polyether group acrylic compound represented by the above formulas (A1) and (A2) can be obtained by: first, preparing a fluorine-containing polyether group having a reactive site such as -NH-, -C(OH)-, etc. polyether-based silane compound, and secondly, the compound having a (meth)acrylic acid group is reacted with the above-mentioned reactive site.

In one aspect, the fluorine-containing polyether group-containing acrylic compound represented by the above formulas (A1) and (A2) can be obtained as follows. Let the compound represented by the following formula,

R ^F1 -COOR ²¹

R ²¹ OOC-R ^F2 -COOR ²¹

(In the formula, R ²¹ is a hydrogen atom or a methyl group, and R ^F1 and R ^F2 are synonymous with the descriptions of formulas (A1) and (A2).)

Reacts with compounds represented by the following formula,

R ²⁴ -R ²³ -NH-R ²² -SiR ¹ _n' R ² _3-n'

(In the formula, R ²² is a divalent base,

R ²³ is a bivalent base,

R ²⁴ is a reactive group such as NH ₂ ,

R ¹ , R ² , and n' are synonymous with the descriptions about formulas (A1) and (A2). )

The compound represented by the following formula was obtained.

R ^F1 -R ²⁵ -R ²³ -NH-R ²² -SiR ¹ _n' R ² _3-n'

R ² _3-n' R ¹ _n' Si-R ²² -HN-R ²³ -R ²⁵ -R ^F2 -R ²⁵ -R ²³ -NH-R ²² -SiR ¹ _n' R ² _3-n'

Next, combine the above compound with the following formula:

R ³⁴ -R ³⁵ -OCOCH=CH ₂

(In the formula, R ³⁴ is a reactive group such as -NCO, -COOH, -COOCl, etc.,

R ³⁵ is a bivalent base), or

R ⁵⁶ -OCOCR ⁵⁷ =Reaction of the compound represented by CH ₂ .

(In the formula, R ⁵⁶ is halogen, H, or a monovalent hydrocarbon group,

R ⁵⁷ is a hydrogen atom or C _1-3 alkyl group)

In one aspect, the fluorine-containing polyether group-containing acrylic compound represented by the above formulas (A1) and (A2) can be obtained as follows. Let the compound represented by the following formula,

R ^F1 -COF

FOC-R ^F2 -COF

(In the formula, R ^F1 and R ^F2 are synonymous with the description of formulas (A1) and (A2).)

React with Br-Mg-CH ₂ CH=CH ₂ to obtain the compound represented by the following formula.

R ^F1 -C(OH)(CH ₂ CH=CH ₂ ) ₂

(CH ₂ =CHCH ₂ ) ₂ (HO)CR ^F2 -C(OH)(CH ₂ CH=CH ₂ ) ₂

Secondly, react the above compound with the following formula:

HSiR ¹ _n' R ² _3-n'

The compound represented by the following formula was obtained.

R ^F1 -C(OH)(CH ₂ CH=CH ₂ ) ₂

(R ² _3-n' R ¹ _n' Si-CH ₂ CH ₂ CH ₂ ) ₂ (HO)CR ^F2 -C(OH)(CH ₂ CH ₂ CH ₂ -SiR ¹ _n' R ² _3-n' ) ₂

Next, the above compound is reacted with a compound represented by the following formula.

R ³⁴ -R ³⁵ -OCOCH=CH ₂

(In the formula, R ³⁴ is a reactive group such as -NCO, -COOH, etc.,

R ³⁵ is a bivalent base)

In one aspect, the fluorine-containing polyether group-containing acrylic compound represented by the above formulas (A1) and (A2) can be obtained as follows. Let the compound represented by the following formula,

HOCH ₂ -R ^F2 -CH ₂ OH

(In the formula, R ^F1 and R ^F2 are synonymous with the description of formulas (A1) and (A2).)

反應，而獲得 and

react, get

Next, react the above compound with OCN-(CH ₂ ) ₃ -SiR ¹ _n' R ² _3-n' ,

(In the formula, each symbol has the same meaning as above.)

The compounds shown below were obtained.

(In the formula, each symbol has the same meaning as above.)

In one aspect, the fluorine-containing polyether group-containing acrylic compound represented by the above formulas (A1) and (A2) can be obtained as follows. Let the compound represented by the following formula,

(In the formula, each symbol has the same meaning as above.)

React with HOOC=CH ₂ to obtain

(In the formula, each symbol has the same meaning as above.)

Next, the above compound is reacted with OCN-(CH ₂ ) ₃ -SiR ¹ _n' R ² _3-n'

(In the formula, each symbol has the same meaning as above.)

And obtain the compound shown below

(In the formula, each symbol has the same meaning as above.)

In one aspect, the fluorine-containing polyether group-containing acrylic compound represented by the above formula (A3) can be obtained as follows. Let the compound represented by the following formula,

R ²¹ OOC-R ^F2 -COOR ²¹

[In the formula, R ²¹ is a hydrogen atom or a methyl group, and R ^F2 is synonymous with the description of formula (A3)]

Reacts with the following formula:

NH ₂ -R ⁹ -(NH-R ⁹ ) _k -NH ₂

[In the formula, R ⁹ and k are synonymous with the description of formula (A3)]

And R ²¹ OOC-( ^RF2 -CONH-R ⁹ -(NH-R ⁹ ) _k -NHCO) _x ^-RF2 -COOR ²¹ is obtained.

[In the formula, R ²¹ is a hydrogen atom or a methyl group, and RF ² , R ⁹ , and k have the same meanings as described in the formula (A3)]

Secondly, the obtained compound is reacted with the compound shown below,

NR ²³ _m H _2-m -R ²² -SiR ¹ _n' R ² _3-n'

[In the formula, R ²³ is a C _1-6 alkyl group or phenyl group, m is 0 or 1, R ²² is a divalent group, R ¹ , R ² , and n' are synonymous with the description of formula (A3) 〕

The compound represented by the following formula was obtained.

R ² _3-n' R ¹ _n' Si-R ²² -HNOC-(R ^F2 -CONH-R ⁹ -(NH-R ⁹ ) _k -NHCO) _x -R ^F2 -CONH-R ²² -SiR ¹ _n' R ² _3-n'

Next, the compound represented by formula (A3) can be obtained by reacting the obtained compound with the compound represented by the following formula.

R ³⁴ -R ³⁵ -OCOCH=CH ₂

[In the formula, R ³⁴ is a reactive group such as -NCO, -COOH, etc.,

R ³⁵ is a bivalent base]

In one aspect, the fluorine-containing polyether group-containing acrylic compound represented by the above formula (A3) can be obtained as follows. Let the compound represented by the following formula,

R ²¹ OOC-R ^F2 -COOR ²¹

[In the formula, R ²¹ is a hydrogen atom or a methyl group, and R ^F2 is synonymous with the description of formula (A3)]

Reacts with the following formula:

NH ₂ -R ⁹ -(CH(OH)-R ⁹ ) _k -NH ₂

[In the formula, R ⁹ and k are synonymous with the description of formula (A3)]

And the following formula is obtained.

R ²¹ OOC-(R ^F2 -CONH-R ⁹ -(CH(OH)-R ⁹ ) _k -NHCO) _x -R ^F2 -COOR ²¹

[In the formula, R ²¹ is a hydrogen atom or a methyl group, and RF ² , R ⁹ , and k have the same meanings as described in the formula (A3)]

Secondly, the obtained compound is reacted with the compound shown below,

NR ²³ _m H _2-m -R ²² -SiR ¹ _n' R ² _3-n'

[In the formula, R ²³ is a C _1-6 alkyl group or phenyl group, m is 0 or 1, R ²² is a divalent group, R ¹ , R ² , and n' are synonymous with the description of formula (A3) 〕

The compound represented by the following formula was obtained.

R ² _3-n' R ¹ _n' Si-R ²² -HNOC-(R ^F2 -CONH-R ⁹ -(CH(OH)-R ⁹ ) _k -NHCO) _x -R ^F2 -CONH-R ²² -SiR ¹ _n' R ² _3-n'

Next, the compound represented by the formula (A3) can be obtained by reacting the obtained compound with the compound represented by the following formula.

R ³⁴ -R ³⁵ -OCOCH=CH ₂

[In the formula, R ³⁴ is a reactive group such as -NCO, -COOH, etc.,

R ³⁵ is a bivalent base]

In one aspect, the fluorine-containing polyether group-containing acrylic compound represented by the above formula (A3) can be obtained as follows. Let the compound represented by the following formula,

R ²¹ OOC-R ^F2 -COOR ²¹

[In the formula, R ²¹ is a hydrogen atom or a methyl group, and R ^F2 is synonymous with the description of formula (A3)]

Reacts with the following formula:

NH ₂ -R ⁹ -(NH-R ⁹ ) _k -NH ₂

[In the formula, R ⁹ and k are synonymous with the description of formula (A3)]

And R ²¹ OOC-( ^RF2 -CONH-R ⁹ -(NH-R ⁹ ) _k -NHCO) _x ^-RF2 -COOR ²¹ is obtained.

[In the formula, R ²¹ is a hydrogen atom or a methyl group, and RF ² , R ⁹ , and k have the same meanings as described in the formula (A3)]

Secondly, the obtained compound is reacted with the compound shown below,

NH ₂ -R ^9' -NH ₂

[In the formula, R ^9' is synonymous with the description of R ⁹ ]

And the following formula is obtained.

R ²¹ OOC-(R ^F2 -CONH-R ⁹ -(NH-R ⁹ ) _k -NHCO) _x -(R ^F2 -CONH-R ^9' -NHCO) _x' -R ^F2 -COOR ²¹

[In the formula, R ²¹ is a hydrogen atom or a methyl group, ^{RF 2} , R ⁹ , and k are synonymous with the description of formula (A3), and R ^9' is synonymous with the description of R ⁹ ]

Secondly, the obtained compound is reacted with the compound shown below,

NR ²³ _m H _2-m -R ²² -SiR ¹ _n' R ² _3-n'

[In the formula, R ²³ is a C _1-6 alkyl group or phenyl group, m is 0 or 1, R ²² is a divalent group, R ¹ , R ² , and n' are synonymous with the description of formula (A3) 〕

The compound represented by the following formula was obtained.

R ² _3-n' R ¹ _n' Si-R ²² -HNOC-(R ^F2 -CONH-R ⁹ -(NH-R ⁹ ) _k -NHCO) _x -(R ^F2 -CONH-R ^9' -NHCO) _x' -R ^F2 -CONH-R ²² -SiR ¹ _n' R ² _3-n'

Next, the compound represented by the formula (A3) can be obtained by reacting the obtained compound with the compound represented by the following formula.

R ³⁴ -R ³⁵ -OCOCH=CH ₂

[In the formula, R ³⁴ is a reactive group such as -NCO, -COOH, etc.,

R ³⁵ is a bivalent base]

The reaction conditions of each step of the above reaction can be appropriately set by those with ordinary knowledge in the technical field to which the invention belongs.

Component (B): fluoropolyether-based silane compound containing fluoropolyether group and hydrolyzable silica group

The curable composition of the present disclosure includes a fluoropolyether-containing silane compound containing a fluoropolyether group and a hydrolyzable silica group. The curable composition of the present disclosure has curability due to moisture (water) due to the silane compound containing the above-mentioned fluorine-containing polyether group.

The above-mentioned fluoropolyether group-containing silane compound contains a fluoropolyether group and a hydrolyzable silica group in the molecule.

In a preferred embodiment, the silane compound containing a fluoropolyether group is a compound represented by the following formula (B1) or (B2),

R ^F3 _α -X ^Z -R ^Si _β (B1)

R ^Si _γ -X ^Z -R ^F4 -X ^Z -R ^Si _γ (B2)

[In the formula:

R ^F3 are independently Rf ³ -R ^FB -O _q3 -;

R ^F4 is -Rf ⁴ _p3 -R ^FB -O _q3 -;

Rf ³ are each independently a C _1-16 alkyl group that may be substituted by 1 or more than 1 fluorine atom;

Rf ⁴ is a C _1-6 alkylene group which may be substituted by 1 or more than 1 fluorine atom;

R ^FB are independently divalent fluoropolyether groups;

p3 is 0 or 1;

q3 is independently 0 or 1;

R ^Si is independently a monovalent group including a Si atom bonded to a hydroxyl group, a hydrolyzable group, a hydrogen atom or a monovalent organic group;

At least one R ^Si is a univalent group including a Si atom bonded to a hydroxyl group or a hydrolyzable group;

X and ^Z are each independently a single bond or an organic group with a valence of 2 to 10;

α is an integer from 1 to 9;

β is an integer from 1 to 9;

γ is independently an integer from 1 to 9].

In the above formula (B1), R ^F3 is each independently Rf ³ -R ^FB -O _q3 -.

In the above formula (B2), R ^F4 is -Rf ⁴ _p3 -R ^FB -O _q3 -.

In the above formula, Rf ³ is each independently a C _1-16 alkyl group that may be substituted by 1 or more than 1 fluorine atom.

The "C _1-16 alkyl group" in the above-mentioned C _1-16 alkyl group that can be substituted by one or more fluorine atoms can be a straight chain or a branched chain, preferably a straight chain or a branched chain of C _1-6 alkyl, especially C _1-3 alkyl, more preferably straight-chain C _1-6 alkyl, especially C _1-3 alkyl.

The above-mentioned Rf ³ is preferably a C _1-16 alkyl group that can be substituted by one or more fluorine atoms, more preferably a CF ₂ HC _1-15 perfluoroalkylene group, and even more preferably a C _1-16 perfluoroalkyl group. Fluoroalkyl.

The above-mentioned C _1-16 perfluoroalkyl group can be a straight chain or branched chain, preferably a straight chain or branched chain C _1-6 perfluoroalkyl group, especially a C _1-3 perfluoroalkyl group, more preferably It is a linear C _1-6 perfluoroalkyl group, especially a C _1-3 perfluoroalkyl group, specifically -CF ₃ , -CF ₂ CF ₃ , or -CF ₂ CF ₂ CF ₃ .

In the above formula, Rf ⁴ is a C _1-6 alkylene group which may be substituted by one or more than one fluorine atom.

The "C _1-6 alkylene group" in the above-mentioned C _1-6 alkylene group that can be substituted by one or more fluorine atoms can be a straight chain or a branched chain, preferably a straight chain or a branched chain. The C _1-3 alkylene group is more preferably a straight-chain C _1-3 alkylene group.

The above-mentioned Rf ⁴ is preferably a C _1-6 alkylene group which may be substituted by one or more fluorine atoms, more preferably a C _1-6 perfluoroalkylene group, and even more preferably a C _1-3 perfluoro group. Alkylene.

The above-mentioned C _1-6 perfluoroalkylene group can be a straight chain or a branched chain, preferably a straight chain or branched chain C _1-3 perfluoroalkylene group, and more preferably a straight chain C _1-3 perfluoroalkylene group. Fluoroalkylene group is specifically -CF ₂ -, -CF ₂ CF ₂ -, or -CF ₂ CF ₂ CF ₂ -.

In the above formula, p3 is 0 or 1. In one aspect, p3 is 0. In other aspects, p3 is 1.

In the above formula, q3 is independently 0 or 1. In one aspect, q3 is 0. In other configurations, q3 is 1.

In the above formulas (B1) and (B2), R ^FB is each independently a divalent fluoropolyether group.

The above-mentioned R ^FB is the same fluoropolyether group as the above-mentioned ^RF and has the same aspect.

R ^FB is preferably a linear divalent fluoropolyether group. By using a linear divalent fluoropolyether group, the viscosity becomes relatively low, and the coating properties and operability are improved.

That is, R ^FB is preferably the basis shown in the formula:

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ R ^Fa ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f -

[In the formula:

R ^Fa are each independently a hydrogen atom, a fluorine atom or a chlorine atom,

a, b, c, d, e and f are each independently an integer from 0 to 200, and the sum of a, b, c, d, e and f is 1 or more. The order of presence of each repeating unit marked a, b, c, d, e or f and enclosed in parentheses in the formula is arbitrary. However, when all R ^Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1 or more].

In one aspect, R ^FB are each independently a basis represented by any one of formulas (f1) to (f6).

-(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1)

[In the formula, d is an integer from 1 to 200, and e is 0 or 1];

-(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f2)

[In the formula, c and d are each independently an integer from 0 to 30, e and f are each independently an integer from 1 to 200,

The sum of c, d, e and f is 2 or more,

The order of the repeating units marked c, d, e or f and enclosed in parentheses in the formula is arbitrary];

-(R ⁶ -R ⁷ ) _g - (f3)

[In the formula, R ⁶ is OCF ₂ or OC ₂ F ₄ ,

R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of 2 or 3 groups independently selected from these groups,

g is an integer from 2 to 100];

-(R ⁶ -R ⁷ ) _g -R ^r -(R ^7' -R ^6' ) _g' - (f4)

[In the formula, R ⁶ is OCF ₂ or OC ₂ F ₄ ,

R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of 2 or 3 groups independently selected from these groups,

R ^6' is OCF ₂ or OC ₂ F ₄ ,

R ^7' is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of 2 or 3 groups independently selected from these groups. ,

g is an integer from 2 to 100,

g’ is an integer from 2 to 100,

R ^r is

(In the formula, * shows the bonding position)];

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f5)

[In the formula, e is an integer from 1 to 200, a, b, c, d and f are each independently an integer from 0 to 200. In addition, a, b, c, d, e or f are marked with brackets The order of the repeated units enclosed in the formula is arbitrary]

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f6)

[In the formula, f is an integer from 1 to 200, a, b, c, d and e are each independently an integer from 0 to 200. In addition, a, b, c, d, e or f are marked with brackets The order of the repeated units enclosed in the formula is arbitrary]

In one aspect, the above-mentioned R ^FB is a base represented by the above-mentioned formula (f1) or (f2).

In one aspect, the above-mentioned R ^FB is the base represented by the above-mentioned formula (f1).

In one aspect, the above-mentioned R ^FB is the base represented by the above-mentioned formula (f2).

In one aspect, the above-mentioned R ^FB is the base represented by the above-mentioned formula (f3) or (f4).

In one aspect, the above-mentioned R ^FB is the base represented by the above-mentioned formula (f3).

In one aspect, the above-mentioned R ^FB is the base represented by the above-mentioned formula (f4).

In one aspect, the above-mentioned R ^FB is the base represented by the above-mentioned formula (f5).

In one aspect, the above-mentioned R ^FB is the base represented by the above-mentioned formula (f6).

In the above formulas (B1) and (B2), R ^Si each independently includes a Si atom bonded to a hydroxyl group, a hydrolyzable group, a hydrogen atom or a monovalent organic group (hereinafter also referred to as "hydrolyzable silicon group") At least one of the monovalent groups of R ^Si contains a monovalent group of a Si atom bonded to a hydroxyl group or a hydrolyzable group.

In a preferred embodiment, R ^Si contains a monovalent group of Si atoms bonded to a hydroxyl group or a hydrolyzable group.

In a preferred embodiment, R ^Si is a group represented by the following formula (S1), (S2), (S3), (S4) or (S5).

-SiR ²⁵ _n1 R ²⁶ _3-n1 (S2)

-SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 (S3)

-CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 (S4)

-NR ^g1 R ^h1 (S5)

[In the formula:

R ²⁵ is independently a hydroxyl group or a hydrolyzable group;

R ²⁶ are each independently a hydrogen atom or a monovalent organic group;

n1 is an integer from 0 to 3 in each (SiR ²⁵ _n1 R ²⁶ _3-n1 ) unit independently;

X ¹¹ is independently a single bond or a divalent organic group;

R ²⁷ are each independently a hydrogen atom or a monovalent organic group;

t is independently an integer above 2;

R ²⁸ is independently a hydrogen atom, a halogen atom or -X ¹¹ -SiR ²⁵ _n1 R ²⁶ _3-n1 ;

R ²⁹ are each independently a single bond, an oxygen atom, an alkylene group with 1 to 6 carbon atoms, or an alkyleneoxy group with 1 to 6 carbon atoms;

R ^a1 are independently -Z ¹ -SiR ²¹ _p1 R ²² _q1 R ²³ _r1 ;

Z ¹ is independently an oxygen atom or a divalent organic group;

R ²¹ are independently -Z ^1' -SiR ^21' _p1' R ^22' _q1' R ^23' _r1' ;

R ²² are each independently a hydroxyl group or a hydrolyzable group;

R ²³ are each independently a hydrogen atom or a monovalent organic group;

p1 are independently integers from 0 to 3;

q1 are independently integers from 0 to 3;

r1 are independently integers from 0 to 3;

Z ^1' are each independently an oxygen atom or a divalent organic group;

R ^21' are independently -Z ^1” -SiR ^22” _q1” R ^23” _r1” ;

R ^22' is independently a hydroxyl group or a hydrolyzable group;

R ^23' are each independently a hydrogen atom or a monovalent organic group;

p1’ are independently integers from 0 to 3;

q1’ are independently integers from 0 to 3;

r1’ are independently integers from 0 to 3;

Z ^1″ are independently oxygen atoms or divalent organic groups;

R ^22″ are each independently a hydroxyl group or a hydrolyzable group;

R ^23″ are each independently a hydrogen atom or a monovalent organic group;

q1” are independently integers from 0 to 3;

r1” are independently integers from 0 to 3;

R ^b1 are each independently a hydroxyl group or a hydrolyzable group;

R ^c1 are each independently a hydrogen atom or a monovalent organic group;

k1 are independently integers from 0 to 3;

l1 are independently integers from 0 to 3;

m1 are independently integers from 0 to 3;

R ^d1 are independently -Z ² -CR ³¹ _p2 R ³² _q2 R ³³ _r2 ;

Z ² are independently a single bond, an oxygen atom or a divalent organic group;

R ³¹ are independently -Z ^2' -CR ^32' _q2' R ^33' _r2' ;

R ³² are independently -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 ;

R ³³ are each independently a hydrogen atom, a hydroxyl group or a monovalent organic group;

p2 are independently integers from 0 to 3;

q2 are independently integers from 0 to 3;

r2 are independently integers from 0 to 3;

Z ^2' are independently a single bond, an oxygen atom or a divalent organic group;

R ^32' are independently -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 ;

R ^33' are independently a hydrogen atom, a hydroxyl group or a monovalent organic group;

q2’ are independently integers from 0 to 3;

r2’ are independently integers from 0 to 3;

Z ³ are independently a single bond, an oxygen atom or a divalent organic group;

R ³⁴ is independently a hydroxyl group or a hydrolyzable group;

R ³⁵ are each independently a hydrogen atom or a monovalent organic group;

n2 are independently integers from 0 to 3;

R ^e1 are independently -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 ;

R ^f1 are independently a hydrogen atom, a hydroxyl group or a monovalent organic group;

k2 are independently integers from 0 to 3;

l2 are independently integers from 0 to 3;

m2 are independently integers from 0 to 3;

R ^g1 and R ^h1 are independently -Z ⁴ -SiR ²⁵ _n1 R ²⁶ _3-n1 , -Z ⁴ -SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 , -Z ⁴ -CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 ;

Z ⁴ are independently a single bond, an oxygen atom or a divalent organic group;

However, in the formulas (S1), (S2), (S3), (S4) and (S5), there is at least one Si atom bonded to a hydroxyl group or a hydrolyzable group]

In the above formula, R ²⁵ is each independently a hydroxyl group or a hydrolyzable group.

R ²⁵ is preferably each independently a hydrolyzable group.

R ²⁵ is preferably independently -OR ^j , -OCOR ^j , -ON=CR ^j ₂ , -NR ^j ₂ , -NHR ^j , -NCO, or halogen (in these formulas, R ^j represents substituted or unsubstituted Substituted C _1-4 alkyl), more preferably -OR ^j (ie, alkoxy). As ^Rj , the series includes: unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, etc.; substituted alkyl groups such as chloromethyl. Among these, an alkyl group is preferable, especially an unsubstituted alkyl group, and a methyl group or an ethyl group is more preferable. In one aspect, R ^j is methyl, in other aspects, R ^j is ethyl.

In the above formula, R ²⁶ is each independently a hydrogen atom or a monovalent organic group. These monovalent organic groups are monovalent organic groups other than the above-mentioned hydrolyzable groups.

In R ²⁶ , the monovalent organic group is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group, and still more preferably a methyl group.

In the above formula, n1 is an integer from 0 to 3 independently in each (SiR ²⁵ _n1 R ²⁶ _3-n1 ) unit. However, when R ^Si belongs to a group represented by formula (S1) or (S2), the R ^Si portion at the end of formula (B1) and formula (B2) (hereinafter also referred to as formula (B1) and formula (B2) (the "terminal part"), there is at least one (SiR ²⁵ _n1 R ²⁶ _3-n1 ) unit where n1 belongs to 1 to 3. That is, in these terminal parts, all n1 will not be 0 at the same time. In other words, at least one Si atom bonded to a hydroxyl group or a hydrolyzable group is present in the terminal portion of formula (B1) and formula (B2).

n1 in each (SiR ²⁵ _n1 R ²⁶ _3-n1 ) unit is preferably an integer of 1 to 3, more preferably 2 to 3, and still more preferably 3.

In the above formula, X ¹¹ is independently a single bond or a divalent organic group. These divalent organic groups are preferably -R ⁴¹ -O _x -R ⁴² - (in the formula, R ⁴¹ and R ⁴² are independently a single bond or a C _1-20 alkylene group, and x is 0 or 1). These C _1-20 alkylene groups may be straight chain or branched chain, preferably straight chain. These C _1-20 alkylene groups are preferably C _1-10 alkylene groups, more preferably C _1-6 alkylene groups, and still more preferably C _1-3 alkylene groups.

In one aspect, X ¹¹ is each independently -C _1-6 alkylene-OC _1-6 alkylene- or -OC _1-6 alkylene-.

In _a preferred _embodiment ^, A linear C _1-2 alkylene group is more preferably a linear C _1-2 alkylene group.

In the above formula, R ²⁷ is each independently a hydrogen atom or a monovalent organic group. These monovalent organic groups are preferably C _1-20 alkyl groups. These C _1-20 alkyl groups may be straight chain or branched chain, preferably straight chain.

In a preferred embodiment, R ²⁷ is independently a hydrogen atom or a linear C _1-6 alkyl group, preferably a hydrogen atom or a linear C _1-3 alkyl group, preferably a hydrogen atom or a methyl group. .

In the above formula, t is independently an integer of 2 or more.

In a preferred embodiment, t is independently an integer from 2 to 10, preferably an integer from 2 to 6.

In the above formula, R ²⁸ is each independently a hydrogen atom, a halogen atom or -X ¹¹ -SiR ²⁵ _n1 R ²⁶ _3-n1 . These halogen atoms are preferably iodine atoms, chlorine atoms or fluorine atoms, more preferably fluorine atoms. In a preferred embodiment, R ²⁸ is a hydrogen atom.

In the above formula, R ²⁹ is each independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms.

In one aspect, R ²⁹ is independently an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms.

In a preferred embodiment, R ²⁹ is a single bond.

In one aspect, formula (S1) is the following formula (S1-a).

[In the formula,

R ²⁵ , R ²⁶ , R ²⁷ , X ¹¹ , and n1 are synonymous with the description of the above formula (S1);

t1 and t2 are each independently an integer above 1, preferably an integer from 1 to 10, more preferably an integer from 2 to 10, such as an integer from 1 to 5 or an integer from 2 to 5;

The order of the repeating units marked t1 and t2 and enclosed in parentheses in the formula is arbitrary]

In a preferred aspect, formula (S1) is the following formula (S1-b).

[In the formula, R ²⁵ , R ²⁶ , R ²⁷ , X ¹¹ , n1 and t are synonymous with the description of the above formula (S1)]

In the above formula, R ^a1 is each independently -Z ¹ -SiR ²¹ _p1 R ²² _q1 R ²³ _r1 .

The above-mentioned Z ¹ are each independently an oxygen atom or a divalent organic group. In the structure described below as ^Z1 , (SiR ²¹ _p1 R ²² _q1 R ²³ _r1 ) is bonded to the right side.

In a preferred embodiment, Z ¹ is a divalent organic group.

In a preferred embodiment, Z ¹ does not contain Si atoms bonded to Z ¹ to form siloxane bonds. Preferably, in formula (S3), (Si-Z ¹ -Si) does not contain siloxane bonds.

The above Z ¹ is preferably a C _1-6 alkylene group, -(CH ₂ ) _z1 -O-(CH ₂ ) _z2 -(in the formula, z1 is an integer from 0 to 6, for example, an integer from 1 to 6, z2 is an integer from 0 to 6, such as an integer from 1 to 6) or -(CH ₂ ) _z3 -phenylene-(CH ₂ ) _z4 -(in the formula, z3 is an integer from 0 to 6, such as an integer from 1 to 6, z4 is an integer from 0 to 6, such as an integer from 1 to 6). These C _1-6 alkylene groups may be straight chain or branched chain, preferably straight chain. These groups, for example, can be substituted with one or more substituents selected from the group consisting of fluorine atom, C _1-6 alkyl group, C _2-6 alkenyl group, and C _2-6 alkynyl group, but preferably Not superseded.

In a preferred embodiment, Z ¹ is C _1-6 alkylene group or -(CH ₂ ) _z3 -phenylene group -(CH ₂ ) _z4 -, preferably -phenylene group -(CH ₂ ) _z4 - . When Z ¹ belongs to these groups, higher light resistance, especially ultraviolet resistance, can be obtained.

In another preferred embodiment, the above-mentioned Z ¹ is a C _1-3 alkylene group. In one aspect, Z ¹ can be -CH ₂ CH ₂ CH ₂ -. In other aspects, Z ¹ is -CH ₂ CH ₂ -.

The above R ²¹ are each independently -Z ^1' -SiR ^21' _p1' R ^22' _q1' R ^23' _r1' .

The above-mentioned Z ^1' are each independently an oxygen atom or a divalent organic group. In the structure described below as Z ^1' , the right side is bonded to (SiR ^21' _p1' R ^22' _q1' R ^23' _r1' ).

In a preferred embodiment, Z ^1' is a divalent organic group.

In a preferred embodiment, Z ^1' does not contain Si atoms bonded to Z ^1' that form siloxane bonds. Preferably, in formula (S3), (Si-Z ^1' -Si) does not contain siloxane bonds.

The above Z ^1' is preferably a C _1-6 alkylene group, -(CH ₂ ) _z1' -O-(CH ₂ ) _z2' -(in the formula, z1' is an integer from 0 to 6, for example, from 1 to 6 Integer, z2' is an integer from 0 to 6, for example, an integer from 1 to 6) or, -(CH ₂ ) _z3' -phenyl-(CH ₂ ) _z4' -(in the formula, z3' is an integer from 0 to 6 An integer, such as an integer from 1 to 6, z4' is an integer from 0 to 6, such as an integer from 1 to 6). These C _1-6 alkylene groups may be straight chain or branched chain, but are preferably straight chain. These groups, for example, can be substituted with one or more substituents selected from the group consisting of fluorine atom, C _1-6 alkyl group, C _2-6 alkenyl group, and C _2-6 alkynyl group, but preferably Not superseded.

In a preferred embodiment, Z ^1' is C _1-6 alkylene or -(CH ₂ ) _z3' -phenylene-(CH ₂ ) _z4' -, preferably -phenylene-(CH ₂ ) _z4' -. When Z ^1' belongs to these groups, higher light resistance, especially ultraviolet resistance, can be obtained.

In another preferred embodiment, the above-mentioned Z ^1' is a C _1-3 alkylene group. In one aspect, Z ^1' can be -CH ₂ CH ₂ CH ₂ -. In other aspects, Z ^1' can be -CH ₂ CH ₂ -.

The above R ^21' are each independently -Z ^1" -SiR ^22" _q1" R ^23" _r1" .

The above-mentioned Z ^1″ are each independently an oxygen atom or a divalent organic group. In the structure described below as Z ^1″ , the right side is bonded to (SiR ^22″ _q1″ R ^23″ _r1″ ).

In a preferred embodiment, Z ^1″ is a divalent organic radical.

In a preferred embodiment, Z ^1″ does not contain Si atoms bonded to Z ^1″ that form siloxane bonds. Preferably, in formula (S3), (Si-Z ^1″ -Si) does not contain siloxane bonds.

The above Z ^1” is preferably a C _1-6 alkylene group, -(CH ₂ ) _z1” -O-(CH ₂ ) _z2” - (in the formula, z1” is an integer from 0 to 6, for example, from 1 to 6 Integer, z2″ is an integer from 0 to 6, for example, an integer from 1 to 6) or, -(CH ₂ ) _z3″ -phenyl-(CH ₂ ) _z4″ -(where z3″ is an integer from 0 to 6) an integer, such as an integer from 1 to 6, z4″ is an integer from 0 to 6, such as an integer from 1 to 6). These C _1-6 alkylene groups may be linear or branched, but are preferably linear. These groups, for example, can be substituted with one or more substituents selected from the group consisting of fluorine atom, C _1-6 alkyl group, C _2-6 alkenyl group, and C _2-6 alkynyl group, but preferably Not superseded.

In a preferred embodiment, Z ^1” is C _1-6 alkylene or -(CH ₂ ) _z3” -phenylene-(CH ₂ ) _z4” -, preferably -phenylene-(CH ₂ ) _z4” -. When Z ^1” belongs to these groups, higher light resistance, especially ultraviolet resistance, can be obtained.

In other preferred embodiments, the above-mentioned Z ^1″ is a C _1-3 alkylene group. In one embodiment, Z ^1″ can be -CH ₂ CH ₂ CH ₂ -. In other aspects, Z ^1″ can be -CH ₂ CH ₂ -.

The above-mentioned R ^22″ are each independently a hydroxyl group or a hydrolyzable group.

The above-mentioned R ^22″ is preferably each independently a hydrolyzable group.

The above-mentioned R ^22″ is preferably independently -OR ^j , -OCOR ^j , -ON=CR ^j ₂ , -NR ^j ₂ , -NHR ^j , -NCO, or halogen (in these formulas, R ^j represents substitution or unsubstituted C _1-4 alkyl), more preferably -OR ^j (that is, alkoxy). As R ^j , the series includes: methyl, ethyl, propyl, isopropyl, n-butyl , unsubstituted alkyl groups such as isobutyl; substituted alkyl groups such as chloromethyl. Among these, an alkyl group is preferred, especially an unsubstituted alkyl group, and a methyl or ethyl group is more preferred. In one state In one aspect, R ^j is methyl, in other aspects, R ^j is ethyl.

The above-mentioned R ^23″ are each independently a hydrogen atom or a monovalent organic group. These monovalent organic groups are monovalent organic groups other than the above-mentioned hydrolyzable group.

Among the above-mentioned R ^23″ , the monovalent organic group is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group, and still more preferably a methyl group.

The above q1″ are each independently an integer from 0 to 3, and the above r1″ are each independently an integer from 0 to 3. Furthermore, the total of q1” and r1” is 3 in the unit (SiR ^22” _q1” R ^23” _r1” ).

The above q1″ in each (SiR ^22″ _q1″ R ^23″ _r1″ ) unit is preferably an integer of 1 to 3, more preferably 2 to 3, and even more preferably 3.

The above-mentioned R ^22' are each independently a hydroxyl group or a hydrolyzable group.

R ^22' is preferably each independently a hydrolyzable group.

R ^22' is preferably independently -OR ^j , -OCOR ^j , -ON=CR ^j ₂ , -NR ^j ₂ , -NHR ^j , -NCO, or halogen (in these formulas, R ^j represents substitution or Unsubstituted C _1-4 alkyl), more preferably -OR ^j (ie, alkoxy). As ^Rj , the series includes: unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, etc.; substituted alkyl groups such as chloromethyl. Among these, an alkyl group is preferable, especially an unsubstituted alkyl group, and a methyl group or an ethyl group is more preferable. In one aspect, R ^j is methyl, in other aspects, R ^j is ethyl.

The above-mentioned R ^23' are each independently a hydrogen atom or a monovalent organic group. These monovalent organic groups are monovalent organic groups other than the above-mentioned hydrolyzable groups.

In R ^23' , the monovalent organic group is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group, and still more preferably a methyl group.

The above p1' is an integer from 0 to 3 independently, q1' is an integer from 0 to 3 independently, and r1' is an integer from 0 to 3 independently. Furthermore, the total of p', q1' and r1' is 3 in the (SiR ^21' _p1' R ^22' _q1' R ^23' _r1' ) unit.

In one aspect, p1’ is 0.

In one aspect, p1' in each (SiR ^21' _p1' R ^22' _q1' R ^23' _r1' ) unit independently may be an integer from 1 to 3, an integer from 2 to 3, or 3. In a preferred embodiment, p1' is 3.

In one aspect, q1' in each (SiR ^21' _p1' R ^22' _q1' R ^23' _r1' ) unit is independently an integer from 1 to 3, preferably an integer from 2 to 3, more preferably is 3.

In one aspect, p1' is 0, and q1' in each (SiR ^21' _p1' R ^22' _q1' R ^23' _r1' ) unit is independently an integer between 1 and 3, preferably between 2 and 3. An integer, preferably 3.

The above-mentioned R ²² are each independently a hydroxyl group or a hydrolyzable group.

R ²² is preferably each independently a hydrolyzable group.

R ²² is preferably independently -OR ^j , -OCOR ^j , -ON=CR ^j ₂ , -NR ^j ₂ , -NHR ^j , -NCO, or halogen (in these formulas, R ^j represents substituted or unsubstituted Substituted C _1-4 alkyl), more preferably -OR ^j (ie, alkoxy). As ^Rj , the series includes unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, etc.; and substituted alkyl groups such as chloromethyl. Among these, an alkyl group is preferable, especially an unsubstituted alkyl group, and a methyl group or an ethyl group is more preferable. In one aspect, R ^j is methyl, in other aspects, R ^j is ethyl.

The above-mentioned R ²³ are each independently a hydrogen atom or a monovalent organic group. These monovalent organic groups are monovalent organic groups other than the above-mentioned hydrolyzable groups.

In R ²³ , the monovalent organic group is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group, and still more preferably a methyl group.

The above p1 is an integer from 0 to 3 independently, q1 is an integer from 0 to 3 independently, and r1 is an integer from 0 to 3 independently. Furthermore, the total of p1, q1, and r1 is 3 in the (SiR ²¹ _p1 R ²² _q1 R ²³ _r1 ) unit.

In one aspect, p1 is 0.

In one aspect, p1 is independently an integer from 1 to 3, an integer from 2 to 3, or 3 in each (SiR ²¹ _p1 R ²² _q1 R ²³ _r1 ) unit. In a preferred embodiment, p1 is 3.

In one aspect, q1 in each (SiR ²¹ _p1 R ²² _q1 R ²³ _r1 ) unit is independently an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3.

In one aspect, p1 is 0, and q1 in each (SiR ²¹ _p1 R ²² _q1 R ²³ _r1 ) unit is independently an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3 .

In the above formula, R ^b1 is each independently a hydroxyl group or a hydrolyzable group.

The above-mentioned R ^b1 is preferably each independently a hydrolyzable group.

The above R ^b1 is preferably independently -OR ^j , -OCOR ^j , -ON=CR ^j ₂ , -NR ^j ₂ , -NHR ^j , -NCO, or halogen (in these formulas, R ^j represents substitution or Unsubstituted C _1-4 alkyl), more preferably -OR ^j (ie, alkoxy). As ^Rj , the series includes: unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, etc.; substituted alkyl groups such as chloromethyl. Among these, an alkyl group is preferable, especially an unsubstituted alkyl group, and a methyl group or an ethyl group is more preferable. In one aspect, R ^j is methyl, in other aspects, R ^j is ethyl.

In the above formula, R ^c1 is each independently a hydrogen atom or a monovalent organic group. These monovalent organic groups are monovalent organic groups other than the above-mentioned hydrolyzable groups.

In the above-mentioned R ^c1 , the monovalent organic group is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group, and still more preferably a methyl group.

The above k1 is an integer from 0 to 3 independently, l1 is an integer from 0 to 3 independently, and m1 is an integer from 0 to 3 independently. Furthermore, the total of k1, l1, and m1 is 3 in the (SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 ) unit.

In one aspect, k1 in each (SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 ) unit is independently an integer from 1 to 3, preferably 2 or 3, more preferably 3. In a preferred embodiment, k1 is 3.

In the above-mentioned formulas (B1) and (B2), when R ^Si belongs to the group represented by the formula (S3), it is preferable that there are at least two terminal parts of the formula (B1) and the formula (B2) related to the hydroxyl group or Si atom bonded with a hydrolyzable group.

In a preferred embodiment, the base represented by formula (S3) has -Z ¹ -SiR ²² _q1 R ²³ _r1 (in the formula, q1 is an integer from 1 to 3, preferably 2 or 3, more preferably 3, r1 is an integer from 0 to 2), -Z ^1' -SiR ^22' _q1' R ^23' _r1' (wherein, q1' is an integer from 1 to 3, preferably 2 or 3, more preferably 3, r1 ' is an integer from 0 to 2), or -Z ^1” -SiR ^22” _q1” R ^23” _r1” (in the formula, q1” is an integer from 1 to 3, preferably 2 or 3, more preferably 3, r1″ is any one of an integer from 0 to 2). ^{Z 1} , Z ^1′ , Z ^1″ , R ²² , R ²³ , R ^22′ , R ^23′ , R ^22″ , and R ^23″ are synonymous with the above.

In a preferred aspect, in formula (S3), when R ^21' exists, at least one, preferably all R ^21' , q1" is an integer from 1 to 3, preferably 2 or 3 , preferably 3.

In a preferred aspect, in formula (S3), when R ²¹ exists, at least one, preferably all R ²¹ , p1' is 0, and q1' is an integer from 1 to 3, preferably 2 or 3, preferably 3.

In a preferred aspect, in formula (S3), when R ^a1 exists, at least one, preferably all R ^a1 , p1 is 0, and q1 is an integer from 1 to 3, preferably 2 or 3, preferably 3.

In a preferred aspect, in formula (S3), k1 is 2 or 3, preferably 3, p1 is 0, and q1 is 2 or 3, preferably 3.

R ^d1 are each independently -Z ² -CR ³¹ _p2 R ³² _q2 R ³³ _r2 .

Z ² is each independently a single bond, an oxygen atom or a divalent organic group. In addition, as the structure described in Z ² below, the right side is bonded to (CR ³¹ _p2 R ³² _q2 R ³³ _r2 ).

In a preferred embodiment, Z ² is a divalent organic radical.

The above Z ² is preferably a C _1-6 alkylene group, -(CH ₂ ) _z5 -O-(CH ₂ ) _z6 -(in the formula, z5 is an integer from 0 to 6, for example, an integer from 1 to 6, z6 is an integer from 0 to 6, such as an integer from 1 to 6) or, -(CH ₂ ) _z7 -phenylene-(CH ₂ ) _z8 -(where z7 is an integer from 0 to 6, such as an integer from 1 to 6) , z8 is an integer from 0 to 6, such as an integer from 1 to 6). These C _1-6 alkylene groups may be straight chain or branched chain, preferably straight chain. These groups, for example, can be substituted with one or more substituents selected from fluorine atom, C _1-6 alkyl group, C _2-6 alkenyl group, and C _2-6 alkynyl group, but preferably Not superseded.

In a preferred embodiment, Z ² is C _1-6 alkylene group or -(CH ₂ ) _z7 -phenylene group -(CH ₂ ) _z8 -, preferably -phenylene group -(CH ₂ ) _z8 - . When Z ² belongs to these groups, higher light resistance, especially ultraviolet resistance, can be obtained.

In another preferred embodiment, the above-mentioned Z ² is a C _1-3 alkylene group. In one aspect, Z ² can be -CH ₂ CH ₂ CH ₂ -. In other aspects, Z ² can be -CH ₂ CH ₂ -.

R ³¹ are each independently -Z ^2' -CR ^32' _q2' R ^33' _r2' .

Z ^2' is independently a single bond, an oxygen atom or a divalent organic group. In addition, as the structure described below Z ^2' , the right side is bonded to (CR ^32' _q2' R ^33' _r2' ).

The above Z ^2' is preferably a C _1-6 alkylene group, -(CH ₂ ) _z5' -O-(CH ₂ ) _z6' -(in the formula, z5' is an integer from 0 to 6, for example, from 1 to 6 Integer, z6' is an integer from 0 to 6, for example, an integer from 1 to 6) or, -(CH ₂ ) _z7' -phenyl-(CH ₂ ) _z8' -(where z7' is an integer from 0 to 6 An integer, such as an integer from 1 to 6, z8' is an integer from 0 to 6, such as an integer from 1 to 6). These C _1-6 alkylene groups may be straight chain or branched chain, but are preferably straight chain. These groups, for example, can be substituted with one or more substituents selected from the group consisting of fluorine atom, C _1-6 alkyl group, C _2-6 alkenyl group, and C _2-6 alkynyl group, but preferably Not superseded.

In a preferred embodiment, Z ^2' is C _1-6 alkylene or -(CH ₂ ) _z7' -phenylene-(CH ₂ ) _z8' -, preferably -phenylene-(CH ₂ ) _z8' -. When Z ^2' belongs to these groups, higher light resistance, especially ultraviolet resistance, can be obtained.

In another preferred embodiment, the above-mentioned Z ^2' is a C _1-3 alkylene group. In one aspect, Z ^2' can be -CH ₂ CH ₂ CH ₂ -. In other aspects, Z ^2' can be -CH ₂ CH ₂ -.

The above-mentioned R ^32' are each independently -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 .

The above Z ³ are each independently a single bond, an oxygen atom or a divalent organic group. In addition, as the structure described in ^Z3 below, the right side is bonded to (SiR ³⁴ _n2 R ³⁵ _3-n2 ).

In one aspect, Z ³ is an oxygen atom.

In one aspect, Z ³ is a divalent organic radical.

The above Z ³ is preferably a C _1-6 alkylene group, -(CH ₂ ) _z5” -O-(CH ₂ ) _z6” - (in the formula, z5” is an integer from 0 to 6, such as an integer from 1 to 6 , z6″ is an integer from 0 to 6, such as an integer from 1 to 6) or, -(CH ₂ ) _z7″ -phenylene-(CH ₂ ) _z8″ -(where z7″ is an integer from 0 to 6) , such as an integer from 1 to 6, z8″ is an integer from 0 to 6, such as an integer from 1 to 6). These C _1-6 alkylene groups may be straight chain or branched chain, but are preferably straight chain. These groups, for example, can be substituted with one or more substituents selected from the group consisting of fluorine atom, C _1-6 alkyl group, C _2-6 alkenyl group, and C _2-6 alkynyl group, but preferably Not superseded.

In a preferred embodiment, Z ³ is C _1-6 alkylene or -(CH ₂ ) _z7” -phenylene-(CH ₂ ) _z8” -, preferably -phenylene-(CH ₂ ) _z8” -. When Z ³ belongs to these groups, higher light resistance, especially ultraviolet resistance, can be obtained.

In another preferred embodiment, the above-mentioned Z ³ is a C _1-3 alkylene group. In one aspect, Z ³ can be -CH ₂ CH ₂ CH ₂ -. In other aspects, Z ³ can be -CH ₂ CH ₂ -.

The above-mentioned R ³⁴ are each independently a hydroxyl group or a hydrolyzable group.

R ³⁴ is preferably each independently a hydrolyzable group.

R ³⁴ is preferably independently -OR ^j , -OCOR ^j , -ON=CR ^j ₂ , -NR ^j ₂ , -NHR ^j , -NCO, or halogen (in these formulas, R ^j represents substituted or unsubstituted Substituted C _1-4 alkyl), more preferably -OR ^j (ie, alkoxy). As R ^j , the series includes unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, etc.; and substituted alkyl groups such as chloromethyl. Among these, an alkyl group is preferable, especially an unsubstituted alkyl group, and a methyl group or an ethyl group is more preferable. In one aspect, R ^j is methyl, in other aspects, R ^j is ethyl.

The above-mentioned R ³⁵ are each independently a hydrogen atom or a monovalent organic group. These monovalent organic groups are monovalent organic groups other than the above-mentioned hydrolyzable groups.

Among the above-mentioned R ³⁵ , the monovalent organic group is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group, and still more preferably a methyl group.

In the above formula, n2 is an integer from 0 to 3 independently in each (SiR ³⁴ _n2 R ³⁵ _3-n2 ) unit. However, when R ^Si belongs to the group represented by formula (S4), there is at least one n2 belonging to 1 to 3 in the terminal part of formula (B1) and formula (B2) (SiR ³⁴ _n2 R ³⁵ _3-n2 ) unit. That is, in these terminal parts, all n2 will not be 0 at the same time. In other words, at least one Si atom bonded to a hydroxyl group or a hydrolyzable group is present in the terminal portion of formula (B1) and formula (B2).

n2 in each (SiR ³⁴ _n2 R ³⁵ _3-n2 ) unit is preferably an integer of 1 to 3, more preferably 2 to 3, and still more preferably 3.

The above-mentioned R ^33' are each independently a hydrogen atom, a hydroxyl group or a monovalent organic group. These monovalent organic groups are monovalent organic groups other than the above-mentioned hydrolyzable groups.

In the above R ^33' , the monovalent organic group is preferably a C _1-20 alkyl group or -(C _s H _2s ) _t1 -(OC _s H _2s ) _t2 (in the formula, s is an integer from 1 to 6, preferably Preferably it is an integer from 2 to 4, t1 is 1 or 0, preferably 0, t2 is an integer from 1 to 20, preferably an integer from 2 to 10, more preferably an integer from 2 to 6), more preferably C _1-20 alkyl group, more preferably C _1-6 alkyl group, particularly preferably methyl group.

In one aspect, R ^33' is hydroxyl.

In other aspects, R ^33' is a monovalent organic group, preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group.

The above q2' are each independently an integer from 0 to 3, and the above r2' are each independently an integer from 0 to 3. Furthermore, the total of q2' and r2' is 3 in the unit (CR ^32' _q2' R ^33' _r2' ).

q2' in each (CR ^32' _q2' R ^33' _r2' ) unit independently is preferably an integer from 1 to 3, more preferably 2 to 3, and even more preferably 3.

R ³² is each independently -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 . These -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 are synonymous with the description of R ^32' above.

The above-mentioned R ³³ are each independently a hydrogen atom, a hydroxyl group or a monovalent organic group. These monovalent organic groups are monovalent organic groups other than the above-mentioned hydrolyzable groups.

In the above R ³³ , the monovalent organic group is preferably a C _1-20 alkyl group or -(C _s H _2s ) _t1 -(OC _s H _2s ) _t2 (in the formula, s is an integer from 1 to 6, preferably is an integer from 2 to 4, t1 is 1 or 0, preferably 0, t2 is an integer from 1 to 20, preferably an integer from 2 to 10, more preferably an integer from 2 to 6), more preferably C _{1 -20} alkyl group, more preferably C _1-6 alkyl group, particularly preferably methyl group.

In one aspect, R ³³ is hydroxyl.

In other aspects, R ³³ is a monovalent organic group, preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group.

The above p2 is an integer from 0 to 3 independently, q2 is an integer from 0 to 3 independently, and r2 is an integer from 0 to 3 independently. Furthermore, the total of p2, q2, and r2 is 3 in the unit (CR ³¹ _p2 R ³² _q2 R ³³ _r2 ).

In one aspect, p2 is 0.

In one aspect, p2 can be an integer from 1 to 3, an integer from 2 to 3, or 3 independently in each (CR ³¹ _p2 R ³² _q2 R ³³ _r2 ) unit. In a preferred embodiment, p2 is 3.

In one aspect, q2 in each (CR ³¹ _p2 R ³² _q2 R ³³ _r2 ) unit is independently an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3.

In one aspect, p2 is 0, and q2 in each (CR ³¹ _p2 R ³² _q2 R ³³ _r2 ) unit is independently an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3 .

The above R ^e1 are each independently -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 . These -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 are synonymous with the description of R ^32' above.

The above-mentioned R ^f1 are each independently a hydrogen atom, a hydroxyl group or a monovalent organic group. These monovalent organic groups are monovalent organic groups other than the above-mentioned hydrolyzable groups.

In the above R ^f1 , the monovalent organic group is preferably a C _1-20 alkyl group or -(C _s H _2s ) _t1 -(OC _s H _2s ) _t2 (in the formula, s is an integer from 1 to 6, preferably is an integer from 2 to 4, t1 is 1 or 0, preferably 0, t2 is an integer from 1 to 20, preferably an integer from 2 to 10, more preferably an integer from 2 to 6), more preferably C _{1 -20} alkyl group, more preferably C _1-6 alkyl group, particularly preferably methyl group.

In one aspect, R ^f1 is hydroxyl.

In other aspects, R ^f1 is a monovalent organic group, preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group.

The above k2 is an integer from 0 to 3 independently, l2 is an integer from 0 to 3 independently, and m2 is an integer from 0 to 3 independently. Furthermore, the total of k2, l2, and m2 is 3 in the (CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 ) unit.

In the above-mentioned formulas (B1) and (B2), when R ^Si belongs to the group represented by the formula (S4), it is preferable that there are at least two terminal parts of the formula (B1) and the formula (B2) related to the hydroxyl group or Si atom bonded with a hydrolyzable group.

In one aspect, when R ^Si belongs to the group represented by formula (S4), n2 is 1 to 3, preferably 2 or 3, more preferably 3 (SiR ³⁴ _n2 R ³⁵ _3-n2 ). The unit is In each terminal part of formula (B1) and formula (B2), there are more than 2, for example, 2 to 27, preferably 2 to 9, more preferably 2 to 6, still more preferably 2 to 3 , the best is 3.

In a preferred aspect, in formula (S4), if R ^32' exists, at least one, preferably all, R ^32' , n2 is an integer from 1 to 3, preferably 2 or 3, Better is 3.

In a preferred aspect, in formula (S4), when R ³² exists, at least one, preferably all R ³² , n2 is an integer from 1 to 3, preferably 2 or 3, and more preferably is 3.

In a preferred aspect, in formula (S4), when R ^e1 exists, at least one, preferably all R ^a1 , n2 is an integer from 1 to 3, preferably 2 or 3, and more preferably is 3.

In a preferred aspect, in formula (S4), k2 is 0, l2 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3.

The above R ^g1 and R ^h1 are independently -Z ⁴ -SiR ²⁵ _n1 R ²⁶ _3-n1 , -Z ⁴ -SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 , -Z ⁴ -CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 . Here, R ²⁵ , R ²⁶ , R ^a1 , R ^b2 , R ^c1 , R ^d1 , R ^e1 , R ^f1 , n1, k1, l1, m1, k2, l2, and m2 are synonymous with the above.

In a preferred embodiment, R ^g1 and R ^h1 are independently -Z ⁴ -SiR ²⁵ _n1 R ²⁶ _3-n1 .

The above Z ⁴ are each independently a single bond, an oxygen atom or a divalent organic group. In addition, as the structure described in Z ⁴ below, the right side is bonded to (SiR ²⁵ _n1 R ²⁶ _3-n1 ).

In one aspect, Z ⁴ is an oxygen atom.

In one aspect, Z ⁴ is a divalent organic radical.

The above Z ⁴ is preferably a C _1-6 alkylene group, -(CH ₂ ) _z5” -O-(CH ₂ ) _z6” - (in the formula, z5” is an integer from 0 to 6, such as an integer from 1 to 6 , z6″ is an integer from 0 to 6, such as an integer from 1 to 6) or, -(CH ₂ ) _z7″ -phenylene-(CH ₂ ) _z8″ -(where z7″ is an integer from 0 to 6) , such as an integer from 1 to 6, z8″ is an integer from 0 to 6, such as an integer from 1 to 6). These C _1-6 alkylene groups may be straight chain or branched chain, but are preferably straight chain. These groups, for example, can be substituted with one or more substituents selected from the group consisting of fluorine atom, C _1-6 alkyl group, C _2-6 alkenyl group, and C _2-6 alkynyl group, but preferably Not superseded.

In a preferred embodiment, Z ⁴ is C _1-6 alkylene or -(CH ₂ ) _z7” -phenylene-(CH ₂ ) _z8” -, preferably -phenylene-(CH ₂ ) _z8” -. When Z ³ belongs to these groups, higher light resistance, especially ultraviolet resistance, can be obtained.

In another preferred embodiment, the above-mentioned Z ⁴ is a C _1-3 alkylene group. In one aspect, Z ⁴ can be -CH ₂ CH ₂ CH ₂ -. In other aspects, Z ⁴ can be -CH ₂ CH ₂ -.

In one aspect, R ^Si is a group represented by formula (S2), (S3), (S4) or (S5). These compounds can form a hardened material layer with high surface slippery properties.

In one aspect, R ^Si is a group represented by formula (S3), (S4) or (S5). Since these compounds have a plurality of hydrolyzable groups at one end, they can form a hardened material layer that has strong adhesion to the base material and has high abrasion durability.

In one aspect, R ^Si is a group represented by formula (S3) or (S4). Since these compounds can have a plurality of hydrolyzable groups branched from one Si atom or C atom at a single terminal, a hardened material layer with higher wear durability can be formed.

In one aspect, R ^Si is a base represented by formula (S1).

In one aspect, R ^Si is a base represented by formula (S2).

In one aspect, R ^Si is a base represented by formula (S3).

In one aspect, R ^Si is a base represented by formula (S4).

In one aspect, R ^Si is a base represented by formula (S5).

In the above ^- mentioned formulas (B1) ^and ( ^B2 ), (R ^Si ) connector. Therefore, as long as the compounds represented by formulas (B1) and (B2) can exist stably, X ^Z may be a single bond or any group.

In the above formula (B1), α is an integer from 1 to 9, and β is an integer from 1 to 9. These α and β can change in response to the valence of X ^Z. The sum of α and β is the same as the valence of X ^Z. For example, when X ^Z is a 10-valent organic group, the sum of α and β is 10. For example, α is 9 and β is 1, α is 5 and β is 5, or α is 1 and β is 9. In addition, when X ^Z is a divalent organic group, α and β are 1.

In the above formula (B2), γ is an integer from 1 to 9. γ can respond to changes in the valence of X ^Z. That is, γ is the value obtained by subtracting 1 from the valence of X ^Z.

X and ^Z are each independently a single bond or an organic group with a valence of 2 to 10;

The organic group with a valence of 2 to 10 in the above-mentioned X ^Z is preferably an organic group with a valence of 2 to 8. In one aspect, these 2- to 10-valent organic groups are preferably 2- to 4-valent organic groups, more preferably 2-valent organic groups. In other aspects, these 2 to 10 valent organic groups are preferably 3 to 8 valent organic groups, more preferably 3 to 6 valent organic groups.

In one aspect, X ^Z is a single bond or a divalent organic group, α is 1, and β is 1.

In one aspect, X ^Z is a single bond or a divalent organic group, and γ is 1.

In one aspect, X ^Z is an organic group with 3 to 6 valences, α is 1, and β is 2 to 5.

In one aspect, X ^Z is an organic group with 3 to 6 valences, and γ is 2 to 5.

In one aspect, X ^Z is a trivalent organic group, α is 1, and β is 2.

In one aspect, X ^Z is a trivalent organic radical, and γ is 2.

When X ^Z is a single bond or a divalent organic group, the formulas (B1) and (B2) are represented by the following formulas (B1') and (B2').

R ^F3 -X ^A -R ^Si (B1')

R ^Si -X ^A -R ^F4 -X ^A -R ^Si (B2')

In one aspect, X ^Z is a single bond.

In other aspects, X ^Z is a divalent organic radical.

In one aspect, as X ^Z , the series includes, for example, a single bond or a divalent organic group represented by the following formula.

-(R ⁵¹ ) _p5 -(X ⁵¹ ) _q5 -

[In the formula:

R ⁵¹ represents a single bond, -(CH ₂ ) _s5 - or o-, m- or p-phenylene group, preferably -(CH ₂ ) _s5 -,

s5 is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, and even more preferably 1 or 2,

X ⁵¹ means -(X ⁵² ) _l5 -,

X ⁵² each independently represents a group selected from -O-, -S-, o-, m- or p-phenylene, -C(O)O-, -Si(R ⁵³ ) ₂ -, -(Si(R ⁵³ ) ₂ O) _m5 -The base of the group consisting of -Si(R ⁵³ ) ₂ -, -CONR ⁵⁴ -, -O-CONR ⁵⁴ -, -NR ⁵⁴ - and -(CH ₂ ) _n5 -,

R ⁵³ independently represents phenyl, C _1-6 alkyl or C _1-6 alkoxy, preferably phenyl or C _1-6 alkyl, more preferably methyl,

R ⁵⁴ each independently represents a hydrogen atom, phenyl or C _1-6 alkyl group (preferably methyl),

Each time m5 appears, it is independently an integer from 1 to 100, preferably an integer from 1 to 20.

Each time n5 appears, it is independently an integer from 1 to 20, preferably an integer from 1 to 6, and more preferably an integer from 1 to 3.

l5 is an integer from 1 to 10, preferably an integer from 1 to 5, more preferably an integer from 1 to 3,

p5 is 0 or 1,

q5 is 0 or 1,

Here, at least one of p5 and q5 is 1, and the order of existence of the repeating units marked p5 or q5 and enclosed in parentheses in the formula is arbitrary]

Here, X ^Z (typically the hydrogen atom of X ^Z ) may be substituted with one or more than one substituent selected from a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group. In a preferred embodiment, X ^Z is not substituted by these groups.

In a preferred aspect, the above-mentioned X ^Z are independently -(R ⁵¹ ) _p5 -(X ⁵¹ ) _q5 -R ⁵² -. R ⁵² represents a single bond, -(CH ₂ ) _t5 - or o-, m- or p-phenylene group, preferably -(CH ₂ ) _t5 -. t5 is an integer from 1 to 20, preferably an integer from 2 to 6, and more preferably an integer from 2 to 3. Here, R ⁵² (typically the hydrogen atom of R ⁵² ) may be substituted with one or more than one substituent selected from a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group. In a preferred embodiment, R ⁵⁶ is not substituted by these groups.

Preferably, the above-mentioned X ^{and Z} can be independently single bonds,

C _1-20 alkylene group,

-R ⁵¹ -X ⁵³ -R ⁵² -, or

-X ⁵⁴ -R ⁵ -

[In the formula, R ⁵¹ and R ⁵² are synonymous with the above,

X ⁵³ means

-O-、

-S-、

-C(O)O-、

-CONR ⁵⁴ -,

-O-CONR ⁵⁴ -,

-Si(R ⁵³ ) ₂ -,

-(Si(R ⁵³ ) ₂ O) _m5 -Si(R ⁵³ ) ₂ -,

-O-(CH ₂ ) _u5 -(Si(R ⁵³ ) ₂ O) _m5 -Si(R ⁵³ ) ₂ -,

-O-(CH ₂ ) _u5 -Si(R ⁵³ ) ₂ -O-Si(R ⁵³ ) ₂ -CH ₂ CH ₂ -Si(R ⁵³ ) ₂ -O-Si(R ⁵³ ) ₂ -,

-O-(CH ₂ ) _u5 -Si(OCH ₃ ) ₂ OSi(OCH ₃ ) ₂ -,

-CONR ⁵⁴ -(CH ₂ ) _u5 -(Si(R ⁵³ ) ₂ O) _m5 -Si(R ⁵³ ) ₂ -,

-CONR ⁵⁴ -(CH ₂ ) _u5 -N(R ⁵⁴ )-, or

-CONR ⁵⁴ -(o-, m- or p-phenyl)-Si(R ⁵³ ) ₂ -

(In the formula, R ⁵³ , R ⁵⁴ and m5 are synonymous with the above,

u5 is an integer from 1 to 20, preferably an integer from 2 to 6, more preferably an integer from 2 to 3),

X ⁵⁴ means

-S-、

-C(O)O-、

-CONR ⁵⁴ -,

-O-CONR ⁵⁴ -,

-CONR ⁵⁴ -(CH ₂ ) _u5 -(Si(R ⁵⁴ ) ₂ O) _m5 -Si(R ⁵⁴ ) ₂ -,

-CONR ⁵⁴ -(CH ₂ ) _u5 -N(R ⁵⁴ )-, or

-CONR ⁵⁴ -(o-, m- or p-phenyl)-Si(R ⁵⁴ ) ₂ -

(In the formula, each symbol has the same meaning as above)].

More preferably, the above-mentioned X ^{and Z} are independently single bonds,

C _1-20 alkylene group,

-(CH ₂ ) _s5 -X ⁵³ -、

-(CH ₂ ) _s5 -X ⁵³ -(CH ₂ ) _t5 -

-X ⁵⁴ -, or

-X ⁵⁴ -(CH ₂ ) _t5 -

[In the formula, X ⁵³ , X ⁵⁴ , s5 and t5 are synonymous with the above].

More preferably, the above X ^Z can be independently

single key,

C _1-20 alkylene group,

-(CH ₂ ) _s5 -X ⁵³ -(CH ₂ ) _t5 -, or

-X ⁵⁴ -(CH ₂ ) _t5 -

[In the formula, each symbol has the same meaning as above].

In a preferred aspect, the above-mentioned X ^Z can be independently a single bond,

C _1-20 alkylene group,

-(CH ₂ ) _s5 -X ⁵³ -, or

-(CH ₂ ) _s5 -X ⁵³ -(CH ₂ ) _t5 -

[In the formula,

X ⁵³ is -O-, -CONR ⁵⁴ -, or -O-CONR ⁵⁴ -,

R ⁵⁴ each independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group,

s5 is an integer from 1 to 20,

t5 is an integer from 1 to 20].

In a preferred aspect, the above X ^Z can be independently

-(CH ₂ ) _s5 -O-(CH ₂ ) _t5 -

-CONR ⁵⁴ -(CH ₂ ) _t5 -

[In the formula,

R ⁵⁴ represents independently, a hydrogen atom, a phenyl group or a C _1-6 alkyl group,

s5 is an integer from 1 to 20,

t5 is an integer from 1 to 20].

In one aspect, the above X ^Z are independently

single key,

C _1-20 alkylene group,

-(CH ₂ ) _s5 -O-(CH ₂ ) _t5 -,

-(CH ₂ ) _s5 -(Si(R ⁵³ ) ₂ O) _m5 -Si(R ⁵³ ) ₂ -(CH ₂ ) _t5 -,

-(CH ₂ ) _s5 -O-(CH ₂ ) _u5 -(Si(R ⁵³ ) ₂ O) _m5 -Si(R ⁵³ ) ₂ -(CH ₂ ) _t5 -, or

-(CH ₂ ) _s5 -O-(CH ₂ ) _t5 -Si(R ⁵³ ) ₂ -(CH ₂ ) _u5 -Si(R ⁵³ ) ₂ -(C _v H _2v )-

[In the formula, R ⁵³ , m5, s5, t5 and u5 are synonymous with the above, v5 is an integer from 1 to 20, preferably an integer from 2 to 6, more preferably an integer from 2 to 3].

In the above formula, -(C _v H _2v )- can be a straight chain or a branched chain, for example, it can be -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )-, - CH(CH ₃ )CH ₂ -.

_{The above -} ^mentioned base substitution. In one aspect, X ^Z is unsubstituted.

Moreover, the left side of the above-mentioned X ^Z is bonded to ^RF3 or ^RF4 , and the right side is bonded to R ^Si .

In one aspect, X ^{and Z} can each independently be other than -OC _1-6 alkylene.

In other forms, as X ^Z , the series is exemplified by the following basis:

[In the formula, R ⁴¹ is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C _1-6 alkoxy group, preferably a methyl group;

D is a basis selected from the following:

-CH ₂ O(CH ₂ ) ₂ -,

-CH ₂ O(CH ₂ ) ₃ -,

-CF ₂ O(CH ₂ ) ₃ -,

-(CH ₂ ) ₂ -,

-(CH ₂ ) ₃ -,

-(CH ₂ ) ₄ -,

-CONH-(CH ₂ ) ₃ -,

-CON(CH ₃ )-(CH ₂ ) ₃ -,

-CON(Ph)-(CH ₂ ) ₃ -(where Ph means phenyl), and

(In the formula, R ⁴² each independently represents a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group)

E is -(CH ₂ ) _n (n is an integer from 2 to 6),

D is bonded to ^RF3 or ^RF4 in the main chain of the molecule, and E is bonded to R ^Si ]

As specific examples of the above X ^Z , a series of examples include:

single key,

-CH ₂ OCH ₂ -,

-CH ₂ O(CH ₂ ) ₂ -,

-CH ₂ O(CH ₂ ) ₃ -,

-CH ₂ O(CH ₂ ) ₄ -,

-CH ₂ O(CH ₂ ) ₅ -,

-CH ₂ O(CH ₂ ) ₆ -,

-CH ₂ O(CH ₂ ) ₃ Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-CH ₂ O(CH ₂ ) ₃ Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ OSi(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-CH ₂ O(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₂ Si(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-CH ₂ O(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₃ Si(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-CH ₂ O(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₁₀ Si(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-CH ₂ O(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₂₀ Si(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-CH ₂ OCF ₂ CHFOCF ₂ -,

-CH ₂ OCF ₂ CHFOCF ₂ CF ₂ -,

-CH ₂ OCF ₂ CHFOCF ₂ CF ₂ CF ₂ -,

-CH ₂ OCH ₂ CF ₂ CF ₂ OCF ₂ -,

-CH ₂ OCH ₂ CF ₂ CF ₂ OCF ₂ CF ₂ -,

-CH ₂ OCH ₂ CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ -,

-CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ )CF ₂ OCF ₂ -,

-CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ )CF ₂ OCF ₂ CF ₂ -,

-CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ )CF ₂ OCF ₂ CF ₂ CF ₂ -,

-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ -,

-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF ₂ -,

-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF ₂ CF ₂ -,

-CH ₂ OCH ₂ CHFCF ₂ OCF(CF ₃ )CF ₂ OCF ₂ -,

-CH ₂ OCH ₂ CHFCF ₂ OCF(CF ₃ )CF ₂ OCF ₂ CF ₂ -,

-CH ₂ OCH ₂ CHFCF ₂ OCF(CF ₃ )CF ₂ OCF ₂ CF ₂ CF ₂ -,

-CH ₂ OCF ₂ CHFOCF ₂ CF ₂ CF ₂ -C(O)NH-CH ₂ -,

- CH ₂ OCH ₂ (CH ₂ ) ₇ CH ₂ Si(OCH ₃ ) ₂ OSi(OCH ₃ ) ₂ (CH ₂ ) ₂ Si(OCH ₃ ) ₂ OSi(OCH ₃ ) ₂ (CH ₂ ) ₂ -,

-CH ₂ OCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₂ OSi(OCH ₃ ) ₂ (CH ₂ ) ₃ -,

-CH ₂ OCH ₂ CH ₂ CH ₂ Si(OCH ₂ CH ₃ ) ₂ OSi(OCH ₂ CH ₃ ) ₂ (CH ₂ ) ₃ -,

-CH ₂ OCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₂ OSi(OCH ₃ ) ₂ (CH ₂ ) ₂ -,

-CH ₂ OCH ₂ CH ₂ CH ₂ Si(OCH ₂ CH ₃ ) ₂ OSi(OCH ₂ CH ₃ ) ₂ (CH ₂ ) ₂ -,

-(CH ₂ ) ₂ -Si(CH ₃ ) ₂ -(CH ₂ ) ₂ -,

-CH ₂ -,

-(CH ₂ ) ₂ -、

-(CH ₂ ) ₃ -,

-(CH ₂ ) ₄ -,

-(CH ₂ ) ₅ -、

-(CH ₂ ) ₆ -,

-CO-、

-CONH-、

-CONH-CH ₂ -,

-CONH-(CH ₂ ) ₂ -,

-CONH-(CH ₂ ) ₃ -,

-CONH-(CH ₂ ) ₄ -,

-CONH-(CH ₂ ) ₅ -,

-CONH-(CH ₂ ) ₆ -,

-CON(CH ₃ )-CH ₂ -,

-CON(CH ₃ )-(CH ₂ ) ₂ -,

-CON(CH ₃ )-(CH ₂ ) ₃ -,

-CON(CH ₃ )-(CH ₂ ) ₄ -,

-CON(CH ₃ )-(CH ₂ ) ₅ -,

-CON(CH ₃ )-(CH ₂ ) ₆ -,

-CON(Ph)-CH ₂ -(where Ph means phenyl),

-CON(Ph)-(CH ₂ ) ₂ -(where Ph means phenyl),

-CON(Ph)-(CH ₂ ) ₃ -(where Ph means phenyl),

-CON(Ph)-(CH ₂ ) ₄ -(where Ph means phenyl),

-CON(Ph)-(CH ₂ ) ₅ -(where Ph means phenyl),

-CON(Ph)-(CH ₂ ) ₆ -(where Ph means phenyl),

-CONH-(CH ₂ ) ₂ NH(CH ₂ ) ₃ -,

-CONH-(CH ₂ ) ₆ NH(CH ₂ ) ₃ -,

-CH ₂ O-CONH-(CH ₂ ) ₃ -,

-CH ₂ O-CONH-(CH ₂ ) ₆ -,

-S-(CH ₂ ) ₃ -,

-(CH ₂ ) ₂ S(CH ₂ ) ₃ -,

-CONH-(CH ₂ ) ₃ Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-CONH-(CH ₂ ) ₃ Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ OSi(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-CONH-(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₂ Si(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-CONH-(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₃ Si(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-CONH-(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₁₀ Si(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-CONH-(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₂₀ Si(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-C(O)O-(CH ₂ ) ₃ -,

-C(O)O-(CH ₂ ) ₆ -,

-CH ₂ -O-(CH ₂ ) ₃ -Si(CH ₃ ) ₂ -(CH ₂ ) ₂ -Si(CH ₃ ) ₂ -(CH ₂ ) ₂ -,

-CH ₂ -O-(CH ₂ ) ₃ -Si(CH ₃ ) ₂ -(CH ₂ ) ₂ -Si(CH ₃ ) ₂ -CH(CH ₃ )-,

-CH ₂ -O-(CH ₂ ) ₃ -Si(CH ₃ ) ₂ -(CH ₂ ) ₂ -Si(CH ₃ ) ₂ -(CH ₂ ) ₃ -,

-CH ₂ -O-(CH ₂ ) ₃ -Si(CH ₃ ) ₂ -(CH ₂ ) ₂ -Si(CH ₃ ) ₂ -CH(CH ₃ )-CH ₂ -,

-OCH ₂ -,

-O(CH ₂ ) ₃ -,

-OCFHCF ₂ -,

、

等。

,

wait.

In other aspects, X ^{and Z} are independently represented by the formula: -(R ¹⁶ ) _x1 -(CFR ¹⁷ ) _y1 -(CH ₂ ) _z1 -. In the formula, x1, y1 and z1 are each independently an integer from 0 to 10, and the sum of x1, y1 and z1 is more than 1. The order of the repeating units enclosed in brackets in the formula is arbitrary.

In the above formula, R ¹⁶ is independently an oxygen atom, a phenylene group, a carbazoline, -NR ¹⁸ - (in the formula, R ¹⁸ represents a hydrogen atom or an organic group) or a divalent organic group. Preferably, R ¹⁸ is an oxygen atom or a divalent polar group.

The above-mentioned "divalent polar group" is not particularly limited, but the series includes: -C(O)-, -C(=NR ¹⁹ )-, and -C(O)NR ¹⁹ - (in these formulas , R ¹⁹ represents a hydrogen atom or lower alkyl group). The "lower alkyl group" is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, which may be substituted by one or more than one fluorine atom.

In the above formula, R ¹⁷ is each independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom. The "lower fluoroalkyl group" is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, and more preferably a trifluoromethyl group. base, pentafluoroethyl, and more preferably trifluoromethyl.

Among other aspects, as an example of X ^Z , the series is based on the following:

[In the formula,

R ⁴¹ is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C _1-6 alkoxy group, preferably a methyl group;

In each X ^Z group, any one of T is bonded to the following groups of ^RF3 or ^RF4 in the main chain of the molecule:

-CH ₂ O(CH ₂ ) ₂ -,

-CH ₂ O(CH ₂ ) ₃ -,

-CF ₂ O(CH ₂ ) ₃ -,

-(CH ₂ ) ₂ -,

-(CH ₂ ) ₃ -,

-(CH ₂ ) ₄ -,

-CONH-(CH ₂ ) ₃ -,

-CON(CH ₃ )-(CH ₂ ) ₃ -,

-CON(Ph)-(CH ₂ ) ₃ -(where Ph means phenyl), or

[In the formula, R ⁴² each independently represents a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group],

If any of the other T's are bonded to ^RSi in the main chain of the molecule and exist, the remaining T's are independently methyl, phenyl, C _1-6 alkoxy, free radical capturing group or ultraviolet absorbing group. .

類之殘基。 The free radical trapping group is not particularly limited as long as it can capture free radicals generated by light irradiation. Examples of the series include: benzophenones, benzotriazoles, benzoate esters, and phenyl salicylate. esters, crotonic acids, malonates, organic acrylates, hindered amines, hindered phenols, or three

Such residues.

酮類、苯并

唑類之殘基。 The ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet rays. Examples of the series include: benzotriazoles, hydroxydiphenylketones, substituted and unsubstituted benzoic acid or salicyloxy compound esters, acrylates or Alkoxycinnamates, oxalamides, oxalanilines, benzo

Ketones, Benzos

Azole residues.

In a preferred embodiment, a series of preferred free radical capturing groups or ultraviolet absorbing groups are as follows:

In this aspect, X ^{and Z} may independently be organic groups with 3 to 10 valences.

Among other aspects, as an example of X ^Z , the series is based on the following:

[In the formula, R ²⁵ , R ²⁶ and R ²⁷ are each independently an organic group of 2 to 6 valence,

R ²⁵ is bonded to at least one R ^F , R ²⁶ and R ²⁷ are each bonded to at least one R ^Si ]

In one aspect, the above R ²⁵ is a single bond, C _1-20 alkylene group, C _3-20 cycloalkylene group, C _5-20 arylene group, -R ⁵⁷ -X ⁵⁸ -R ⁵⁹ -, - X ⁵⁸ -R ⁵⁹ -, or -R ⁵⁷ -X ⁵⁸ -. The above-mentioned R ⁵⁷ and R ⁵⁹ are each independently a single bond, a C _1-20 alkylene group, a C _3-20 cycloalkylene group, or a C _5-20 arylene group. The above X ⁵⁸ is -O-, -S-, -CO-, -O-CO- or -COO-.

In one aspect, the above-mentioned R ²⁶ and R ²⁷ are each independently a hydrocarbon, or a group having at least 1 atom selected from N, O and S at the end or main chain of the hydrocarbon, preferably C _{1- 6} alkyl, -R ³⁶ -R ³⁷ -R ³⁶ -, -R ³⁶ -CHR ³⁸ ₂ -, etc. Here, R ³⁶ is each independently a single bond or an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. R ³⁷ is N, O or S, preferably N or O. R ³⁸ is -R ⁴⁵ -R ⁴⁶ -R ⁴⁵ -, -R ⁴⁶ -R ⁴⁵ - or -R ⁴⁵ -R ⁴⁶ -. Here, R ⁴⁵ is each independently an alkyl group having 1 to 6 carbon atoms. R ⁴⁶ is N, O or S, preferably O.

In this aspect, X ^{and Z} may independently be organic groups with 3 to 10 valences.

In other cases, as an example of X ^Z , the series is based on the following:

[In the formula, X ^a is a single bond or a divalent organic group]

The above-mentioned X ^a is a single bond or a divalent linking group directly bonded to the isocyanuric acid ring. X ^a is preferably a divalent group containing at least one bond selected from the group consisting of a single bond, an alkylene group, or an ether bond, an ester bond, an amide bond, and a sulfur bond. , more preferably, it contains at least one bonded carbon selected from the group consisting of a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether bond, an ester bond, an amide bond, and a sulfur bond. Divalent hydrocarbon groups numbered 1 to 10.

X ^a is more preferably a base represented by the following formula:

-(CX ¹²¹ X ¹²² ) _x1 -(X ^a1 ) _y1 -(CX ¹²³ X ¹²⁴ ) _z1 -

⁽ In the ^formula , ^{X 121} _to

The above X ^a1 is -C(=O)NH-, -NHC(=O)-, -O-, -C(=O)O-, -OC(=O)-, -OC(=O)O- , or -NHC(=O)NH-(the left side of each bond is bonded to CX ¹²¹ X ¹²² ),

x1 is an integer from 0 to 10, y1 is 0 or 1, z1 is an integer from 1 to 10).

As the above-mentioned X ^a1 , -O- or -C(=O)O- is preferred.

As the above-mentioned X ^a , the following formula is particularly preferred:

-(CF ₂ ) _m11 -(CH ₂ ) _m12 -O-(CH ₂ ) _m13 -the base shown

(In the formula, m11 is an integer from 1 to 3, m12 is an integer from 1 to 3, and m13 is an integer from 1 to 3),

-(CF ₂ ) _m14 -(CH ₂ ) _m15 -O-CH ₂ CH(OH)-(CH ₂ ) _m16 -the group shown

(In the formula, m14 is an integer from 1 to 3, m15 is an integer from 1 to 3, and m16 is an integer from 1 to 3),

-(CF ₂ ) _m17 -(CH ₂ ) _m18 -the base shown

(In the formula, m17 is an integer from 1 to 3, m18 is an integer from 1 to 3),

-(CF ₂ ) _m19 -(CH ₂ ) _m20 -O-CH ₂ CH(OSi(OCH ₃ ) ₃ )-(CH ₂ ) _m21 -The base shown

(In the formula, m19 is an integer from 1 to 3, m20 is an integer from 1 to 3, m21 is an integer from 1 to 3), or

-(CH ₂ ) _m22 -the base shown

(In the formula, m22 is an integer from 1 to 3).

The above-mentioned X ^a is not particularly limited, but specifically, the series includes:

-CH ₂ -, -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -, -C ₄ H ₈ -O-CH ₂ -, -CO-O-CH ₂ -CH(OH) -CH ₂ -, -(CF ₂ ) _n5 -(n5 is an integer from 0 to 4), -(CF ₂ ) _n5 -(CH ₂ ) _m5 -(n5 and m5 are independently an integer from 0 to 4), -CF ₂ CF ₂ CH ₂ OCH ₂ CH(OH)CH ₂ -, -CF ₂ CF ₂ CH ₂ OCH ₂ CH(OSi(OCH ₃ ) ₃ )CH ₂ -etc.

In this aspect, X ^{and Z} can be independently divalent or trivalent organic groups.

The fluoropolyether group-containing silane compound represented by the above formula (B1) or formula (B2) is not particularly limited, but may have an average molecular weight of 5×10 ² to 1×10 ⁵ . Within this range, in terms of the balance between the viscosity of the composition, the solubility of each component, and the physical properties of the cured product, it is preferable to have an average molecular weight of 1,000 to 32,000, more preferably 1,500 to 8,000. In addition, these "average molecular weights" are called number average molecular weights, and the "average molecular weight" is a value measured by ¹⁹ F-NMR.

The fluorine-containing polyether group silane compound represented by the above formula (B1) or formula (B2), for example, can be prepared by a conventional method, such as International Publication No. 97/07155, Japanese Patent Publication No. 2008-534696, Japanese Patent Publication No. 2008-534696, Obtained by methods recorded in Opening No. 2014-218639, Special Opening No. 2017-82194, etc.

In another preferred embodiment, the fluorine-containing polyether group silane compound is a compound represented by the following formula (B3),

R ³⁹ _j -R ³⁸ -NR ³⁷ CO-(R ^F4 -CONR ³⁷ -R ³⁶ -NR ³⁷ CO) _r -R ^F4 -CONR ³⁷ -R ³⁸ -R ³⁹ _j (B3)

[In the formula:

R ^F4 is -Rf ⁴ _p3 -R ^FB -O _q3 -;

Rf ⁴ is a C _1-6 alkylene group which may be substituted by 1 or more than 1 fluorine atom;

R ^FB are independently divalent fluoropolyether groups;

p3 is 0 or 1;

q3 is 0 or 1;

R ³⁶ are each independently a divalent organic group,

R ³⁷ is each independently a hydrogen atom or an organic group with one valence of carbon atoms from 1 to 8,

R ³⁸ are each independently an organic radical with (j+1) valence,

R ³⁹ are each independently -SiR ²⁵ _n1 R ²⁶ _3-n1 ,

R ²⁵ is independently a hydroxyl group or a hydrolyzable group;

R ²⁶ are each independently a hydrogen atom or a monovalent organic group;

Each n1 (SiR ²⁵ _n1 R ²⁶ _3-n1 ) unit is independently an integer from 0 to 3;

j are independently integers from 1 to 9,

r is an integer above 1].

In the formula (B3), R ^F4 , Rf ⁴ , R ^FB , R ²⁵ , R ²⁶ , n1, p3, and q3 are synonymous with the above descriptions of the formulas (B1) and (B2), and include the same aspects.

In the above formula (B3), R ³⁸ is each independently an organic group with a valence of (j+1).

R ³⁸ is a group that serves as a linker between R ³⁹ and the amide bond (CONR ³² ). R ³⁸ independently represents an organic radical with a valence of j+1 on each occurrence. Here, the value of j represents the number of silicon atom-containing groups present at the terminals of the fluorine-containing polyether group-containing silane compound (B3), and its value is in the range of 1 to 9. Thus, each occurrence of R ³⁸ independently represents an organic radical with a valence of 2 to 10. Therefore, R ³⁸ may be any group as long as it is a 2- to 10-valent organic group that can stably exist in the silane compound (B3) containing the fluorine polyether group. As a specific example of R ³⁸ , in the above-mentioned formulas (B1) and (B2), it is synonymous with X ^Z and may include the same aspect. R ³⁸ preferably has a valence of 2 to 7, more preferably a valence of 2 to 4, and more preferably a divalent organic base.

R ³⁸ preferably has no heteroatom or aromatic structure on the molecular chain directly connecting R ³⁹ and the amide bond, and more preferably has no aromatic structure. R ³⁸ is preferably an aliphatic hydrocarbon group which may have a heteroatom depending on the situation, more preferably an unsubstituted aliphatic hydrocarbon group, and still more preferably a divalent alkylene group. R ³⁸ is more preferably a C _1-20 alkylene group, more preferably a C _1-6 alkylene group, and particularly specifically, a methylene group, an ethylene group, a propylene group, or a methyl ethylene group. base, butylene, hexamethylene, etc. The two R ³⁸ present in the above-mentioned silane compound (B3) containing a fluorine-containing polyether group may be the same or different. However, in order to facilitate the preparation of the compound, the two R 38s are preferably the same. In addition, R ³⁸ will have j+1 bonding locations, but it can be partially bonded with -C(=O)NR ³⁷ - at any bonding location.

In the above formula (B3), j is each independently an integer from 1 to 9, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, and still more preferably 1.

In the above formula (B3), R ³⁶ is each independently a divalent organic group.

R ³⁶ is a divalent organic group connecting the structures shown by -C(=O)NR ³⁷ - at both ends thereof. The definition of "divalent organic group" is the same as when R ³⁸ is a divalent organic group. However, R ³⁶ is preferably a divalent alkylene group, more preferably a C _1-20 alkylene group, and More preferably, it is a C _1-6 alkylene group, and specifically, it is a methylene group, an ethylene group, a propylene group, a methyl ethylene group, a butylene group, a hexamethylene group, etc. In addition, R ³⁶ is a group connecting two -C(=O)NR ³⁷ - moieties. However, as long as this can be formulated into a stable compound, the two bonding positions of R ³⁶ can be combined with the -C(= O)NR ³⁷ - Any bond in the section. For example, when R ³⁶ in formula (B3) belongs to methylethylidene (-CH(CH ₃ )CH ₂ -), the CH ₂ - part of the methylethylidene group can be bonded to the position in formula (B3). The -C(=O)NR ³⁷ -part on the right can be bonded to the -C(=O)NR ³⁷ -part on the left. For example, the R ³⁶ moiety can be introduced by using a diamine and a compound having a reactive functional group capable of forming a bond with R ³⁸ or R ³⁶ at both ends of ^{RF 4} through an amide bond. The number of R ³⁶ moieties in the molecular chain (in other words, the value of r) can be manipulated by adjusting the amount relationship of the reactants.

In a preferred embodiment, R ³⁸ and R ³⁶ are both divalent alkylene groups.

In the above formula (B3), R ³⁷ is each independently a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms.

The monovalent organic group having 1 to 8 carbon atoms in R ³⁷ is preferably a C _1-8 alkyl group, a C _3-8 cycloalkyl group, or a C _5-8 aryl group, and more preferably a C _1-6 alkyl group. Or phenyl, more preferably C _1-3 alkyl, particularly preferably methyl.

In one aspect, R ³⁷ is a hydrogen atom.

In one aspect, R ³⁷ is C _1-8 alkyl, preferably methyl.

In the above formula (B3), r is an integer of 1 or more.

In one aspect, r is preferably an integer from 1 to 100, more preferably an integer from 1 to 10, and more preferably an integer from 1 to 5, such as an integer from 2 to 10, and more preferably an integer from 2 to 5. integer.

The fluorine-containing polyether group-containing silane compound represented by the above formula (B3) is not particularly limited, but may have an average molecular weight of 5×10 ² to 1×10 ⁵ . Among these ranges, in terms of the balance between the viscosity of the composition, the solubility of each component, and the physical properties of the cured product, an average molecular weight of 1,000 to 32,000 is more preferred, and an average molecular weight of 1,500 to 8,000 is more preferred. In addition, these "average molecular weights" are called number average molecular weights, and the "average molecular weight" is a value measured by ¹⁹ F-NMR.

The fluorine-containing polyether group silane compound represented by the above formula (B3) can be produced, for example, by the method described in International Publication No. 2021/125058 and the like.

In one aspect, the above-mentioned fluorine-containing polyether group silane compound includes a compound represented by formula (B1) or (B2). For example, the above-mentioned fluorine-containing polyether group silane compound is a compound represented by formula (B1) or (B2).

In one aspect, the above-mentioned fluoropolyether group-containing silane compound includes a compound represented by formula (B1). For example, the above-mentioned fluorine-containing polyether group silane compound is a compound represented by formula (B1).

In one aspect, the above-mentioned fluoropolyether group-containing silane compound includes a compound represented by formula (B2). For example, the above-mentioned silane compound containing a fluorine polyether group is a compound represented by formula (B2).

In one aspect, the above-mentioned fluoropolyether group-containing silane compound includes a compound represented by formula (B3). For example, the above-mentioned silane compound containing a fluorine polyether group is a compound represented by formula (B3).

In a preferred embodiment, the above-mentioned silane compound containing a fluoropolyether group includes a compound represented by formula (B2) and/or a compound represented by formula (B3). For example, the above-mentioned fluorine-containing polyether group silane compound is a compound represented by formula (B2) and/or a compound represented by formula (B3).

In another preferred embodiment, the above-mentioned silane compound containing a fluoropolyether group includes a compound represented by formula (B2) and a compound represented by formula (B3). For example, the fluorine-containing polyether group-containing silane compound is a compound represented by formula (B2) and a compound represented by formula (B3).

Compounds having hydrolyzable silicon groups at both ends (for example, compounds represented by formula (B2) and compounds represented by formula (B3)), and compounds having hydrolyzable silicon groups at one end (for example, compounds represented by formula (B1) The molar ratio (two-terminal compound/single-terminal compound) of the compound shown) is preferably 50/50 to 100/0, more preferably 60/40 to 100/0, and more preferably 90/10 to 100/0.

In the curable composition of the present disclosure, the content of component (A) is preferably 10 to 90 mass%, more preferably 20 to 80 mass%, relative to the total amount of component (A) and component (B), and More preferably, it is 30 to 70 mass %. By setting the content of the acrylic compound of the fluorine-containing polyether group to the above range, the UV curability and flexibility of the obtained cured product can be further improved, and bleeding can be further reduced.

Ingredient (C): Cross-linking agent

The cross-linking agent is not particularly limited, but may be, for example, an alkoxysilane compound.

In a preferred aspect, the above-mentioned cross-linking agent is preferably a compound represented by formula (C1),

(R ^g1 -O) _δ -Si-R ^g2 _4-δ (C1)

[In the formula:

Each time R ^g1 appears, it is independently a hydrogen atom or a 1-valent organic group;

R ^g2 are independently univalent organic groups;

δ is an integer from 2 to 4].

R ^g1 can each be independently preferably a monovalent organic group, more preferably a C _1-6 alkyl group, still more preferably a methyl or ethyl group.

R ^g2 can be independently preferably C _1-16 alkyl, C _3-16 cycloalkyl, C _6-16 aryl, or C _1-16 alkenyl, more preferably C _1-16 alkyl, and More preferably, it is a C _1-10 alkyl group, still more preferably, a C _1-3 alkyl group.

Examples of R ^g2 include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl , alkyl groups such as decyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, etc.; aryl groups such as phenyl, tolyl, xylyl, naphthyl, etc.; benzyl, phenylethyl, phenyl, etc. Aralkyl groups such as propyl groups; alkenyl groups such as vinyl, allyl, propenyl, butenyl, etc.

δ is preferably 3 or 4. In one aspect, δ is 3. In other aspects, δ is 4.

The above-mentioned cross-linking agent is preferably tetraethoxysilane, tetramethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, or dimethyltrimethoxysilane , aminopropyltriethoxysilane, aminopropyltrimethoxysilane, tridecafluoro-n-octyltriethoxysilane, or tridecafluoro-n-octyltrimethoxysilane.

The content of component (C) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and still more preferably 1 to 5 parts by mass relative to 100 parts by mass in total of the above-mentioned component (A) and component (B). share.

Ingredient (D): Catalyst

The above-mentioned catalyst is not particularly limited, but for example, it can be acid (such as acetic acid, trifluoroacetic acid, etc.), alkali (such as ammonia, triethylamine, diethylamine, etc.), transition metal (such as Ti, Ni, Sn, etc.) ), metal fault Compounds, such as tin-based catalysts, titanium-based catalysts, zirconia-based catalysts, bismuth-based catalysts, organic amine-based catalysts, etc.

As the tin-based catalyst, di-n-butyltin(IV) dilaurate is exemplified.

Examples of the titanium-based catalyst include diisopropoxybis(acetylethylacetate)titanium, tetra-n-butoxytitanium, tetrakis-2-ethylhexyloxytitanium, and tetraacetylacetyltitanium acetonate.

Examples of the zirconium oxide-based catalyst include zirconium tetraacetyl acetonate, zirconium tetra-n-butoxide, and zirconium dibutoxybis(ethyl acetate acetate).

As the above-mentioned bismuth-based catalyst, bismuth (ethyl 2-hexanoate) is exemplified in the series.

As the above-mentioned organic amine catalyst, diazabicycloundecene can be exemplified in series.

The above-mentioned catalyst can be added to the curable composition immediately before use.

Depending on the usage method, the above catalyst can be additionally added to the curable composition just before use.

The content of the above-mentioned component (D) is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, and still more preferably 0.5 to 5 parts with respect to 100 parts by mass of the total of the above-mentioned component (A) and component (B). parts by mass.

Ingredient (E): Free radical polymerization initiator

啉基-1-丙酮、2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁-1-酮等之苯乙酮類、蒽醌、1,4-萘醌等之醌類、2-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸(正丁氧基)乙酯、4-二甲基胺基苯甲酸異戊酯、4-二甲基胺基苯甲酸2-乙基己酯等之胺基苯甲酸類、苯甲醯氯、三鹵甲基苯基碸等之鹵素化合物、醯基氧化膦類、二-三級丁基過氧化物等之過氧化物等。 The above-mentioned radical polymerization initiator may preferably be a radical photopolymerization initiator. Examples of free radical photopolymerization initiators include benzyl, diethyl and other diketones, benzoin and other diogins, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc. Thioxanthone, benzophenone, thioxanthone, thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, etc. Benzophenones such as methylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, acetophenone, 2-(4-toluenesulfonyloxy) -2-Phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl[ 4-(Methylthio)phenyl]-2-

Phino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-

Acetophenones such as linylphenyl)-butan-1-one, anthraquinones, quinones such as 1,4-naphthoquinone, ethyl 2-dimethylaminobenzoate, 4-dimethylamine Ethyl 4-dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, isopentyl 4-dimethylaminobenzoate, 2-ethyl 4-dimethylaminobenzoate Amino benzoic acids such as hexyl ester, halogen compounds such as benzoyl chloride, trihalomethylphenyl trifluoride, hydroxyl phosphine oxides, di-tertiary butyl peroxides, etc.

啉基-1-丙酮、2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁-1-酮、蒽醌、1,4-萘醌、2-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸(正丁氧基)乙酯、4-二甲基胺基苯甲酸異戊酯、4-二甲基胺基苯甲酸2-乙基己酯、苯甲醯氯、三鹵甲基苯基碸、醯基氧化膦、或二-三級丁基過氧化物、苯甲醯甲酸甲酯、1-羥基-環己基-苯基-酮、1-〔4-(2-羥基乙氧基)-苯基〕-2-羥基-2-甲基-1-丙-1-酮、2-羥基-1-{4-〔4-(2-羥基-2-甲基-丙醯基)-苄基〕苯基}-2-甲基-丙-1-酮、2-甲基-1-(4-甲基硫基苯基)-2-

啉基丙-1-酮、2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-1-丁酮、2-(二甲基胺基)-2-〔(4-甲基苯基)甲基〕-1-〔4-(4-

啉基)苯基〕-1-丁酮、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、雙(η5-2,4-環戊二烯-1-基)-雙(2,6-二氟-3- (1H-吡咯-1-基)-苯基)鈦、1,2-辛二酮，1-〔4-(苯基硫基)-,2-(O-苯甲醯基肟)〕、乙酮，1-〔9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基〕-,1-(0-乙醯肟)、2-羥基-2-甲基-1-苯基-丙-1-酮、2,4,6-三甲基苯甲醯基-二苯基-氧化膦、三級丁基氫過氧化物、氫過氧化異丙苯、二異丙苯氫過氧化物、對薄荷烷氫過氧化物、或三級甲基丁基氫過氧化物。 In a preferred embodiment, the above-mentioned free radical polymerization initiator is benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, thioxanthone, 2,4-diethyl thioxanthone, thioxanthone Keto-4-sulfonic acid, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, phenethyl Ketone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-Methoxyacetophenone, 2-methyl[4-(methylthio)phenyl]-2-

Phino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-

Phinylphenyl)-butan-1-one, anthraquinone, 1,4-naphthoquinone, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethyl (n-butoxy)ethyl aminobenzoate, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, benzoyl chloride, trihalogen Methylphenyl trisulfide, hydroxyl phosphine oxide, or di-tertiary butyl peroxide, methyl benzoate, 1-hydroxy-cyclohexyl-phenyl-one, 1-[4-(2-hydroxy Ethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propanol) methyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-

Oxylinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-

Phylinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-

Phinyl)phenyl]-1-butanone, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(eta5-2,4-cyclopentadien-1-yl )-Bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 1,2-octanedione, 1-[4-(phenylthio)-,2 -(O-benzoyl oxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl oxime)-9H-carbazol-3-yl]-, 1-( 0-acetyl oxime), 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, tertiary Butyl hydroperoxide, cumene hydroperoxide, dicumyl hydroperoxide, p-menthane hydroperoxide, or tertiary methyl butyl hydroperoxide.

Examples of commercially available products of the radical photopolymerization initiator include the following.

OMNIRAD 651: 2,2-dimethoxy-1,2-diphenylethan-1-one,

OMNIRAD 184: 1-Hydroxy-cyclohexyl-phenyl-ketone,

OMNIRAD 2959: 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one,

OMNIRAD 127: 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propyl)-benzyl]phenyl}-2-methyl-propan-1-one,

啉基丙-1-酮、 OMNIRAD 907: 2-methyl-1-(4-methylthiophenyl)-2-

Oxylinopropan-1-one,

啉基苯基)-丁酮-1、 OMNIRAD 369: 2-benzyl-2-dimethylamino-1-(4-

linylphenyl)-butanone-1,

啉基)苯基〕-1-丁酮、 OMNIRAD 379: 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-

Phylyl)phenyl]-1-butanone,

OMNIRAD 819: bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide,

OMNIRAD 784: bis(eta5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium,

OMNIRAD OXE 01: 1,2-Octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyl oxime)],

OMNIRAD OXE 02: Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-, 1-(0-acetyl oxime),

OMNIRAD261, OMNIRAD369, OMNIRAD500,

DAROCUR 1173: 2-hydroxy-2-methyl-1-phenyl-propan-1-one,

DAROCUR TPO: 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide,

DAROCUR1116, DAROCUR2959, DAROCUR1664, DAROCUR4043,

OMNIRAD 754 Hydroxyphenylacetic acid: 2-[2-Pendant oxy-2-phenylethyloxyethoxy]ethyl ester and hydroxyphenylacetic acid, 2-(2-hydroxyethoxy)ethyl ester mixture,

OMNIRAD 500: a mixture of OMNIRAD 184 and benzophenone (1:1),

OMNIRAD 1300: a mixture of OMNIRAD 369 and OMNIRAD 651 (3:7),

OMNIRAD 1800: a mixture of CGI403 and OMNIRAD 184 (1:3),

OMNIRAD 1870: a mixture of CGI403 and OMNIRAD 184 (7:3),

DAROCUR 4265: A mixture (1:1) of DAROCUR TPO and DAROCUR 1173.

In addition, OMNIRAD is manufactured by BASF, and DAROCUR is manufactured by MERCK Group Japan.

The content of component (E) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and still more preferably 1 to 5 parts by mass relative to 100 parts by mass of the total of the above-mentioned component (A) and component (B). share.

Ingredient (F): Fluorinated polyether alcohol

The above-mentioned fluorine-containing polyether alcohol is an alcohol containing a fluoropolyether group.

The above-mentioned fluorine-containing polyether alcohol is preferably a fluorine-containing polyether carboxylic acid compound represented by the following formula (F1) or (F2),

R ^F5 -X ^L -OH (F1)

HO-X ^L -R ^F6 -X ^L -OH (F2)

[In the formula:

R ^F5 are independently Rf ⁵ -R ^FF -O _q6 -;

R ^F6 is -Rf ⁶ _p6 -R ^FF -O _q6 -;

Rf ⁵ are each independently a C _1-16 alkyl group that may be substituted by 1 or more than 1 fluorine atom;

Rf ⁶ is a C _1-6 alkylene group which may be substituted by 1 or more than 1 fluorine atom;

R ^FF are independently divalent fluoropolyether groups;

p6 is 0 or 1;

q6 are independently 0 or 1;

X ^L are each independently a single bond or an organic group with 2 to 10 valences].

In the above formula (F1), R ^F5 are each independently Rf ⁵ -R ^FF -O _q6 -.

In the above formula (F2), R ^F6 is -Rf ⁶ _p6 -R ^FF -O _q6 -.

In the above formula, Rf ⁵ is each independently a C _1-16 alkyl group that may be substituted by one or more than one fluorine atom.

Among the above-mentioned C _1-16 alkyl groups that may be substituted by one or more fluorine atoms, the "C _1-16 alkyl group" can be a straight chain or a branched chain, preferably a straight chain or a branched chain of C _1-6 alkyl, especially C _1-3 alkyl, more preferably straight-chain C _1-6 alkyl, especially C _1-3 alkyl.

The above-mentioned Rf ⁵ is preferably a C _1-16 alkyl group that can be substituted by one or more fluorine atoms, more preferably a CF ₂ HC _1-15 perfluoroalkylene group, and even more preferably a C _1-16 perfluoroalkyl group. Fluoroalkyl.

The above-mentioned C _1-16 perfluoroalkyl group can be a straight chain or branched chain, preferably a straight chain or branched chain C _1-6 perfluoroalkyl group, especially a C _1-3 perfluoroalkyl group, more preferably It is a linear C _1-6 perfluoroalkyl group, especially a C _1-3 perfluoroalkyl group, specifically -CF ₃ , -CF ₂ CF ₃ , or -CF ₂ CF ₂ CF ₃ .

In the above formula, Rf ⁶ is a C _1-6 alkylene group which may be substituted by 1 or more than 1 fluorine atom.

The "C _1-6 alkylene group" in the above-mentioned C _1-6 alkylene group that can be substituted by one or more fluorine atoms can be a straight chain or a branched chain, preferably a straight chain or a branched chain. The C _1-3 alkylene group is more preferably a straight-chain C _1-3 alkylene group.

The above-mentioned Rf ⁶ is preferably a C _1-6 alkylene group which may be substituted by 1 or more than 1 fluorine atom, more preferably a C _1-6 perfluoroalkylene group, and even more preferably a C _1-3 perfluoro group. Alkylene.

The above-mentioned C _1-6 perfluoroalkylene group can be a straight chain or a branched chain, preferably a straight chain or branched chain C _1-3 perfluoroalkylene group, and more preferably a straight chain C _1-3 perfluoroalkylene group. Fluoroalkylene group is specifically -CF ₂ -, -CF ₂ CF ₂ -, or -CF ₂ CF ₂ CF ₂ -.

In the above formula, p6 is 0 or 1. In one aspect, p6 is 0. In other configurations p6 is 1.

In the above formula, q6 is independently 0 or 1. In one aspect, q6 is 0. In other configurations q6 is 1.

In the above formulas (F1) and (F2), R ^FF are each independently a divalent fluoropolyether group.

The above-mentioned R ^FF is the same fluoropolyether group as the above-mentioned ^RF and has the same aspect.

That is, R ^FF is preferably a base represented by the following formula:

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ R ^Fa ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f -

[In the formula:

R ^Fa are each independently a hydrogen atom, a fluorine atom or a chlorine atom,

a, b, c, d, e and f are each independently an integer from 0 to 200, and the sum of a, b, c, d, e and f is 1 or more. The order of presence of each repeating unit marked a, b, c, d, e or f and enclosed in parentheses in the formula is arbitrary. However, when all R ^Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1 or more].

In one aspect, R ^FF are each independently a basis represented by any one of formulas (f1) to (f6).

-(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1)

[In the formula, d is an integer from 1 to 200, and e is 0 or 1];

-(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f2)

[In the formula, c and d are independently integers above 0 and below 30, and e and f are independently The land is an integer above 1 and below 200,

The sum of c, d, e and f is 2 or more,

The order of the repeating units marked c, d, e or f and enclosed in parentheses in the formula is arbitrary];

-(R ⁶ -R ⁷ ) _g - (f3)

[In the formula, R ⁶ is OCF ₂ or OC ₂ F ₄ ,

R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of 2 or 3 groups independently selected from these groups,

g is an integer from 2 to 100];

-(R ⁶ -R ⁷ ) _g -R ^r -(R ^7' -R ^6' ) _g' - (f4)

[In the formula, R ⁶ is OCF ₂ or OC ₂ F ₄ ,

R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of 2 or 3 groups independently selected from these groups,

R ^6' is OCF ₂ or OC ₂ F ₄ ,

R ^7' is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of 2 or 3 groups independently selected from these groups. ,

g is an integer from 2 to 100,

g’ is an integer from 2 to 100,

R ^r is

(In the formula, * shows the bonding position)];

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f5)

[In the formula, e is an integer from 1 to 200, a, b, c, d and f are each independently an integer from 0 to 200. In addition, a, b, c, d, e or f are marked with brackets The order of the repeated units enclosed in the formula is arbitrary]

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f6)

[In the formula, f is an integer from 1 to 200, a, b, c, d and e are each independently an integer from 0 to 200. In addition, a, b, c, d, e or f are marked with brackets The order of the repeated units enclosed in the formula is arbitrary]

In one aspect, the above-mentioned R ^FF is the base represented by the above-mentioned formula (f1) or (f2).

In one aspect, the above-mentioned R ^FF is the base represented by the above-mentioned formula (f1).

In one aspect, the above-mentioned R ^FF is the base represented by the above-mentioned formula (f2).

In one aspect, the above-mentioned R ^FF is the base represented by the above-mentioned formula (f3) or (f4).

In one aspect, the above-mentioned R ^FF is the base represented by the above-mentioned formula (f3).

In one aspect, the above-mentioned R ^FF is the base represented by the above-mentioned formula (f4).

In one aspect, the above-mentioned R ^FF is the base represented by the above-mentioned formula (f5).

In one aspect, the above-mentioned R ^FF is the base represented by the above-mentioned formula (f6).

In one aspect, X ^L is a single bond.

In other aspects, X ^L is a divalent organic radical.

In one aspect, as X ^L , the series includes, for example, a single bond or a divalent organic group represented by the following formula.

-(R ⁵¹ ) _p5 -(X ⁵¹ ) _q5 -

[In the formula:

R ⁵¹ represents a single bond, -(CH ₂ ) _s5 - or o-, m- or p-phenylene group, preferably -(CH ₂ ) _s5 -,

s5 is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, and more preferably 1 or 2,

X ⁵¹ means -(X ⁵² ) _l5 -,

X ⁵² each independently represents a group selected from -O-, -S-, o-, m- or p-phenylene, -C(O)O-, -Si(R ⁵³ ) ₂ -, -(Si(R ⁵³ ) ₂ O) _m5 -The base of the group consisting of -Si(R ⁵³ ) ₂ -, -CONR ⁵⁴ -, -O-CONR ⁵⁴ -, -NR ⁵⁴ - and -(CH ₂ ) _n5 -,

R ⁵³ independently represents phenyl, C _1-6 alkyl or C _1-6 alkoxy, preferably phenyl or C _1-6 alkyl, more preferably methyl,

R ⁵⁴ each independently represents a hydrogen atom, phenyl or C _1-6 alkyl group (preferably methyl),

Each time m5 appears, it is independently an integer from 1 to 100, preferably an integer from 1 to 20.

Each time n5 appears, it is independently an integer from 1 to 20, preferably an integer from 1 to 6, and more preferably an integer from 1 to 3.

l5 is an integer from 1 to 10, preferably an integer from 1 to 5, more preferably an integer from 1 to 3,

p5 is 0 or 1,

q5 is 0 or 1,

Here, at least one of p5 and q5 is 1, and the order in which the repeating units marked with p5 or q5 and enclosed in parentheses in the formula is arbitrary].

Here, X ^L (typically the hydrogen atom of X ^L ) may be substituted with one or more than one substituent selected from a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group. In a preferred embodiment, X ^L is not substituted by these groups.

In a preferred aspect, the above-mentioned X ^L are independently -(R ⁵¹ ) _p5 -(X ⁵¹ ) _q5 -R ⁵² -. R ⁵² represents a single bond, -(CH ₂ ) _t5 - or o-, m- or p-phenylene group, preferably -(CH ₂ ) _t5 -. t5 is an integer from 1 to 20, preferably an integer from 2 to 6, and more preferably an integer from 2 to 3. Here, R ⁵² (typically the hydrogen atom of R ⁵² ) may be substituted with one or more than one substituent selected from a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group. In a preferred embodiment, R ⁵⁶ is not substituted by these groups.

In a preferred aspect, the above-mentioned X ^L can be independently a single bond,

C _1-6 alkylene group,

-(CH ₂ ) _z21 -O-(CH ₂ ) _z22 -(In the formula, z21 is an integer from 0 to 6, such as an integer from 1 to 6, z22 is an integer from 0 to 6, such as an integer from 1 to 6), Or -(CH ₂ ) _z23 -phenylene -(CH ₂ ) _z24 -(in the formula, z23 is an integer from 0 to 6, such as an integer from 1 to 6, z24 is an integer from 0 to 6, such as an integer from 1 to 6 ).

Moreover, the ^XL mentioned above is bonded to ^RF5 or ^RF6 on the left side, and is bonded to OH on the right side.

The content of component (F) is preferably 0.1 to 30 mass%, more preferably 0.5 to 30 mass%, further preferably 0.5 to 20 mass%, based on the total amount of component (A) to component (F). More preferably, it is 0.5 to 10% by mass, particularly preferably 0.5 to 15% by mass, for example, 1 to 5% by mass.

The curable composition of the present disclosure may include a solvent.

The above-mentioned solvents can preferably be aliphatic hydrocarbons, aromatic hydrocarbons, esters, ketones, glycol ethers, alcohols, glycols, cyclic ethers, amides, ether alcohols, carbon Perfluoroaliphatic hydrocarbons, polyfluoroaromatic hydrocarbons, polyfluoroaliphatic hydrocarbons, hydrofluorocarbons, hydrochlorofluorocarbons, or hydrofluoroethers with numbers 5 to 12. The solvent may be a mixture of two or more of these solvents.

In a preferred embodiment, the solvent is alcohol, hydrofluoroether, or a mixed solvent of two or more of these.

Examples of the aliphatic hydrocarbons include: hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, mineral spirits, etc.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, naphthalene, solvent naphtha, and the like.

As the above-mentioned esters, the series includes: methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, cellosine acetate, propylene glycol methyl ether acetic acid, carbitol acetate, Diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, etc.

Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methylaminoketone, 2-heptanone, and the like.

As the above-mentioned ethylene glycol ethers, the following series include: ethyl cellulosine, methyl cellulosine, methyl cellulosine acetate, ethyl cellulose acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, etc.

Examples of the above alcohols include: methanol, ethanol, isopropanol, n-butanol, isobutanol, tertiary butanol, secondary butanol, 3-pentanol, octyl alcohol, 3-methyl-3- Methoxybutanol, tertiary amyl alcohol, etc. Alcohols, preferably methanol, ethanol, and isopropyl alcohol.

Examples of the aforementioned glycols include ethylene glycol, propylene glycol, and the like.

烷等。 As the above-mentioned cyclic ethers, a series of examples include: tetrahydrofuran, tetrahydropyran, dihydropyran

Alkane etc.

Examples of the above-mentioned amides include N,N-dimethylformamide, N,N-dimethylacetamide, and the like.

Examples of the above-mentioned ether alcohols include: methyl cellulosine, cellulose, isopropyl cellulosine, butyl cellulosine, diethylene glycol monomethyl ether, and the like.

Examples of the perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms include perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, and the like.

Examples of the polyfluoroaromatic hydrocarbon include bis(trifluoromethyl)benzene and the like.

Examples of the polyfluoroaliphatic hydrocarbon include C ₆ F ₁₃ CH ₂ CH ₃ (for example, ASAHIKLIN (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), 1, 1, 2, 2, 3, 3, 4 -Heptafluorocyclopentane (for example, ZEORORA (registered trademark) H manufactured by Japan ZEON Co., Ltd.), etc.

Examples of hydrofluorocarbons (HFC) include 1,1,1,3,3-pentafluorobutane (HFC-365mfc)) and the like.

As hydrochlorofluorocarbon (HCFC), 1,1,2-trichloro-1,2,2-trifluoroethane and 1,2-dichloro-1,1,2,2- Tetrafluoroethane, 1,1-dichloro-1,2,2,3,3-pentafluoropropane (HCFC225) (for example, ASAHIKLIN (registered trademark) AK225)), etc.

Examples of the hydrofluoroether (HFE) include perfluoropropyl methyl ether (C ₃ F ₇ OCH ₃ ) (for example, Novec (trademark) 7000 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) (for example, Novec (trademark) 7100 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl ethyl ether (C ₄ F ₉ OC ₂ H ₅ ) (for example, Novec (trademark) 7100 manufactured by Sumitomo 3M Co., Ltd. Alkyl perfluorocarbons such as Novec (trademark) 7200), perfluorohexyl methyl ether (C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ ) (for example, Novec (trademark) 7300 manufactured by Sumitomo 3M Co., Ltd.) Alkyl ether (perfluoroalkyl and alkyl groups may be linear or branched), CF ₃ CH ₂ OCF ₂ CHF ₂ (for example, ASAHIKLIN (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.), etc.

In a preferred embodiment, the solvent is methanol, ethanol, isopropyl alcohol, perfluoropropyl methyl ether, perfluorobutyl methyl ether, perfluorobutyl ethyl ether, perfluorohexyl methyl ether, or CF ₃ CH ₂ OCF ₂ CHF ₂ , or a mixed solvent of two or more of these.

The content of the above-mentioned solvent is 20 to 90 mass %, preferably 40 to 90 mass %, relative to the total amount of component (A) to component (F).

The curable composition of the present disclosure may include: (non-reactive) fluoropolyether compounds which can be understood as fluorine-containing oils, preferably perfluoro(poly)ether compounds (hereinafter collectively referred to as "fluorinated oils"), which can be understood as A (non-reactive) polysiloxane compound that is silicone oil (hereinafter referred to as "silicone oil"), alcohols, surfactants, polymerization inhibitors, sensitizers, etc.

The fluorine-containing oil is not particularly limited, but a series of examples include compounds represented by the following general formula (3) (perfluoro(poly)ether compounds).

Rf ⁵ -(OC ₄ F ₈ ) _a' -(OC ₃ F ₆ ) _b' -(OC ₂ F ₄ ) _c' -(OCF ₂ ) _d' -Rf ⁶ ‧‧‧(3)

In the formula, Rf ⁵ represents an alkyl group with 1 to 16 carbon atoms (preferably a perfluoroalkyl group with C _1-16 ) that can be substituted by 1 or more than 1 fluorine atom, and Rf ⁶ represents an alkyl group with 1 to 16 carbon atoms that can be substituted by 1 or more than 1 fluorine atoms. C 1 to 16 alkyl groups (preferably C _1-16 perfluoroalkyl), fluorine atoms or hydrogen atoms substituted by fluorine atoms, Rf ⁵ and Rf ⁶ are each independently more preferably C _1-3 perfluoroalkyl alkyl.

a', b', c' and d' respectively represent the number of repeating units of the four perfluoro (poly) ethers constituting the main skeleton of the polymer, and are independently integers from 0 to 300, a', b The sum of ', c' and d' is at least 1, preferably 1 to 300, more preferably 20 to 300. The order of presence of each repeating unit marked a', b', c' or d' and enclosed in parentheses in the formula is arbitrary. These repeating units may be linear or branched, and may also contain cyclic structures. For example, -(OC ₄ F ₈ )- can be -(OCF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ )-, -(OCF ₂ CF(CF ₃ )CF ₂ )-,- (OCF ₂ CF ₂ CF(CF ₃ ))-,-(OC(CF ₃ ) ₂ CF ₂ )-,-(OCF ₂ C(CF ₃ ) ₂ )-,-(OCF(CF ₃ ) Any one of CF(CF ₃ ))-, -(OCF(C ₂ F ₅ )CF ₂ )- and (OCF ₂ CF(C ₂ F ₅ ))-, but preferably -(OCF ₂ CF ₂ CF ₂ CF ₂ )-. -(OC ₃ F ₆ )- can be any one of -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )- and (OCF ₂ CF(CF ₃ ))-, but it is more The best is -(OCF ₂ CF ₂ CF ₂ )-. -(OC ₂ F ₄ )- can be any one of -(OCF ₂ CF ₂ )- and (OCF(CF ₃ ))-, but is preferably -(OCF ₂ CF ₂ )-.

The above ring structure may be the following three-membered ring or four-membered ring:

[In the formula, * shows the bonding position].

For example, (OC ₄ F ₈ ) can be

[In the formula, * shows the bonding position].

As an example of the perfluoro(poly)ether compound represented by the above-mentioned general formula (3), a series of compounds represented by any one of the following general formulas (3a) and (3b) (which may be one type or two or more types) are listed. mixture).

Rf ⁵ -(OCF ₂ CF ₂ CF ₂ ) _b” -Rf ⁶ ‧‧‧(3a)

Rf ⁵ -(OCF ₂ CF ₂ CF ₂ CF ₂ ) _a” -(OCF ₂ CF ₂ CF ₂ ) _b” -(OCF ₂ CF ₂ ) _c” -(OCF ₂ ) _d” -Rf ⁶ ‧‧‧(3b )

In these formulas, Rf ⁵ and Rf ⁶ are as above; in formula (3a), b” is an integer from 1 to 100; in formula (3b), a” and b” are independently from 0 to 30 of integers, c” and d” are independently integers above 1 and below 300. The order of existence of the repeating units marked a”, b”, c”, d” and enclosed in parentheses in the formula is arbitrary.

In addition, from other viewpoints, the fluorine-containing oil can be a compound represented by the general formula Rf ³ -F (in the formula, Rf ³ is a C _5-16 perfluoroalkyl group). In addition, it may also be a chlorotrifluoroethylene oligomer.

The above-mentioned fluorine-containing oil may have an average molecular weight of 500 to 10,000. The molecular weight of fluorinated oil can be determined using GPC.

The content of the fluorine-containing oil relative to the curable composition of the present disclosure may be, for example, 0 to 50 mass%, preferably 0 to 30 mass%, and more preferably 0 to 5 mass%. In one aspect, the curable composition of the present disclosure contains substantially no fluorinated oil. Substantially free of fluorinated oil means completely free of fluorinated oil, or may contain a very small amount of fluorinated oil.

As the silicone oil, for example, a linear or cyclic silicone oil having a siloxane bond number of 2,000 or less can be used. Straight-chain silicone oil can be so-called straight silicone oil and modified silicone oil. As pure silicone oil, the series includes dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil. As modified silicone oil, a series of examples are those that use alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amine, epoxy, carboxyl, alcohol, etc. to modify pure silicone oil. Cyclic silicone oils include: cyclic dimethylsiloxane oil, etc.

In the curable composition of the present disclosure, relative to the total of 100 parts by mass of the fluorine-containing polyether group acrylic compound and the fluorine-containing polyether group silane compound of the present disclosure (in the case of two or more types, the total of these is: Likewise), the content of these silicone oils can be, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass.

Examples of the alcohols include alcohols with 1 to 6 carbon atoms that may be substituted by one or more fluorine atoms, such as methanol, ethanol, isopropyl alcohol, tertiary butanol, and CF ₃ CH ₂ OH. , CF ₃ CF ₂ CH ₂ OH, (CF ₃ ) ₂ CHOH. By adding these alcohols to the curable composition, the stability of the curable composition can be improved, and the relationship between the perfluoropolyether group-containing acrylic compound and the fluoropolyether group-containing silane compound and the solvent can be improved. Compatibility.

The above-mentioned alcohol is preferably methanol, ethanol, 2,2,3,3,3-pentafluoro-1-propanol or 2,2,2-trifluoroethanol.

In addition to the above components, the curable composition of the present disclosure may contain trace amounts of impurities. Examples of impurities include: Pt, Rh, RU, 1,3-divinyltetramethyldisiloxane, triphenylphosphine , NaCl, KCl, silane condensates, etc.

The viscosity of the curable composition of the present disclosure is preferably 5000mPa‧s or less, more preferably 3000mPa‧s or less, and still more preferably 2000mPa‧s or less. By reducing the viscosity of the curable composition, the curable composition can be applied to areas with finer shapes. In addition, the viscosity of the curable composition of the present disclosure is preferably 100 mPa‧s or more, more preferably 500 mPa‧s or more, and even more preferably 1000 mPa‧s or more. By increasing the viscosity of the hardening composition, it is beneficial to the formation of thick films and the control of wetting and spreading.

In one aspect, the viscosity of the curable composition of the present disclosure is preferably 100 to 5000 mPa‧s, more preferably 500 to 3000 mPa‧s, and even more preferably 1000 to 2000 mPa‧s.

(use)

The cured product of the curable composition of the present disclosure can be used, for example, in potting materials, sealing materials, and the like. The cured product of the curable composition of the present disclosure can be obtained, for example, by filling gaps in electronic components (for example, the joint portion between the casing and the printed circuit board, or the gap between the resin molded metal terminal portion and the molded resin), and Let it harden before use.

In order to form a hardened material (for example, a potting material, a sealing material) with higher wear resistance, before treatment with the curable composition of the present disclosure, in order to remove the oil on the wall surface of the void, it is preferred to use acetone or hydrogen. The object to be processed is washed with fluoroether and then dried. Moreover, in addition to the above-mentioned washing, pretreatment with UV ozone, oxygen plasma, etc. can further improve the wear resistance of the hardened product.

Before treatment with the curable composition of the present disclosure, if necessary, by performing primer treatment on the cavity wall surface, etc., the adhesion of the potting material formed of the curable composition can be improved, and the wear resistance can be further improved. sex. The primer treatment can be carried out according to conventional methods under the same conditions as the primer treatment in the case of using a silane coupling agent.

Moreover, when the hardened|cured material obtained from the curable composition of this disclosure is adhered to various base materials, various primers may be used together.

In one aspect, the hardenable composition can harden at room temperature. Such a curable composition is particularly useful as a composition for forming casting materials.

In one aspect, when using the curable composition of the present disclosure, the composition can be further diluted with a solvent according to its use and purpose. As a solvent used for dilution, the fluorine-type agent exemplified above can be used. For example, it can be used by dissolving it in a solvent such as 1,3-bis(trifluoromethyl)benzene, Fluorinert (manufactured by 3M Company), perfluorobutyl methyl ether, perfluorobutyl ethyl ether, etc. to a desired concentration. In particular, it is preferable to use the above-mentioned solvent for film coating applications.

Since the curable composition of the present disclosure can form a cured product having good adhesion to metal or plastic substrates, it is particularly useful as an adhesive or sealing material around electrical and electronic components and vehicle-mounted components. Since the curable composition of the present disclosure has a good elastic modulus especially even at low temperature, it can be effectively used in automobile parts (for example, sealing materials, Specifically, gasket sheets), etc., especially in automobile parts used in cold regions (for example, below -50°C). Furthermore, the cured product of the curable composition of the present disclosure can also be used as a resin mold (replication mold) for nanoimprinting.

The cured product of the curable composition disclosed in the present disclosure has good drug resistance, acid resistance, and alkali resistance. The cured product of the curable composition disclosed in this way can also be used in chemical plants, semiconductor manufacturing equipment, and the like.

The present disclosure provides a hardened product obtained from the curable composition of the present disclosure. Since the curable composition of the present disclosure is excellent in curability and coating properties, it can be used as a cured product for various applications.

The present disclosure includes an article including a base material and a hardened material layer formed by hardening the curable composition of the present disclosure on the base material.

The substrate that can be used in the present disclosure can be made of, for example: glass, resin (natural or synthetic resin, for example, it can be a general plastic material), OCA (Optical Clear Adhesive), polarizing plate metal, ceramics, semiconductor (silicon) , germanium, etc.), electronic products, fibers (fabrics, non-woven fabrics, etc.), fur, leather, wood, ceramics, stone, etc., building components, etc., sanitary products, and any suitable material.

In a preferred aspect, the above-mentioned substrate is glass, resin, polarizing plate, OCA (Optical Clear Adhesive) or metal, preferably glass, resin, polarizing plate or OCA (Optical Clear Adhesive).

As the above-mentioned glass, sapphire glass, soda-lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass are used. Preferably, chemically strengthened soda-lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded borosilicate glass are particularly preferred.

The shape of the above-mentioned base material is not particularly limited, and may be, for example, plate-shaped, film-shaped, or other forms. In addition, the surface area of the base material where the hardened material layer should be formed can be at least part of the surface of the base material, and can be appropriately determined according to the use and specific specifications of the article to be manufactured.

The article of the present disclosure can be manufactured by forming a layer from the curable composition of the present disclosure by forming a layer of the curable composition of the present disclosure on the surface of the above-mentioned base material, and post-processing the layer if necessary. .

The layer formation of the curable composition of the present disclosure can be implemented by applying the curable composition to the surface of the base material to cover the surface. The covering method is not particularly limited. For example, wet covering methods and dry covering methods can be used.

Examples of wet coating methods include dip coating, rod coating, spin coating, flow coating, spray coating, roller coating, gravure coating, needle dispensing, spray dispensing and similar methods. The wet covering method is preferably rod coating, spin coating, flow coating, roller coating, needle dispensing or spray dispensing.

In a preferred aspect, the articles of the present disclosure may be electrical and electronic components, automotive components, automotive parts (for example, sealing materials, specifically gasket sheets), chemical plants, semiconductor manufacturing equipment, etc.

In addition, the items disclosed herein may also be medical equipment or medical materials.

The thickness of the above layer is not particularly limited, but may be, for example, 1 μm or more, 10 μm or more, or 100 μm or more. In addition, the thickness of the above layer is not particularly limited, but may be 1000 μm or less, 500 μm or less, or 100 μm or less.

The above is a detailed description of the curable composition, cured product, article, etc. of the present disclosure. In addition, the curable composition, cured product, article, etc. of this disclosure are not limited to those illustrated above.

[Example]

The compounds of the present disclosure are described in the examples below, but the present disclosure is not limited to the following examples. In addition, in this example, the order in which the repeating units constituting the fluoropolyether exists is arbitrary, and the chemical formula shown below represents the average composition.

Component (A): Synthesis of fluoropolyether-based acrylic compound

Synthesis example 1

In a 100mL 3-neck flask equipped with a reflux cooler, a thermometer and a stirrer, feed the perfluoropolymer with an average composition of CH ₃ COOCF ₂ O (CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ COOCH ₃ 10.0g of ether modified ester, 5.0g of 1,3-bis(trifluoromethyl)benzene, and 0.10g of 3-(2-aminoethylamino)propyltrimethoxysilane, stir at 25°C for 1 hours. Thereafter, volatile components are distilled off under reduced pressure, thereby obtaining the silane compound (A) represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ CONHCH ₂ CH 2 NHCH ₂ CH _{2 CH 2 Si} (OCH ₃ ) ₃

Synthesis example 2

Into a 100 mL 3-neck flask equipped with a reflux cooler, a thermometer, and a stirrer, 10.0 g of the silane compound (A) obtained in Synthesis Example 1 and 2-isocyanatoethyl acrylate (Karenz, manufactured by Showa Denko Co., Ltd. (Registered Trademark) AOI) 0.60 g and stirred at 25° C. for 1 hour to obtain a perfluoropolyether group-containing acrylic compound (B) represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ N(X)CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ CONHCH ₂ CH ₂ N(X)CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

X=-CONHCH ₂ CH ₂ OCOCH=CH ₂

Component (B): Synthesis of fluoropolyether-based silane compound

Synthesis example 3

In a 100mL 3-neck flask equipped with a reflux cooler, a thermometer and a stirrer, feed the perfluoropolymer with an average composition of CH ₃ OCOCF ₂ O (CF ₂ O) ₁₂ (CF ₂ CF ₂ O) ₁₂ CF ₂ COOCH ₃ 10.0 g of ether modified ester, 5.0 g of 1,3-bis(trifluoromethyl)benzene, and 0.11 g of ethylenediamine were stirred at 25°C for 1 hour under a nitrogen flow. Next, 0.62 g of 3-aminopropylmethyldimethoxysilane was added, and the mixture was stirred at 25° C. for 1 hour. Thereafter, volatile components are distilled off under reduced pressure, thereby obtaining a perfluoropolyether group-containing silane compound (C) represented by the following formula.

(CH ₃ O) ₂ CH ₃ SiCH ₂ CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂

Ingredient (C): Cross-linking agent

(C-1) Methyltrimethoxysilane

Ingredient (D): Catalyst

(D-1) Diisopropoxybis(acetylethylacetate)titanium (Olgatrix TC750, manufactured by Matsumoto Fine Chemical Co., Ltd.)

Ingredient (E): Free radical polymerization initiator

(E-1) Methyl benzoate

Component (F): Carboxylic acid compound containing fluoropolyether group

(F-1)CF ₃ CF ₂ CF ₂ O-(CF(CF ₃ )CF ₂ O) ₁₁ -CF(CF ₃ )-CH ₂ OH

Examples and Comparative Examples

The components (A) to (F) were mixed at a ratio (weight ratio) shown in the table below to prepare a curable composition. The following evaluation was performed on the obtained curable composition.

UV hardening test

After forming a film with a thickness of 200 μm on the glass plate using an applicator, UV irradiation with a cumulative light intensity of 1000 mJ was performed using a high-pressure mercury lamp in the atmosphere. The hardened state of the coating film thereafter was evaluated. After forming a 200 μm film on the glass plate using an applicator, UV irradiation was performed using a high-pressure mercury lamp in the atmosphere with an integrated light intensity of 1000 mJ.

◎: A state where both the surface and the inside are hardened and fluidity is lost.

○: The surface is hardened, but the inside is liquid, or although there is no fluidity, the surface bonding and hardening are insufficient.

×: Both the inside and the surface are not sufficiently hardened and remain liquid.

Exudation test

After the cured film was placed in an electric furnace at 80°C for 2 hours, it was evaluated whether unreacted matter exuded to the surface in the form of oil droplets.

◎: No bleeding

○: A little oil seeps out from the surface

×: Oil droplet-like agglomerates were present and leakage was confirmed.

Chemical resistance test

The cured film was immersed in a toluene solution at room temperature for 3 days, and the weight swelling rate was calculated.

◎: Weight swelling rate is less than 3%

○: Weight swelling rate is more than 3% and less than 10%

×: Weight swelling rate is more than 10%

Water contact angle measurement

The water contact angle of the cured film surface was measured using DMs-600 manufactured by Kyowa Chemical Co., Ltd. using 2 μl of pure water.

Liquid repellency test

Use ZEBRA oil pen to evaluate the liquid repellency of the hardened film surface. Use an oil-based pen to draw three 5cm lines on the surface of the hardened film to evaluate the repellency of the surface. Moreover, after drying for 1 minute, gently wipe the surface with Kimwipe 5 times to confirm the wipeability of the ink.

○: Oil-based pens repel oil droplets and do not leave traces of wiping even after drying.

△: Oil-based pens can be written on (not repellent), but can be wiped after drying.

×: Oil-based pens can be written on (not repellent), but cannot be wiped off after drying.

[Table 1]

From the above results, it was confirmed that the curable composition of the present disclosure can obtain a cured product with high water and oil repellency by containing a fluorine-containing polyether alcohol. In addition, it was confirmed that by including components (A) to (E), especially component (A), it is possible to immediately cure (fix) by UV irradiation, which cannot be achieved in conventional moisture curing systems.

[Industrial Applicability]

The curable composition of the present disclosure can be suitably used to form a cured layer on various substrates.

Claims (45)

A hardening composition containing: Component (A): A fluoropolyether-based acrylic compound containing an acrylic group, a hydrolyzable silane group, and a fluoropolyether group, Component (B): a fluoropolyether-based silane compound containing a fluoropolyether group and a hydrolyzable silica group, Ingredient (C): cross-linking agent, Ingredients (D): Catalyst, Ingredient (E): free radical polymerization initiator, and Ingredient (F): Fluorine-containing polyether alcohol. The curable composition according to claim 1, wherein the content of component (F) is 0.5 to 30% by mass relative to the total amount of component (A) to component (F). The curable composition according to claim 1 or 2, wherein the content of component (F) is 0.5 to 5% by mass relative to the total amount of component (A) to component (F). The curable composition according to any one of claims 1 to 3, wherein the fluorine-containing polyether alcohol is a fluorine-containing polyether carboxylic acid compound represented by the following formula (F1) or (F2) , R ^F5 -X ^L -OH (F1) HO-X ^L -R ^F6 -X ^L -OH (F2) In the formula: R ^F5 are independently Rf ⁵ -R ^FF -O _q5 -; R ^F6 - is Rf ⁶ _p5 -R ^FF -O _q5 -; Rf ⁵ are each independently a C _1-16 alkyl group that may be substituted by 1 or more than 1 fluorine atom; Rf ⁶ is a C _1-6 alkylene group which may be substituted by 1 or more than 1 fluorine atom; R ^FF are independently divalent fluoropolyether groups; p5 is 0 or 1; q5 are independently 0 or 1; X ^L is independently a single bond or a divalent base. The curable composition according to claim 4, wherein R ^FF are each independently a base represented by the following formula: -(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ R ^Fa ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - In the formula, R ^Fa are independently a hydrogen atom, a fluorine atom or a chlorine atom, a, b, c, d, e and f are each independently an integer from 0 to 200. The sum of a, b, c, d, e and f is more than 1. Mark a, b, c, d, e or f The order in which the repeating units enclosed in parentheses are present in the formula is arbitrary. However, when all R ^Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1. above. _The curable composition according ^to _{claim 4 or 5} , wherein where, z21 is an integer from 0 to 6, z22 is an integer from 0 to 6), or -(CH ₂ ) _z23 -phenylene-(CH ₂ ) _z24 -(where z23 is an integer from 0 to 6, z24 is an integer from 0 to 6). The curable composition according to any one of claims 1 to 6, wherein the fluorine-containing polyether group-containing acrylic compound contains a compound represented by the following formula (A1), (A2) or (A3), R ^F1 -X ^A -X ^B R ^Ac _m (A1) R ^Ac _m X ^B -X ^A -R ^F2 -X ^A -X ^B R ^Ac _m (A2) R ^Ac _m X ^B -X ^A -(R ^F2 -R ^g -R ^a (R ^Ac ) _m3 -R ^g ) _x -R ^F2 -X ^A -X ^B R ^Ac _m (A3) In the formula: R ^F1 is Rf ¹ -R ^F -O _q -, R ^F2 are independently -Rf ² _p -R ^F -O _q -, Rf ¹ is a C _1-16 alkyl group which may be substituted by 1 or more than 1 fluorine atom, Rf ² is a C _1-6 alkylene group which may be substituted by 1 or more than 1 fluorine atom, R ^F are independently divalent fluoropolyether groups, p is 0 or 1, q is independently 0 or 1, X ^A is independently a single bond or a divalent organic group, X ^B are independently the basis of (m+1) valence, However, in each formula, at least one X ^B is a (m+1) valent group containing a hydrolyzable silicon group, R ^Ac are each independently -X ^D -X ^E (-X ^F -OCO-CR ⁵ =CH ₂ ) _m' , X ^D is a single bond or a divalent base, X ^E is the basis of a single bond or (m'+1) valence, X ^F are independently single bonds or divalent bases, R ⁵ is a hydrogen atom, a halogen atom, or an organic group with one valence from 1 to 8 carbon atoms, m’ is an integer from 1 to 10, m are independently integers from 0 to 10, R ^a are independently organic radicals with (m3+2) valence, m3 is an integer from 0 to 4, However, at least one of m and m3 is 1 or more, R ^g is independently -NR ^c CO-R ^e -, -NR ^c COO-R ^e -, or -NR ^c CONR ^c -R ^e -, where the left side of these groups is bonded to R ^a , R ^c is each independently a hydrogen atom, C _1-6 alkyl group, or C _6-16 aryl group, R ^e are each independently a single bond or a divalent organic group, x is an integer above 1. The curable composition according to claim 7, wherein R ^F are each independently a base represented by the following formula: -(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ R ^Fa ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - In the formula, R ^Fa are independently a hydrogen atom, a fluorine atom or a chlorine atom, a, b, c, d, e and f are each independently an integer from 0 to 200. The sum of a, b, c, d, e and f is more than 1. Mark a, b, c, d, e or f The order in which the repeating units enclosed in parentheses are present in the formula is arbitrary. However, when all R ^Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1. above. The curable composition according to claim 7 or 8, wherein R ^F are independently represented by the following formulas (f1), (f2), (f3), (f4), (f5), or (f6) The basis of the indication: -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1) In the formula, d is an integer from 1 to 200, and e is 0 or 1; -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f2) In the formula, c and d are independently integers from 0 to 30; e and f are independently integers from 1 to 200; The sum of c, d, e and f is an integer from 10 to 200; The order of the repeating units marked c, d, e or f and enclosed in parentheses in the formula is arbitrary; -(R ⁶ -R ⁷ ) _g - (f3) In the formula, R ⁶ is OCF ₂ or OC ₂ F ₄ ; R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of 2 or 3 groups selected from these groups; g is an integer from 2 to 100; -(R ⁶ -R ⁷ ) _g -R ^r -(R ^7' -R ^6' ) _g' - (f4) In the formula, R ⁶ is OCF ₂ or OC ₂ F ₄ , R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of 2 or 3 groups independently selected from these groups, R ^6' is OCF ₂ or OC ₂ F ₄ , R ^7' is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of 2 or 3 groups independently selected from these groups. , g is an integer from 2 to 100, g’ is an integer from 2 to 100, R ^r is

In the formula, * shows the bonding position; -(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f5) In the formula, e is an integer from 1 to 200, a, b, c, d and f are each independently an integer from 0 to 200, and the sum of a, b, c, d, e and f is at least 1. In addition , the order of the repeating units marked a, b, c, d, e or f and enclosed in brackets in the formula is arbitrary; -(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f6) In the formula, f is an integer from 1 to 200, a, b, c, d and e are each independently an integer from 0 to 200, and the sum of a, b, c, d, e and f is at least 1. In addition , the order of the repeating units marked a, b, c, d, e or f and enclosed in brackets in the formula is arbitrary. The curable composition according to any one of claims 7 to 9, wherein X ^E is a single bond. The curable composition according to any one of claims 7 to 10, wherein X ^E is -X ^G -X ^H ; X ^G is a single bond, C _1-6 alkylene group, -(CH ₂ ) _z9 -O-(CH ₂ ) _z10 -(in the formula, z9 is an integer from 0 to 6, z10 is an integer from 0 to 6), or -(CH ₂ ) _z11 -phenylene-(CH ₂ ) _z12 - (in the formula, z11 is an integer from 0 to 6, z12 is an integer from 0 to 6); X ^H is as follows

R ⁸ is a hydrogen atom or a C _1-6 alkyl group. The curable composition according to any one of claims 7 to 11, wherein X ^D is -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -OCONH- , -NHCOO-, -NH-CO-NH-, -CH ₂ CH(OH)CH ₂ -, -CH(CH ₂ OH)CH ₂ --(OSiR ¹⁴ ₂ ) _d5 -;

In the formula, * and ** show the bonding position, * is bonded to X ^B , and ** is bonded to X ^E ; R ¹⁴ is C _1-6 alkyl or C _6-16 aryl; d5 is an integer from 1 to 10. The curable composition according to any one of claims 7 to 12, wherein X ^F is a single bond, C _1-6 alkylene group, -(CH ₂ ) _z5 -O-(CH ₂ ) _z6 -(in the formula, z5 is an integer from 0 to 6, z6 is an integer from 0 to 6), or -(CH ₂ ) _z7 -phenylene-(CH ₂ ) _z8 -(In the formula, z7 is an integer from 0 to 6, z8 is an integer from 0 to 6). The curable composition according to any one of claims 7 to 13, wherein R ⁵ is a hydrogen atom or a methyl group. The curable composition according to any one of claims 7 to 14, wherein X ^A is independently a single bond or a group represented by the following formula; -(C _α R ¹¹ _2α ) _s1 -R ¹² _t1 - In the formula: R ¹¹ is independently a hydrogen atom or a fluorine atom, α is independently an integer from 1 to 10, R ¹² is independently -O-, -CO-, -NR ¹⁰ -, -CONR ¹⁰ -, -NR ¹⁰ CO-, -COO-, -OCO-, or -OCONH-, R ¹⁰ is a hydrogen atom or C _1-6 alkyl group, s1 is an integer from 0 to 3, t1 is an integer from 0 to 3, The total of s1 and t1 is more than 1, The order of existence of the repeating units marked s1 or t1 and enclosed in parentheses in the formula is arbitrary. The curable composition according to any one of claims 7 to 15, wherein X ^A is -CONR ¹⁰ -C _α1 H _2α1 -, -(C _α2 H _2α2 ) -OCONR ¹⁰ -, -(C _α3 H _2α3 )-, or-(C _α4 H _2α4 )-O-(C _α5 H _2α5 ), R ¹⁰ is a hydrogen atom or C _1-6 alkyl group, α1 is an integer from 1 to 10, α2 is an integer from 1 to 10, α3 is an integer from 1 to 10, α4 is an integer from 0 to 6, α5 is an integer from 0 to 6. The curable composition according to any one of claims 7 to 16, wherein X ^B are each independently a group including a group represented by the following formula; SiR ¹ _nb R ^sb _4-nb In the formula: R ¹ is a hydroxyl group or a hydrolyzable group, R ^sb is a single bond, nb is 1 or 2. The curable composition according to any one of claims 7 to 17, wherein X ^B are each independently a group represented by X ^Ba (R ^Si ) _na ; In the formula: X ^Ba are independently the basis of (m+na+1) valence, R ^Si are independently -X ^C -SiR ¹ _n' R ² _3-n' , X ^C is a divalent organic radical with carbon number from 1 to 10, R ¹ are each independently a hydroxyl group or a hydrolyzable group, R ² are each independently a hydrogen atom or a monovalent organic group, n’ is an integer from 1 to 3, na is an integer from 1 to 10. The curable composition according to claim 18, wherein X ^C is C _1-6 alkylene group, -(CH ₂ ) _z1 -O-(CH ₂ ) _z2 -(in the formula, z1 is an integer from 0 to 6, z2 is an integer from 0 to 6), or -(CH ₂ ) _z3 -phenylene-(CH ₂ ) _z4 -(In the formula, z3 is an integer from 0 to 6, z4 is an integer from 0 to 6). The curable composition according to claim 18 or 19, wherein n' is 3. The curable composition according to any one of claims 18 to 20, wherein X ^Ba is a trivalent group, n is 1, and m is 1. The curable composition according to any one of claims 18 to 21, wherein X ^Ba is N or -C(-O-)-, n is 1, and m is 1. The curable composition according to any one of claims 7 to 22, wherein formula (A3) is R ^b ₂ NR ^d -CO-(R ^F2 -CO-NR ^c -R ^a (R ^Ac ) _m3 -NR ^c -CO) _x -R ^F2 -CO-R ^d -NR ^b ₂ (A3-b) In the formula, R ^b is independently R ^Si , R ^Ac , or R ^c , However, at least one of R ^b is R ^Si , R ^Si are independently -X ^C -SiR ¹ _n' R ² _3-n' , X ^C is a divalent organic radical with carbon number from 1 to 10, R ¹ are each independently a hydroxyl group or a hydrolyzable group, R ² are each independently a hydrogen atom or a monovalent organic group, n’ is an integer from 1 to 3, R ^d are each independently a single bond or a divalent organic group, R ^F2 , R ^a , R ^c , R ^Ac , m3, and x are synonymous with the description in claim 4. The curable composition according to Claim 23, wherein one of the R ^b's bonded to the N atoms located at each terminal in the formula (A3) is R ^Si , and the others are R ^c or R ^Ac . The curable composition according to claim 23 or 24, wherein R ^d is independently a single bond, or -(CH ₂ ) _z17 -NR ¹⁰ -(CH ₂ ) _z18 -(in the formula, R ¹⁰ is hydrogen atom or C _1-6 alkyl group, z17 is an integer from 0 to 6, z18 is an integer from 0 to 6). The curable composition according to any one of claims 7 to 25, wherein R ^a is each independently a group represented by the following formula: -R ⁹ -(R ^a' -R ⁹ ) _k - In the formula: R ⁹ are each independently C _1-6 alkylene group, R ^a' are independently 3-valent bases, k is an integer from 1 to 4. The curable composition according to claim 26, wherein R ^a' is independently between N, -C(-O-)-, and carbon-carbon atoms and may include amine bonding, amide bonding, amine bonding, etc. A trivalent group of ethyl formate bond, urea bond, ether bond, or ester bond. The curable composition according to claim 26 or 27, wherein k is 1 or 2. The curable composition according to any one of claims 7 to 28, wherein R ^c is each independently a hydrogen atom or a C _1-6 alkyl group. The curable composition according to any one of claims 7 to 29, wherein x is an integer from 1 to 5. The curable composition according to any one of claims 7 to 30, wherein the fluorine-containing polyether group-containing acrylic compound contains a compound represented by formula (A1) or (A2). The curable composition according to any one of claims 7 to 31, wherein the fluorine-containing polyether group-containing acrylic compound contains a compound represented by formula (A3). The curable composition according to any one of claims 1 to 32, wherein the fluorine-containing polyether group silane compound is a fluorine-containing polyether group silane represented by the following formula (B1) or (B2) compound, R ^F3 _α -X ^Z -R ^Si _β (B1) R ^Si _γ -X ^Z -R ^F4 -X ^Z -R ^Si _γ (B2) In the formula: R ^F3 are independently Rf ³ -R ^FB -O _q3 -; R ^F4 is -Rf ⁴ _p3 -R ^FB -O _q3 -; Rf ³ are each independently a C _1-16 alkyl group that may be substituted by 1 or more than 1 fluorine atom; Rf ⁴ is a C _1-6 alkylene group which may be substituted by 1 or more than 1 fluorine atom; R ^FB are independently divalent fluoropolyether groups; p3 is 0 or 1; q3 is independently 0 or 1; R ^Si is independently a monovalent group including a Si atom bonded to a hydroxyl group, a hydrolyzable group, a hydrogen atom or a monovalent organic group; At least one R ^Si is a univalent group including a Si atom bonded to a hydroxyl group or a hydrolyzable group; X and ^Z are each independently a single bond or an organic group with a valence of 2 to 10; α is an integer from 1 to 9; β is an integer from 1 to 9; γ is independently an integer from 1 to 9. The curable composition according to claim 33, wherein R ^Si is a group represented by the following formula (S1), (S2), (S3), (S4) or (S5):

-SiR ²⁵ _n1 R ²⁶ _3-n1 (S2) -SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 (S3) -CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 (S4) -NR ^g1 R ^h1 (S5) In the formula: R ²⁵ is independently a hydroxyl group or a hydrolyzable group; R ²⁶ are each independently a hydrogen atom or a monovalent organic group; n1 is an integer from 0 to 3 in each (SiR ²⁵ _n1 R ²⁶ _3-n1 ) unit independently; X ¹¹ is independently a single bond or a divalent organic group; R ²⁷ are each independently a hydrogen atom or a monovalent organic group; t is independently an integer above 2; R ²⁸ is independently a hydrogen atom, a halogen atom or -X ¹¹ -SiR ²⁵ _n1 R ²⁶ _3-n1 ; R ²⁹ are each independently a single bond, an oxygen atom, an alkylene group with 1 to 6 carbon atoms, or an alkyleneoxy group with 1 to 6 carbon atoms; R ^a1 are independently -Z ¹ -SiR ²¹ _p1 R ²² _q1 R ²³ _r1 ; Z ¹ is independently an oxygen atom or a divalent organic group; R ²¹ are independently -Z ^1' -SiR ^21' _p1' R ^22' _q1' R ^23' _r1' ; R ²² are each independently a hydroxyl group or a hydrolyzable group; R ²³ are each independently a hydrogen atom or a monovalent organic group; p1 are independently integers from 0 to 3; q1 are independently integers from 0 to 3; r1 are independently integers from 0 to 3; Z ^1' are each independently an oxygen atom or a divalent organic group; R ^21' are independently -Z ^1” -SiR ^22” _q1” R ^23” _r1” ; R ^22' is independently a hydroxyl group or a hydrolyzable group; R ^23' are each independently a hydrogen atom or a monovalent organic group; p1’ are independently integers from 0 to 3; q1’ are independently integers from 0 to 3; r1’ are independently integers from 0 to 3; Z ^1″ are independently oxygen atoms or divalent organic groups; R ^22″ are each independently a hydroxyl group or a hydrolyzable group; R ^23″ are each independently a hydrogen atom or a monovalent organic group; q1” are independently integers from 0 to 3; r1” are independently integers from 0 to 3; R ^b1 are each independently a hydroxyl group or a hydrolyzable group; R ^c1 are each independently a hydrogen atom or a monovalent organic group; k1 are independently integers from 0 to 3; l1 are independently integers from 0 to 3; m1 are independently integers from 0 to 3; R ^d1 are independently -Z ² -CR ³¹ _p2 R ³² _q2 R ³³ _r2 ; Z ² are independently a single bond, an oxygen atom or a divalent organic group; R ³¹ are independently -Z ^2' -CR ^32' _q2' R ^33' _r2' ; R ³² are independently -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 ; R ³³ are each independently a hydrogen atom, a hydroxyl group or a monovalent organic group; p2 are independently integers from 0 to 3; q2 are independently integers from 0 to 3; r2 are independently integers from 0 to 3; Z ^2' are independently a single bond, an oxygen atom or a divalent organic group; R ^32' are independently -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 ; R ^33' are independently a hydrogen atom, a hydroxyl group or a monovalent organic group; q2’ are independently integers from 0 to 3; r2’ are independently integers from 0 to 3; Z ³ are independently a single bond, an oxygen atom or a divalent organic group; R ³⁴ is independently a hydroxyl group or a hydrolyzable group; R ³⁵ are each independently a hydrogen atom or a monovalent organic group; n2 are independently integers from 0 to 3; R ^e1 are independently -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 ; R ^f1 are each independently a hydrogen atom, a hydroxyl group or a monovalent organic group; k2 are independently integers from 0 to 3; l2 are independently integers from 0 to 3; m2 are independently integers from 0 to 3; R ^g1 and R ^h1 are independently -Z ⁴ -SiR ²⁵ _n1 R ²⁶ _3-n1 , -Z ⁴ -SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 , -Z ⁴ -CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 ; Z ⁴ are independently a single bond, an oxygen atom or a divalent organic group; However, in the formulas (S1), (S2), (S3), (S4) and (S5), there is at least one Si atom bonded to a hydroxyl group or a hydrolyzable group. The curable composition according to any one of claims 1 to 32, wherein the fluorine-containing polyether group silane compound is a fluorine-containing polyether group silane compound represented by the following formula (B3), R ³⁹ _j -R ³⁸ -NR ³⁷ CO-(R ^F4 -CONR ³⁷ -R ³⁶ -NR ³⁷ CO) _r -R ^F4 -CONR ³⁷ -R ³⁸ -R ³⁹ _j (B3) In the formula: R ^F4 is -Rf ⁴ _p3 -R ^FB -O _q3 -; Rf ⁴ is a C _1-6 alkylene group which may be substituted by 1 or more than 1 fluorine atom; R ^FB are independently divalent fluoropolyether groups; p3 is 0 or 1; q3 is 0 or 1; R ³⁶ are each independently a divalent organic group, R ³⁷ is each independently a hydrogen atom or an organic group with one valence of carbon atoms from 1 to 8, R ³⁸ are each independently an organic radical with (j+1) valence, R ³⁹ are each independently -SiR ²⁵ _n1 R ²⁶ _3-n1 , R ²⁵ is independently a hydroxyl group or a hydrolyzable group; R ²⁶ are each independently a hydrogen atom or a monovalent organic group; n1 is an integer from 0 to 3 in each (SiR ²⁵ _n1 R ²⁶ _3-n1 ) unit independently; j are independently integers from 1 to 9, r is an integer above 1. The curable composition according to any one of claims 33 to 35, wherein R ^FB are each independently a group represented by the following formula: -(OC ₆ F ₁₂ ) _a -(OC ₄ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ R ^Fa ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - In the formula, R ^Fa are independently a hydrogen atom, a fluorine atom or a chlorine atom, a, b, c, d, e and f are each independently an integer from 0 to 200. The sum of a, b, c, d, e and f is more than 1. Mark a, b, c, d, e or f The order of the repeating units enclosed in brackets in the formula is arbitrary. However, when all R ^Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1. above. The curable composition according to any one of claims 1 to 36, wherein the cross-linking agent is a compound represented by formula (C1), (R ^g1 -O) _δ -Si-R ^g2 _4-δ (C1) in the formula; Each time R ^g1 appears, it is independently a hydrogen atom or a 1-valent organic group; R ^g2 are independently univalent organic groups; δ is an integer from 2 to 4. The curable composition according to any one of claims 1 to 37, wherein the cross-linking agent is tetraethoxysilane, tetramethoxysilane, methyltriethoxysilane, methyltrimethoxysilane Silane, dimethyldimethoxysilane, dimethyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, tridecafluoro-n-octyltriethoxysilane, or tridecafluoro-n-octyltrimethoxysilane. The curable composition according to any one of claims 1 to 38, wherein the catalyst is an acid, an alkali, a transition metal, or is selected from the group consisting of tin-based catalysts, titanium-based catalysts, and zirconium oxide-based catalysts. , bismuth-based catalysts, and metal complexes of organic amine-based catalysts. The curable composition according to any one of claims 1 to 39, wherein the catalyst is acetic acid, trifluoroacetic acid, ammonia, triethylamine, diethylamine, Ti, Ni, Sn, dilaurate n-Butyltin(IV), diisopropoxybis(acetylethylacetate)titanium, tetra-n-butoxytitanium, tetraethylhexyltitanium, tetraacetylacetonetitanium, tetraacetylacetonezirconium , Tetra-n-butoxyzirconium, dibutoxybis(acetyl ethyl acetate) zirconium, or ginseng (2-ethyl hexanoate) bismuth. The curable composition according to any one of claims 1 to 40, wherein the radical polymerization initiator is diketones, gallioins, gallioin ethers, thioxanthones, diphenyls Ketones, acetophenones, quinones, aminobenzoic acids, halogen compounds, acylphosphine oxides, or peroxides. The curable composition according to any one of claims 1 to 41, wherein the radical polymerization initiator is benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis( Diethylamino)benzophenone, acetophenone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'- Dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl[4-(methylthio)phenyl]-2-

Phino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-

Phinylphenyl)-butan-1-one, anthraquinone, 1,4-naphthoquinone, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethyl (n-butoxy)ethyl aminobenzoate, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, benzoyl chloride, trihalogen Methylphenyl trisulfide, hydroxyl phosphine oxide, or di-tertiary butyl peroxide, methyl benzoate, 1-hydroxy-cyclohexyl-phenyl-one, 1-[4-(2-hydroxy Ethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propanol) base)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-

Oxylinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-

Phylinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-

Phyllinyl)phenyl]-1-butanone, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis( eta 5-2,4-cyclopentadiene-1- base)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyl oxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl oxime)-9H-carbazol-3-yl]-,1- (0-acetyl oxime), 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, tris Grade butyl hydroperoxide, cumene hydroperoxide, dicumyl hydroperoxide, p-menthane hydroperoxide, or tertiary methyl butyl hydroperoxide. The curable composition according to any one of claims 1 to 42, further containing a solvent. A hardened product obtained from the hardenable composition described in any one of claims 1 to 43. An article including a base material and a layer formed on the surface of the base material by the curable composition according to any one of claims 1 to 43.