TW202336025A - Surface treatment agent - Google Patents

Abstract

The present invention provides a compound represented by the following formula (1) (wherein each symbol has the same meaning as described in the specification). R<SP>b</SP>2N-R<SP>d</SP>-CO-(R<SP>F2</SP>-CO-NR<SP>c</SP>-R<SP>a</SP>(R<SP>Ac</SP>m)-NR<SP>c</SP>-CO)x-R<SP>F2</SP>-CO-R<SP>d</SP>-NR<SP>b</SP>2 (1).

Description

surface treatment agent

The present disclosure relates to novel fluoropolyether-based acrylic compounds and surface treatment agents containing the compounds.

Certain fluoropolyether-based silane compounds are known to provide excellent water repellency, oil repellency, antifouling properties, etc. when used in surface treatment of substrates. A layer obtained from a surface treatment agent containing a silane compound containing a fluoropolyether group (hereinafter also referred to as a "surface treatment layer") is applied as a so-called functional film to, for example, glass, plastics, fibers, and sanitary products. , building materials and other various base materials (Patent Document 1).

[Prior technical literature]

[Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2003-238577

Although the fluoropolyether group-containing silane compound described in Patent Document 1 can provide a surface treatment layer with excellent functions, there is still a need for a surface treatment layer with higher durability.

An object of the present disclosure is to provide a fluorine-containing polyether-based compound that can provide a surface treatment layer with excellent durability.

This disclosure includes the following aspects.

[1] A compound represented by the following formula (1),

R ^b ₂ NR ^d -CO-(R ^F2 -CO-NR ^c -R ^a (R ^Ac _m )-NR ^c -CO) _x -R ^F2 -CO-R ^d -NR ^b ₂ (1)

In the formula,

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

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

R ^F is a divalent fluoropolyether group,

p is 0 or 1,

q is 0 or 1,

R ^a are independently (m+2)-valent organic groups,

m is an integer from 1 to 4,

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

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

X ^C is a divalent organic group with 1 to 10 carbon atoms,

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

R ² is independently a hydrogen atom or a monovalent organic group,

n’ is an integer from 1 to 3,

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

X ^D is a divalent organic radical,

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

X ^F are each independently a divalent organic group having 1 to 10 carbon atoms,

R ⁵ is a hydrogen atom or a monovalent organic group with 1 to 8 carbon atoms,

m’ is an integer from 1 to 10,

R ^c are each independently a hydrogen atom or a C _1-6 alkyl group,

R ^d are independently single bonds or divalent organic groups,

x is an integer above 1.

[2] The compound as described in the above [1], 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 of existence of each repeating unit enclosed in parentheses is arbitrary in the formula, but when all R ^Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1 or more.

[3] The compound according to [1] or [2] above, wherein R ^Fa is a fluorine atom.

[4] The compound according to any one of the above [1] to [3], wherein R ^F is each independently the following formula (f1), (f2), (f3), (f4), (f5) ) or the basis represented by (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 an integer from 0 to 2. The order of existence of each repeating unit marked with the subscript d or e and enclosed in brackets is arbitrary in the formula;

-(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 existence of each repeating unit marked with the subscript c, d, e or f and enclosed in parentheses is arbitrary in the formula;

-(R ⁶ -R ⁷ ) _g -R ⁹ - (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,

R ⁹ is a single bond, or a group selected from OCF ₂ , OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ ,

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 as shown in the following chemical formula,

In the formula, * represents 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, the sum of a, b, c, d, e and f is at least 1, and then Or, the order of existence of each repeating unit marked a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula,

-(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, the sum of a, b, c, d, e and f is at least 1, and then Otherwise, the order of existence of each repeating unit marked a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula.

[5] The compound according to any one of the above [1] to [4], wherein ^RF2 is each independently a C _1-6 perfluoroalkylene group.

[6] The compound according to any one of the above [1] to [5], 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 each independently a trivalent organic group,

k is an integer from 1 to 4.

[7] The compound according to the above [6], wherein R ^a' is each independently a trivalent organic group containing an N atom or an O atom.

[8] The compound as described in the above [6], wherein R ^a' can independently contain an amine bond, an amide bond, a urethane bond, a urea bond, or an ether bond between carbon-carbon atoms. Or the 3-valent organic group of the ester bond.

[9] The compound according to any one of the above [6] to [8], wherein R ^a' is each independently the following group,

In the formula, R ⁸ is a hydrogen atom or a C _1-6 alkyl group.

[10] The compound according to any one of [6] to [9] above, wherein R ^a' is N.

[11] The compound according to any one of [6] to [10] above, wherein k is 1.

[12] The compound according to any one of [6] to [10] above, wherein k is 2.

[13] The compound according to any one of the above [1] to [12], wherein at least one R ^b is R ^Si .

[14] The compound according to any one of the above [1] to [13], wherein one of the R ^b 's bonded to the N atom at each terminal is R ^Si and the others are R ^c .

[15] The compound according to any one of the above [1] to [13], wherein one of the R ^b 's bonded to the N atom at each terminal is R ^Si and the others are R ^Ac .

[16] The compound according to any one of [1] to [15] above, wherein X ^C is:

C _1-6 alkylene group,

-(CH ₂ ) _z1 -O-(CH ₂ ) _z2 -(where 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, and z4 is an integer from 0 to 6).

[17] The compound according to any one of [1] to [16] above, wherein X ^C is a C _1-6 alkylene group.

[18] The compound according to any one of the above [1] to [17], wherein n' is 2 or 3.

[19] The compound according to any one of [1] to [18] above, wherein n' is 3.

[20] The compound according to any one of the above [1] to [19], wherein X ^D is -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -OCONH-, -NHCOO-, -NH-CO-NH-, -CH ₂ CH(OH)CH ₂ - or -CH(CH ₂ OH)CH ₂ -.

[21] The compound according to any one of the above [1] to [20], wherein X ^D is -CONH-, -CH ₂ CH(OH)CH ₂ - or -CH(CH ₂ OH)CH ₂ -.

[22] The compound according to any one of [1] to [21] above, wherein X ^D is -CONH-.

[23] The compound according to any one of the above [1] to [22], wherein X ^E is a single bond.

[24] The compound according to any one of the above [1] to [23], wherein X ^E is -X ^G -X ^H ,

X ^G is:

single key,

C _1-6 alkylene group,

-(CH ₂ ) _z9 -O-(CH ₂ ) _z10 -(where 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 shown in the following chemical formula,

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

[25] The compound according to any one of [1] to [24] above, wherein X ^F is:

C _1-6 alkylene group,

-(CH ₂ ) _z5 -O-(CH ₂ ) _z6 -(where 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, and z8 is an integer from 0 to 6).

[26] The compound according to any one of the above [1] to [25], wherein R ^c is each independently a hydrogen atom or a C _1-6 alkyl group.

[27] The compound according to any one of the above [1] to [26], 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).

[28] The compound according to any one of the above [1] to [27], wherein x is an integer from 1 to 5.

[29] A surface treatment agent containing the compound described in any one of [1] to [28] above.

[30] The surface treatment agent as described in the above [29], which further contains one or more other components selected from the group consisting of fluorine-containing oil, polysilicone oil and catalyst.

[31] The surface treatment agent according to the above [29] or [30], which is used as an antifouling coating agent or a waterproof coating agent.

[32] An article composed of a base material and the compound described in any one of the above [1] to [28] or the surface treatment agent described in any one of the above [29] to [31]. layer on the surface of the substrate.

According to the present disclosure, a fluoropolyether-based acrylic compound capable of providing a surface treatment layer with excellent durability can be provided.

When used in this specification, "monovalent organic group" means a monovalent group containing carbon. The monovalent organic group is not particularly limited and may be a hydrocarbon group or a derivative thereof. The derivative of a hydrocarbon group means having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy and other groups at the end of the hydrocarbon group or in the molecular chain. In addition, when simply expressed as "organic group", it means a monovalent organic group. Furthermore, the so-called "bivalent organic group" means a divalent group containing carbon. The divalent organic group is not particularly limited, and examples include a divalent group obtained by detaching one hydrogen atom from an organic group.

When used in this specification, the term "hydrocarbyl group" means a group containing carbon and hydrogen and further detaching one hydrogen atom from a hydrocarbon. The hydrocarbon group is not particularly limited, and examples thereof include C _1-20 hydrocarbon groups that may be substituted by one or more substituents, such as aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and the like. The above-mentioned "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. Furthermore, the hydrocarbon group may contain one or more ring structures.

When used in this specification, the substituent of the "hydrocarbyl group" is not particularly limited. Examples include: selected from halogen atoms; C _1-6 alkyl groups and C _2-6 alkenyl groups which may be substituted by one or more halogen atoms. , C _2-6 alkynyl, C _3-10 cycloalkyl, C _3-10 unsaturated cycloalkyl, 5 to 10 membered heterocyclyl, 5 to 10 membered unsaturated heterocyclyl, C _6-10 aryl and more than 1 of 5 to 10 membered heteroaryl groups.

The term "hydrolyzable group" in this specification means a group that can undergo hydrolysis reaction, that is, a group that can be separated from the main skeleton of the compound by hydrolysis reaction. Examples of hydrolyzable groups include -OR ^h , -OCOR ^h , -ON=CR ^h ₂ , -NR ^h ₂ , -NHR ^h , halogen, etc. In this equation, R ^h represents substituted or unsubstituted C _1-4 alkyl.

The fluorine-containing polyether group acrylic compound of the present disclosure is a fluorine-containing polyether group acrylic compound represented by the following formula (1),

R ^b ₂ NR ^d -CO-(R ^F2 -CO-NR ^c -R ^a (R ^Ac _m )-NR ^c -CO) _x -R ^F2 -CO-R ^d -NR ^b ₂ (1)

In the formula,

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

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

R ^F is a divalent fluoropolyether group,

p is 0 or 1,

q is 0 or 1,

R ^a are independently (m+2)-valent organic groups,

m is an integer from 1 to 4,

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

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

X ^C is a divalent organic group with 1 to 10 carbon atoms,

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

R ² is independently a hydrogen atom or a monovalent organic group,

n’ is an integer from 1 to 3,

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

X ^D is a divalent organic radical,

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

X ^F are each independently a divalent organic group having 1 to 10 carbon atoms,

R ⁵ is a hydrogen atom or a monovalent organic group with 1 to 8 carbon atoms,

m’ is an integer from 1 to 10,

R ^c are each independently a hydrogen atom or a C _1-6 alkyl group,

R ^d are independently single bonds or divalent organic groups,

x is an integer above 1.

In the above formula (1), R ^F2 is -Rf ² _p -R ^F -O _q -.

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

The "C _1-6 alkylene group" in the above-mentioned C _1-6 alkylene group which may be substituted by more than one fluorine atom can be a straight chain or a branched chain, preferably a straight chain or branched chain C _{1 -3} alkylene group, more preferably linear C _1-3 alkylene group.

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

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 group, 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 formula (1), R ^F are each independently a divalent fluoropolyether group.

The preferred system of R ^F may contain a group represented by the following formula,

-(OCH ₁ R ^Fa _2h1 ) _h3 -(OCH ₂ R ^Fa _2h2-2 ) _h4 -

In the formula,

Each occurrence of R ^Fa is independently a hydrogen atom, a fluorine atom, or a chlorine atom,

h1 is an integer from 1 to 6,

h2 is an integer from 4 to 8,

h3 is an integer above 0,

h4 is an integer above 0,

However, the combination of h3 and h4 is 1 or more, preferably 2 or more, more preferably 5 or more, and the order of existence of the repeating units marked h3 and h4 and enclosed in parentheses is arbitrary in the formula.

In one aspect, ^RF can be linear or branched. R ^F is preferably the basis 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, and the sum of a, b, c, d, e and f is more than 1; label a, b, c, d, e or f And the order of existence of each repeating unit enclosed in parentheses is arbitrary in the formula. 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, 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, more preferably 60 or less, for example, it can be 50 or less or 30 or less.

These repeating units may be linear or branched. 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 )) - either. -(OC ₂ F ₄ )- may be any one of -(OCF ₂ CF ₂ )- and -(OCF(CF ₃ ))-.

In one aspect, the repeating units are linear. By making the above-mentioned repeating unit into a linear chain, the surface smoothness, abrasion durability, etc. of the surface treatment layer can be improved.

In one aspect, the repeating units are in the form of branched chains. By forming the repeating unit into a branched chain shape, the dynamic friction coefficient of the surface treatment layer can be increased.

In one aspect, R ^F may contain a ring structure.

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, * represents the bonding position.

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

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

In the formula, * represents the bonding position.

In one aspect, R ^F are 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, and e is an integer from 0 to 2. The order of existence of each repeating unit marked with the subscript d or e and enclosed in brackets is arbitrary in the formula;

-(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 existence of each repeating unit marked with the subscript c, d, e or f and enclosed in parentheses is arbitrary in the formula;

-(R ⁶ -R ⁷ ) _g -R ⁹ - (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,

R ⁹ is a single bond, or a group selected from OCF ₂ , OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ ,

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 as shown in the following chemical formula:

In the formula, * represents 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. Furthermore, a, b, c, d, e or f are marked with brackets The order of existence of each bracketed repeating unit 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. Furthermore, a, b, c, d, e or f are marked with brackets The order of existence of each bracketed repeating unit in the formula is arbitrary.

In the above formula (f1), d is preferably an integer of 5 to 200, more preferably 10 to 100, more preferably 15 to 50, for example, 25 to 35. In one aspect, e is 1. In other aspects, e is 0. In other aspects, e is 2. In one aspect, the above formula (f1) is -(OCF ₂ CF ₂ CF ₂ ) _d -(OCF ₂ CF ₂ ) _e -or -(OCF(CF ₃ )CF ₂ ) _d -(OCF(CF ₃ )) _e - the basis represented. In other aspects, the above formula (f1) is a basis represented by -(OC ₃ F ₆ ) _d1 -(OC ₂ F ₄ ) _e1 -(OC ₃ F ₆ ) _d2 -(OC ₂ F ₄ ) _e2 - (In the formula, d1 and d2 are each independently an integer from 1 to 200, the sum of d1 and d2 is less than 200, and e1 and e2 are each independently 0 or 1).

In one aspect, formula (f1) is -(OCF ₂ CF ₂ CF ₂ ) _d -(OCF ₂ CF ₂ ) _e -, preferably -(OCF ₂ CF ₂ CF ₂ ) _d -(OCF ₂ CF ₂ )-.

In other aspects, formula (f1) is a base represented by -(OCF(CF ₃ )CF ₂ ) _d -(OCF(CF ₃ )) _e -, preferably -(OCF(CF ₃ )CF ₂ ) _d -(OCF(CF ₃ ))-.

In other aspects, formula (f1) is -(OC ₃ F ₆ ) _d1 -(OC ₂ F ₄ ) _e1 -(OC ₃ F ₆ ) _d2 -(OC ₂ F ₄ ) _e2 -, preferably -( OC ₃ F ₆ ) _d1 -(OC ₂ F ₄ )-(OC ₃ F ₆ ) _d2 -(OC ₂ F ₄ ), more preferably -(OCF(CF ₃ )CF ₂ ) _d1 -(OCF ₂ CF ₂ ) -(OCF(CF ₃ )CF ₂ ) _d2 -(OCF(CF ₃ ))-.

In the above formula (f2), e and f are preferably each independently an integer of 5 to 200, more preferably an integer of 10 to 200. Furthermore, the sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, 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 represented. In other aspects, formula (f2) may be a base 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, and more Preferably, the base is selected from OC ₃ F ₆ and OC ₄ F ₈ . The combination of 2 or 3 groups independently selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ is not particularly limited, and examples thereof include: -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 one aspect, R ⁹ is a single bond. In other aspects, R ⁹ is a group selected from OCF ₂ , OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ , and OC ₆ F ₁₂ . 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-mentioned (R ⁶ -R ⁷ ) _g is preferably -(OC ₂ F ₄ -OC ₃ F ₆ ) _g - or -(OC ₂ F ₄ -OC ₄ F ₈ ) _g -.

In the above-mentioned formula (f4), R ⁶ , R ⁷ and g have the same meaning and the same aspect as those described in the above-mentioned formula (f3). R ^6' , R ^7' and g' respectively have the same meaning and the same aspect as R ⁶ , R ⁷ and g described in the above formula (f3). R ^r is preferably represented by the following chemical formula:

In the formula, * represents the bonding position;

More preferably, it is represented by the following chemical formula:

In the formula, * represents 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 group represented by the above-mentioned formula (f1).

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

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

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

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

In one aspect, the above-mentioned R ^F is a group 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, more preferably 0.2 to 1.5, and More preferably, it is 0.2 to 0.85. By setting the e/f ratio to 10 or less, the smoothness, abrasion durability, and chemical resistance (for example, durability against artificial sweat) of the surface treatment layer obtained from this compound are further improved. The smaller the e/f ratio, the smoother and abrasion durability of the surface treatment layer are improved. On the other hand, by setting the e/f ratio to 0.1 or more, the stability of the compound can be further improved. The larger the e/f ratio, the more stable the compound is.

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 ^RF2 part is not particularly limited, for example, it is 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 10,000. In this specification, the number average molecular weight of ^RF2 is set to the value measured by ¹⁹ F-NMR.

In the above formula (1), R ^a is each independently an (m+2)-valent organic group.

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 organic group,

k is an integer from 1 to 4.

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

In a preferred embodiment, k is an integer from 1 to 2.

In one aspect, k is 1.

In one aspect, k is 2.

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

In a preferred embodiment, R ^a' is independently a trivalent organic group that can contain an amine bond, an amide bond, a urethane bond, a urea bond, an ether bond or an ester bond between carbon-carbon atoms. .

In one aspect, R ^a' are independently the following bases:

In the formula, R ⁸ is a hydrogen atom or a C _1-6 alkyl group (preferably methyl or ethyl, more preferably methyl). The O in -CR ⁸ (-O-)- mentioned above is bonded to R ^Ac .

In one aspect, R ^a' is N.

In one aspect, R ^a' is -CR ⁸ (-O-)-.

In the above formula (1), m is an integer from 1 to 4.

In a preferred embodiment, m is 1 or 2.

In one aspect, m is 1.

In one aspect, m is 2.

In the above formula (1), R ^b is independently R ^Si , R ^Ac , or R ^c .

In the above formula (1), at least one R ^b is R ^Si .

In a preferred embodiment, at least one R ^b bonded to the N atom located at each terminal of the formula (1) is R ^Si .

In one aspect, one of the R ^b 's bonded to the N atoms located at each terminal of the formula (1) is R ^Si , and the others are R ^c .

In other aspects, one of the R ^b 's bonded to the N atoms located at each terminal of the formula (1) is R ^Si , and the others are R ^Ac .

The above R ^Si are 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 group, -(CH ₂ ) _z1 -O-(CH ₂ ) _z2 -(in the formula, z1 is an integer from 0 to 6, for example, it is an integer from 1 to 6, and z2 is an integer from 0 to 6 , for example, an integer from 1 to 6), or -(CH ₂ ) _z3 -phenylene-(CH ₂ ) _z4 -(where z3 is an integer from 0 to 6, for example, an integer from 1 to 6, z4 is an integer from 0 to 6, for example an integer from 1 to 6).

These groups may be substituted by one or more substituents selected from, for example, fluorine atom, C _1-6 alkyl group, C _2-6 alkenyl group and C _2-6 alkynyl group, but are preferably unsubstituted. The right side of these groups is bonded to Si.

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 this equation, R ^h represents substituted or unsubstituted C _1-4 alkyl), more preferably -OR ^h (that is, alkoxy). Examples of R ^h include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl and isobutyl; substituted alkyl groups such as chloromethyl. Among these, an alkyl group is preferred, particularly an unsubstituted alkyl group, and a methyl or ethyl group is more preferred. 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. This monovalent organic group is a monovalent organic group excluding the above-mentioned hydrolyzable group.

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

In the above formula (1), R ^Ac is each independently -X ^D -X ^E (-X ^F -OCO-CR ⁵ =CH ₂ ) _m' .

The above-mentioned X ^D is 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 - or -CH(CH ₂ OH)CH ₂ -, more preferably -CONH-, -CH ₂ CH(OH)CH ₂ - or -CH(CH ₂ OH)CH ₂ -, more preferably - CONH-. The right side of these bases are bonded to X ^E.

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

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

In one aspect, X ^E is a trivalent or tetravalent base represented by -X ^G -X ^H ,

X ^G is:

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, for example, an integer from 1 to 6, z10 is an integer from 0 to 6, for example, an integer from 1 to 6 ),or

-(CH ₂ ) _z11 -phenylene-(CH ₂ ) _z12 -(where z11 is an integer from 0 to 6, for example, 1 to 6, z12 is an integer from 0 to 6, for example, 1 to 6 an integer),

X ^H is represented by the following chemical formula:

R ⁸ is a hydrogen atom or a 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 divalent organic group having 1 to 10 carbon atoms.

In one aspect, X ^F is:

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, for example, 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, for example, from 1 to 6, and z8 is an integer from 0 to 6, for example, from 1 to 6 integer).

These groups may be substituted by one or more substituents selected from, for example, fluorine atom, C _1-6 alkyl group, C _2-6 alkenyl group and C _2-6 alkynyl group, but are preferably unsubstituted. The left side of these bases are bonded to X ^E.

The above-mentioned C _1-6 alkylene group may be a straight chain or a branched chain. In one aspect, the C _1-6 alkylene group is straight chain. In other aspects, the C _1-6 alkylene group is branched.

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

In other preferred embodiments, X ^F is -O-(CH ₂ ) _z6 -, preferably -O-(CH ₂ ) _2-4 -.

The above R ⁵ is a hydrogen 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, more preferably C _1-3 Alkyl group, particularly preferably methyl group.

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

In the above formula (1), R ^c is each independently a hydrogen atom or a C _1-6 alkyl 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.

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

In one aspect, R ^c is methyl.

In the above formula (1), R ^d is 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 group.

The divalent organic group in R ^d 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, for example, an integer from 1 to 6, z14 is an integer from 0 to 6, for example, an integer from 1 to 6 ),

-(CH ₂ ) _z15 -phenylene-(CH ₂ ) _z16 -(where z15 is an integer from 0 to 6, for example, 1 to 6, z16 is an integer from 0 to 6, for example, 1 to 6 an integer), 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, and z18 is an integer from 0 to 6). These groups may be substituted by one or more substituents selected from, for example, fluorine atom, C _1-6 alkyl group, C _2-6 alkenyl group and C _2-6 alkynyl group, but are preferably unsubstituted. 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 can be a straight chain or a branched chain, preferably a straight chain.

In the above formula (1), x is an integer equal to or greater than 1.

In one aspect, An integer above 5 and below.

The fluorine-containing polyether group-containing acrylic compound represented by the formula (1) is not particularly limited, and may have a number average molecular weight of 5×10 ² to 2×10 ⁵ . Within this range, from the viewpoint of abrasion durability, it is preferable to have a number average molecular weight of 2×10 ³ to 1×10 ⁵ , more preferably 3×10 ³ to 2×10 ⁴ . The "number average molecular weight" is a value measured by ¹⁹ F-NMR.

In one aspect, the above-mentioned fluorine-containing polyether group acrylic compound represented by formula (1) is a 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 has the same meaning as described in formula (1)]

React with the compound represented by the following chemical formula,

NH ₂ -R ⁹ -(NH-R ⁹ ) _k -NH ₂

[In the formula, R ⁹ and k have the same meaning as described in formula (1)]

And obtain the compound represented by the following formula

R ²¹ OOC-(R ^F2 -CONH-R ⁹ -(NH-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 (1)].

Next, the obtained compound is reacted with a compound represented by the following formula:

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' have the same meanings as described in formula (1) ]

And the compound represented by the following formula is 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 obtained 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 divalent base]

Thereby, the compound represented by formula (1) can be obtained.

In one aspect, the above-mentioned fluorine-containing polyether group acrylic compound represented by formula (1) is a 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 has the same meaning as described in formula (1)]

React with the compound represented by the following chemical formula,

NH ₂ -R ⁹ -(CH(OH)-R ⁹ ) _k -NH ₂

[In the formula, R ⁹ and k have the same meaning as described in formula (1)]

And obtain the compound represented by the following formula

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 (1)].

Next, the obtained compound is reacted with a compound represented by the following formula:

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' have the same meanings as described in formula (1) ]

And the compound represented by the following formula is 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 obtained 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 divalent base]

Thereby, the compound represented by formula (1) can be obtained.

In one aspect, the fluorine-containing polyether group acrylic compound represented by the above formula (1) is a 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 has the same meaning as described in formula (1)]

React with the compound represented by the following chemical formula,

NH ₂ -R ⁹ -(NH-R ⁹ ) _k -NH ₂

In the formula, R ⁹ and k have the same meaning as described in formula (1);

And the compound represented by the following formula is obtained,

R ²¹ OOC-(R ^F2 -CONH-R ⁹ -(NH-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 (1)].

Next, the obtained compound is reacted with a compound represented by the following formula:

NH ₂ -R ^9' -NH ₂

[In the formula, R ^9' has the same meaning as the description about R ⁹ ]

And the compound represented by 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 have the same meanings as described in formula (1), and R ^9′ has the same meaning as described in R ⁹ ].

Next, the obtained compound is reacted with a compound represented by the following formula:

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' have the same meanings as described in formula (1) ]

And the compound represented by the following formula is 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 obtained 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 divalent base]

Thereby, the compound represented by formula (1) can be obtained.

The reaction conditions of each step of the above reaction can be appropriately set by those with ordinary knowledge in the art.

Next, the surface treatment agent of this disclosure will be described.

The surface treatment agent of the present disclosure contains an acrylic compound represented by formula (1) and containing at least one fluoropolyether group.

In one aspect, in the surface treatment agent of the present disclosure, the fluorine-containing polyether group-containing acrylic compound is a compound represented by formula (1).

Relative to the entire surface treatment agent, the content of the compound represented by the above formula (1) is preferably 0.1 to 50.0 mass%, more preferably 1.0 to 30.0 mass%, more preferably 5.0 to 25.0 mass%, and particularly preferably 10.0 to 20.0% by mass. By setting the content of the acrylic compound of the fluorine-containing polyether group within the above range, higher water and oil repellency and abrasion durability can be obtained.

The surface treatment agent of the present disclosure may contain: a solvent, a (non-reactive) fluoropolyether compound that can be understood as a fluorine-containing oil, preferably a perfluoro(poly)ether compound (hereinafter collectively referred to as "fluorine-containing oil"), It can be understood as the (non-reactive) polysilicone compound of polysilicone oil (hereinafter referred to as "polysilicone oil"), alcohols, catalysts, surfactants, polymerization inhibitors, sensitizers, etc.

Examples of the solvent include aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral spirits; benzene, toluene, xylene, naphthalene, Aromatic hydrocarbons such as solvent naphtha; methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate , carbitol acetate, diethyl oxalate, ethyl pyruvate, ethyl butyrate-2-hydroxy ester, ethyl acetate, amyl acetate, methyl lactate, ethyl lactate, 3-methoxypropyl Methyl acid ester, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate and other esters; acetone, butanone, methyl isobutyl ketone, 2-hexanone , cyclohexanone, methylamine ketone, 2-heptanone and other ketones; ethyl cellosolve, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol mono Methyl 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, ethylene glycol monoalkyl ether and other glycols Ethers; methanol, ethanol, isopropanol, n-butanol, isobutanol, tert-butanol, sec-butanol, 3-pentanol, octanol, 3-methyl-3-methoxybutanol, Alcohols such as pentanol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; N,N-dimethylformamide , N,N-dimethylacetamide and other amide; methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether and other ether alcohols; Ethylene glycol monoethyl ether acetate; 1,1,2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, dichloroethane Methylene, 1,1-dichloro-1,2,2,3,3-pentafluoropropane (HCFC225), Zeorora H, HFE7100, HFE7200, HFE7300, CF ₃ CH ₂ OH, CF ₃ CF ₂ CH ₂ Fluorine-containing solvents such as OH, (CF ₃ ) ₂ CHOH, etc. Alternatively, a mixed solvent of two or more of these may be used.

The fluorine-containing oil is not particularly limited, and examples thereof 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 having 1 to 16 carbon atoms that may be substituted by one or more fluorine atoms (preferably a C _1-16 perfluoroalkyl group), and Rf ⁶ represents an alkyl group that may be substituted with one or more fluorine atoms. an alkyl group having 1 to 16 carbon atoms (preferably a C _1-16 perfluoroalkyl group), a fluorine atom or a hydrogen atom, and Rf ⁵ and Rf ⁶ are more preferably each independently a C _1-3 perfluoroalkyl group.

a', b', c' and d' respectively represent the number of the four repeating units of the perfluoro (poly) ether 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 existence of each repeating unit marked with the subscript a', b', c' or d' and enclosed in parentheses is arbitrary in the formula. Among these repeating units, -(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 Any one of (CF ₃ )CF(CF ₃ ))-, -(OCF(C ₂ F ₅ )CF ₂ )- and (OCF ₂ CF(C ₂ F ₅ ))-, 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 ))-, preferably is -(OCF ₂ CF ₂ CF ₂ )-. -(OC ₂ F ₄ )- may be any one of -(OCF ₂ CF ₂ )- and (OCF(CF ₃ ))-, and is preferably -(OCF ₂ CF ₂ )-.

Examples of perfluoro(poly)ether compounds represented by the above general formula (3) include: compounds represented by either of the following general formulas (3a) and (3b) (which may be one type or a mixture of two or more types) ).

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 this equation, Rf ⁵ and Rf ⁶ are as described above; in formula (3a), b” is an integer from 1 to 100; in formula (3b), a” and b” are independently from 0 to 30 The following integers, c” and d” are independently integers from 1 to 300. The order of existence of each repeating unit marked with subscripts a”, b”, c”, d” and enclosed in parentheses is in the formula: Any.

Furthermore, from another point of view, 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). Furthermore, 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.

Relative to the surface treatment agent of the present disclosure, the fluorine-containing oil may contain, for example, 0 to 50 mass%, preferably 0 to 30 mass%, and more preferably 0 to 5 mass%. In one aspect, the surface treatment agent of the present disclosure is substantially free of fluorinated oil. The so-called substantially free of fluorinated oil means that it does not contain fluorinated oil at all or may contain a very small amount of fluorinated oil.

In one aspect, the average molecular weight of the fluorine-containing oil can be set to be greater than the average molecular weight of the acrylic compound containing the fluorine-containing polyether group. By setting the average molecular weight to this, more excellent abrasion durability and surface smoothness can be obtained, especially when the surface treatment layer is formed by vacuum evaporation.

In one aspect, the average molecular weight of the fluorine-containing oil can be set to be smaller than the average molecular weight of the acrylic compound containing the fluorine-containing polyether group. By setting the average molecular weight to this, it is possible to suppress a decrease in the transparency of the surface treatment layer obtained from this compound and form a hardened product having high abrasion durability and high surface smoothness.

Fluorine-containing oil is beneficial to improving the surface smoothness of the layer formed by the surface treatment agent of the present disclosure.

As the polysiloxane oil, for example, a linear or cyclic polysiloxane oil having a siloxane bond number of 2,000 or less can be used. The linear polysilicone oil can be so-called straight silicone oil and modified polysilicone oil. Pure polysilicone oil can be listed as: dimethyl polysilicone oil, methylphenyl polysiloxane Oxygen oil, methyl hydrogen polysiloxane oil. Modified polysilicone oil can be enumerated: pure polysilicone oil is modified by alkyl groups, aralkyl groups, polyethers, higher fatty acid esters, fluoroalkyl groups, amine groups, epoxy groups, carboxyl groups, alcohols, etc. By. Examples of the cyclic polysiloxane oil include cyclic dimethylsiloxane oil.

In the surface treatment agent of the present disclosure, the polysiloxane oil may be, for example, relative to a total of 100 parts by mass of the fluorine-containing polyether group acrylic compounds of the present disclosure (when there are two or more types, the total of these, the same applies below). 0 to 300 parts by mass, preferably 50 to 200 parts by mass.

Polysilicone oil is beneficial to improve the surface smoothness of the surface treatment layer.

The above-mentioned alcohols are, for example, alcohols having 1 to 6 carbon atoms which may be substituted by one or more fluorine atoms. Examples include: methanol, ethanol, isopropyl alcohol, tert-butanol, CF ₃ CH ₂ OH, CF ₃ CF ₂ CH ₂ OH, (CF ₃ ) ₂ CHOH. By adding these alcohols to the surface treatment agent, the stability of the surface treatment agent is enhanced, and the compatibility between the perfluoropolyether group-containing acrylic compound and the solvent is improved.

The above-mentioned alcohol is preferably 2,2,3,3,3-pentafluoro-1-propanol or 2,2,2-trifluoroethanol.

Examples of the catalyst include acids (such as acetic acid, trifluoroacetic acid, etc.), bases (such as ammonia, triethylamine, diethylamine, etc.), transition metals (such as Ti, Ni, Sn, etc.).

The catalyst promotes the hydrolysis, dehydration condensation or polymerization of the fluorine-containing polyether group acrylic compound of the present disclosure, and promotes the formation of the layer formed by the surface treatment agent of the present disclosure.

In addition to the above, examples of other ingredients include: tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and methyltriethoxysilane. Oxysilane, etc.

The surface treatment agent of the present disclosure can be impregnated with porous materials (such as porous ceramic materials) or metal fibers (such as steel wool) and fixed into cotton-like shapes to form particles. The particles can be used in vacuum evaporation, for example.

In addition to the above-mentioned components, the surface treatment agent of the present disclosure may also contain trace amounts of Pt, Rh, Ru, 1,3-divinyltetramethyldisiloxane, triphenylphosphine, NaCl, KCl, and silane. Condensation products and other impurities.

The following describes the items disclosed.

The article of the present disclosure includes: a substrate, and a layer (surface treatment layer) formed on the surface of the substrate by the surface treatment agent of the present disclosure.

The substrate that can be used in the present disclosure can be made of, for example, glass, resin (natural or synthetic resin, such as general plastic materials), metal, ceramics, semiconductors (silicon, germanium, etc.), fibers (fabrics, non-woven fabrics, etc.), fur, It can be composed of any suitable material such as leather, wood, ceramics, stone, etc., building components, etc., and sanitary products.

For example, when the article to be manufactured is an optical component, the material constituting the surface of the base material may be a material for optical components, such as glass or transparent plastic. Furthermore, when the article to be manufactured is an optical component, certain layers (or films), such as hard coating layers or anti-reflective layers, can be formed on the surface (outermost layer) of the substrate. As the anti-reflection layer, either a single-layer anti-reflection layer or a multi-layer anti-reflection layer can be used. Examples of inorganic substances that can be used in the anti-reflective layer include: SiO ₂ , SiO, ZrO ₂ , TiO ₂ , TiO, Ti ₂ O ₃ , Ti ₂ O ₅ , Al ₂ O ₃ , Ta ₂ O ₅ , Ta ₃ O ₅ , Nb ₂ O ₅ , HfO ₂ , Si ₃ N ₄ , CeO ₂ , MgO, Y ₂ O ₃ , SnO ₂ , MgF ₂ , WO ₃ , etc. These inorganic substances can be used individually or in combination of 2 or more types (for example, a mixture). When forming a multi-layer anti-reflection layer, SiO ₂ and/or SiO is preferably used in the outermost layer. When the article to be manufactured is an optical glass component for a touch panel, a transparent electrode may be provided on part of the surface of the base material (glass), such as using indium tin oxide (ITO: Indium Tin Oxide) or indium zinc oxide. film. Furthermore, the base material can have an insulating layer, an adhesive layer (Pressure-sensitive Layer), a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating layer, and a polarizing film according to its specific specifications, etc. , phase difference film and liquid crystal display module, etc.

The shape of the base material is not particularly limited, and may be, for example, plate-shaped, film-shaped, or other forms. Furthermore, the surface area of the base material where the surface treatment agent layer should be formed only needs to be at least a 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.

In one aspect, at least a surface portion of the substrate may be composed of a material that originally has hydroxyl groups. Examples of the material include glass, metals (especially base metals) with natural oxide films or thermal oxide films formed on their surfaces, ceramics, and semiconductors. Alternatively, when resins and the like have hydroxyl groups but are insufficient, or when they do not originally have hydroxyl groups, hydroxyl groups can be introduced or added to the surface of the base material by subjecting the base material to some kind of pretreatment. Examples of this pretreatment include plasma treatment (such as corona discharge) or ion beam irradiation. Plasma treatment can introduce or add hydroxyl groups on the surface of the substrate, and is also suitable for use in purifying the surface of the substrate (removing impurities, etc.). Furthermore, other examples of this pretreatment can include: using the LB method (Langmuir-Blodgett method) or chemical adsorption method to form an interfacial adsorbent with a carbon-carbon unsaturated bond in the form of a monomolecular film in advance. A method of cracking unsaturated bonds on the surface of a substrate and then cracking the unsaturated bonds in an environment containing oxygen or nitrogen.

In other aspects, at least the surface portion of the substrate may be composed of a polysiloxy compound having one or more other reactive groups, such as Si-H groups, or a material containing alkoxysilane.

In a preferred aspect, the above-mentioned base material is glass. The glass is preferably sapphire glass, soda-lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystallized glass, quartz glass Glass, particularly preferably chemically strengthened soda-lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded borosilicate glass.

Articles of the present disclosure may be formed from the surface treatment agent of the present disclosure by forming a layer of the surface treatment agent of the present disclosure on the surface of the substrate and post-processing the layer as necessary, thereby forming a layer of the surface treatment agent of the present disclosure. manufacturing.

The layer formation of the surface treatment agent of the present disclosure can be carried out by applying the above surface treatment agent to the surface of the substrate in a manner that covers the surface. The covering method is not particularly limited. For example, a wet coating method and a dry coating method can be used.

Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and similar methods.

Examples of dry coating methods include evaporation (usually vacuum evaporation), sputtering, CVD and similar methods. Specific examples of the evaporation method (usually a vacuum evaporation method) include resistance heating, electron beam, high-frequency heating using microwaves, ion beam, and similar methods. Specific examples of the CVD method include plasma CVD, optical CVD, thermal CVD and similar methods.

Furthermore, it can also be coated by atmospheric pressure plasma method.

When using the wet coating method, the surface treatment agent of the present disclosure can be applied to the surface of the substrate after being diluted with a solvent. From the viewpoint of the stability of the composition of the present disclosure and the volatility of the solvent, the following solvents are suitable for use: perfluoroaliphatic hydrocarbons with 5 to 12 carbon atoms (such as perfluorohexane, perfluoromethylcyclohexane and Perfluoro-1,3-dimethylcyclohexane); Polyfluoroaromatic hydrocarbons (e.g. bis(trifluoromethyl)benzene); Polyfluoroaliphatic hydrocarbons (e.g. C ₆ F ₁₃ CH ₂ CH ₃ (e.g. Asahi Glass Asahiklin (registered trademark) AC-6000 manufactured by Zeon Japan Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (such as Zeorora (registered trademark) H manufactured by Zeon Japan Co., Ltd.) ; Hydrofluoroether (HFE) (such as perfluoropropyl methyl ether (C ₃ F ₇ OCH ₃ ) (such as 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 ether (C ₄ F 9 OC 2 H 5 ) (for example, Novec (trademark) 7200 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl ether (C 4 F ₉ OC ₂ H ₅ ) (for example, Novec (trademark) 7200 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl ether Alkyl _{perfluoroalkyl} ethers ( _{perfluoroalkyl and alkyl} groups _can be linear or branched), or CF ₃ CH ₂ OCF ₂ CHF ₂ (for example, Asahiklin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.)), etc. These solvents can be used alone or as a mixture of two or more kinds. Among them, hydrofluoroethers are preferred, and perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) and/or perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) are particularly preferred.

When using the dry coating method, the surface treatment agent of the present disclosure can be used directly in the dry coating method, or can be used in the dry coating method after being diluted with the above solvent.

The layer formation of the surface treatment agent is preferably carried out in such a manner that the surface treatment agent of the present disclosure and the catalyst for hydrolysis and dehydration condensation coexist in the layer. To put it simply, when the wet coating method is used, after diluting the surface treatment agent of the present disclosure with a solvent, a catalyst can be added to the diluted liquid of the surface treatment agent of the present disclosure when it is about to be applied to the surface of the substrate. When carried out by the dry coating method, the surface treatment agent disclosed in the disclosure with a catalyst added can be directly evaporated (usually vacuum evaporation), or the surface treatment agent disclosed in the disclosure added with a catalyst can be used. It is impregnated into a porous metal such as iron or copper to form a granular substance, and the granular substance is used to perform evaporation (usually vacuum evaporation) processing.

Any suitable acid or alkali can be used as the catalyst. As the acid catalyst, for example, acetic acid, formic acid, trifluoroacetic acid, etc. can be used. In addition, ammonia, organic amines, etc. can be used as an alkali catalyst, for example.

Articles of the present disclosure contain surface treatments that provide high wear durability. Furthermore, in addition to high abrasion durability, the above-mentioned surface treatment layer may also have water repellency, oil repellency, and antifouling properties (for example, preventing the adhesion of dirt such as fingerprints) depending on the composition of the surface treatment agent used. ), waterproofing (preventing water from penetrating into electronic parts, etc.), surface smoothness (or lubricity, such as the ability to remove dirt such as fingerprints, or excellent touch to fingers), drug resistance, etc., It is suitable for use as a functional film.

Therefore, the present disclosure further relates to optical materials having the above-mentioned surface treatment layer on the outermost layer.

In addition to the optical materials related to displays and the like exemplified below, the optical materials are preferably various optical materials: for example, cathode ray tubes (CRT; for example, computer monitors), liquid crystal displays, plasma displays, and organic EL displays. , inorganic thin film EL dot matrix display, rear projection display, vacuum fluorescent display (VFD; Vacuum Fluorescent Display), field emission display (FED; Field Emission Display) and other displays or the protective plates of such displays, or in such displays Those with anti-reflective film treatment on the surface.

The object of the present disclosure is not particularly limited and may be an optical component. Examples of optical components include the following: lenses such as glasses; front protective plates, anti-reflective plates, polarizing plates, and anti-glare plates for displays such as PDP and LCD; touch panels for mobile phones, portable information terminals, and other equipment; The disc surface of Blu-ray (registered trademark) discs, DVD discs, CD-R, MO and other optical discs; optical fiber; the display surface of clocks, etc.

Furthermore, the items disclosed herein may be medical machines or medical materials. Furthermore, the article having the layer obtained by the present disclosure may also be an interior or exterior component of a car. Examples of exterior components The following can be listed: car windows, headlight covers, exterior lens covers. Examples of interior components include the following: instrument panel covers, navigation system touch panels, and decorative interior components.

The thickness of the above layer is not particularly limited. In the case of optical components, from the viewpoint of optical performance, abrasion durability and antifouling properties, the thickness of the above layer is preferably in the range of 1 to 50 nm, 1 to 30 nm, and more preferably in the range of 1 to 15 nm.

The items disclosed herein have been described in detail above. However, the articles and methods of manufacturing the articles disclosed herein are not limited to the above examples.

[Example]

In the following, the compounds of the present disclosure will be described in Examples, but the present disclosure is not limited to the following Examples. In this embodiment, the order of the repeating units constituting the fluoropolyether is arbitrary, and the chemical formula shown below represents the average composition.

Synthesis example 1

10.0g of perfluoropolyether modified ester body represented by the average composition CH ₃ OCOCF ₂ O(CF ₂ O) ₁₂ (CF ₂ CF ₂ O) ₁₂ CF ₂ COOCH ₃ , 1,3-bis(trifluoromethyl 5.0 g of benzene and 0.20 g of diethylenetriamine were put into a 100 mL three-neck flask equipped with a reflux cooler, a thermometer and a stirrer, and stirred at 25°C for 1 hour under nitrogen flow. Next, after adding 0.68 g of 3-aminopropyltrimethoxysilane, the mixture was stirred at 25° C. for 1 hour. Then, the volatile matter is distilled off under reduced pressure, thereby obtaining the perfluoropolyether group-containing silane compound (A) represented by the following formula.

(CH ₃ O) 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 NHCH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Synthesis example 2

10.0 g of the perfluoropolyether group-containing silane compound (A) obtained in Synthesis Example 1 and 0.27 g of 2-ethyl acrylate (Karenz (registered trademark) AOI manufactured by Showa Denko Co., Ltd.) were added to A 100 mL three-neck flask equipped with a reflux cooler, a thermometer and a stirrer was stirred at 25° C. for 1 hour under a nitrogen flow to obtain a perfluoropolyether group-containing silane compound (B) represented by the following formula.

(CH ₃ O) 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 N(X)CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

-X=-CONHCH ₂ CH ₂ OCOCH=CH ₂

Synthesis example 3

10.0 g of the perfluoropolyether group-containing silane compound (A) obtained in Synthesis Example 1 and 1,1-(bisacrylyloxymethyl)ethyl isocyanate (Karenz (manufactured by Showa Denko Co., Ltd.) Registered trademark) BEI) 0.46g was put into a 100mL three-neck flask equipped with a reflux cooler, a thermometer and a stirrer, and stirred at 25°C for 1 hour under a nitrogen flow to obtain a perfluoropolyether group-containing compound represented by the following formula Silane compound (C).

(CH ₃ O) 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 N(X)CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

-X=-CONHC(CH ₃ )(CH ₂ OCOCH=CH ₂ ) ₂

Synthesis example 4

10.0g of perfluoropolyether modified ester body represented by the average composition CH ₃ OCOCF ₂ O(CF ₂ O) ₁₂ (CF ₂ CF ₂ O) ₁₂ CF ₂ COOCH ₃ , 1,3-bis(trifluoromethyl 5.0 g of benzene and 0.28 g of triethylenetetramine were put into a 100 mL three-neck flask equipped with a reflux cooler, a thermometer and a stirrer, and stirred at 25°C for 1 hour under nitrogen flow. Next, 0.68 g of 3-aminopropyltrimethoxysilane was added, and the mixture was stirred at 25° C. for 1 hour. Then, the volatile components are distilled off under reduced pressure, thereby obtaining the perfluoropolyether group-containing silane compound (D) represented by the following formula.

(CH ₃ O) 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 NHCH 2 CH 2} NHCH ₂ CH _{2 NHCOCF 2} O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Synthesis example 5

10.0 g of the perfluoropolyether group-containing silane compound (D) obtained in Synthesis Example 4 and 0.54 g of 2-ethyl acrylate (Karenz (registered trademark) AOI manufactured by Showa Denko Co., Ltd.) were added to A 100 mL three-neck flask equipped with a reflux cooler, a thermometer and a stirrer was stirred at 25° C. for 1 hour under a nitrogen flow to obtain a perfluoropolyether group-containing silane compound (E) represented by the following formula.

(CH ₃ O) 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 N(X)CH ₂ CH ₂ N(X)CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

-X=-CONHCH ₂ CH ₂ OCOCH=CH ₂

Synthesis example 6

The average composition will be CH ₃ OCOCF(CF ₃ ){OCF ₂ CF(CF ₃ )} _m OCF ₂ CF ₂ O{CF(CF ₃ )CF ₂ O} _n CF(CF ₃ )COOCH ₃ (m+n≒34 ), 10.0g of the perfluoropolyether modified ester body, 5.0g of hexafluorobenzene and 0.085g of diethylenetriamine represented by Stir at 70°C for 13 hours. Next, after adding 0.29 g of 3-aminopropyltrimethoxysilane, the mixture was stirred at 70° C. for 12 hours. Then, the volatile components are distilled off under reduced pressure, thereby obtaining the perfluoropolyether group-containing silane compound (F) represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCF(CF ₃ ){OCF ₂ CF(CF ₃ )} _m OCF ₂ CF ₂ O{CF(CF ₃ )CF ₂ O} _n CF(CF ₃ )CONHCH ₂ CH ₂ NHCH ₂ CH ₂ NHCOCF(CF ₃ ){OCF ₂ CF(CF ₃ )} _m OCF ₂ CF ₂ O{CF(CF ₃ )CF ₂ O} _n CF(CF ₃ )CONHCH ₂ CH ₂ CH ₂ Si( OCH ₃ ) ₃

Synthesis Example 7

10.0 g of the perfluoropolyether group-containing silane compound (F) obtained in Synthesis Example 6 and 0.12 g of 2-ethyl acrylate (Karenz (registered trademark) AOI manufactured by Showa Denko Co., Ltd.) were added to A 100 mL three-neck flask equipped with a reflux cooler, a thermometer and a stirrer was stirred at 25° C. for 1 hour under a nitrogen flow to obtain a perfluoropolyether group-containing silane compound (G) represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCF(CF ₃ ){OCF ₂ CF(CF ₃ )} _m OCF ₂ CF ₂ O{CF(CF ₃ )CF ₂ O} _n CF(CF ₃ )CONHCH ₂ CH ₂ N(X)CH ₂ CH ₂ NHCOCF(CF ₃ ){OCF ₂ CF(CF ₃ )} _m OCF ₂ CF ₂ O{CF(CF ₃ )CF ₂ O} _n CF(CF ₃ )CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

-X=-CONHCH ₂ CH ₂ OCOCH=CH ₂

Synthesis example 8

10.0 g of the perfluoropolyether group-containing silane compound (A) obtained in Synthesis Example 1 and 0.38 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE manufactured by Mitsubishi Chemical Co., Ltd.) were put into a reflux cooling device. A 100 mL three-neck flask was equipped with a thermometer, a thermometer, and a stirrer, and stirred at 50°C for 3 hours under a nitrogen flow to obtain a perfluoropolyether group-containing silane compound (H) represented by the following formula.

(CH ₃ O) 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 N(X)CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

-X is a mixture of the following -X ¹ and -X ² (X ¹ : X ² =80: 20)

-X ¹ =-CH ₂ CH(OH)CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCOCH=CH ₂

-X ² =-CH(CH ₂ OH)CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCOCH=CH ₂

Synthesis example 9

10.0g of perfluoropolyether modified ester body represented by the average composition CH ₃ OCOCF ₂ O(CF ₂ O) ₁₂ (CF ₂ CF ₂ O) ₁₂ CF ₂ COOCH ₃ , 1,3-bis(trifluoromethyl 5.0 g of benzene and 0.20 g of 1,3-diamino-2-propanol were put into a 100 mL three-neck flask equipped with a reflux cooler, a thermometer and a stirrer, and stirred at 25°C for 1 hour under nitrogen flow. Next, 0.68 g of 3-aminopropyltrimethoxysilane was added, and the mixture was stirred at 25° C. for 1 hour. Then, the volatile components are distilled off under reduced pressure, thereby obtaining the perfluoropolyether group-containing silane compound (I) represented by the following formula.

(CH ₃ O) 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(OH)CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Synthesis example 10

10.0 g of the perfluoropolyether group-containing silane compound (I) obtained in Synthesis Example 9, 0.27 g of 2-isocyanate ethyl acrylate (Karenz (registered trademark) AOI manufactured by Showa Denko Co., Ltd.) and laurel 0.012g of dibutyltin acid was put into a 100mL three-neck flask equipped with a reflux cooler, a thermometer and a stirrer, and stirred at 50°C for 2 hours under a nitrogen flow to obtain a perfluoropolyether group-containing silane represented by the following formula Compound (J).

(CH ₃ O) 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(OX)CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

-X=-CONHCH ₂ CH ₂ OCOCH=CH ₂

Synthesis Example 11

10.0g of perfluoropolyether modified ester body represented by the average composition CH ₃ OCOCF ₂ O(CF ₂ O) ₁₂ (CF ₂ CF ₂ O) ₁₂ CF ₂ COOCH ₃ , 1,3-bis(trifluoromethyl 5.0 g of benzene and 0.20 g of diethylenetriamine were put into a 100 mL three-neck flask equipped with a reflux cooler, a thermometer and a stirrer, and stirred at 25°C for 1 hour under nitrogen flow. Next, after adding 0.85 g of 3-(2-aminoethylamino)propyltrimethoxysilane, the mixture was stirred at 25° C. for 1 hour. Then, the volatile matter is distilled off under reduced pressure, thereby obtaining a perfluoropolyether group-containing silane compound (K) 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) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH 2 NHCH ₂ CH ₂ NHCOCF ₂ O( _{CF 2 CF 2} O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Synthesis example 12

10.0 g of the perfluoropolyether group-containing silane compound (K) obtained in Synthesis Example 11 and 0.81 g of 2-ethyl acrylate (Karenz (registered trademark) AOI manufactured by Showa Denko Co., Ltd.) were added to A 100 mL three-neck flask equipped with a reflux cooler, a thermometer and a stirrer was stirred at 25° C. for 2 hours under a nitrogen flow to obtain a perfluoropolyether group-containing silane compound (L) 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) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ N(X)CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ 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

Synthesis example 13

10.0g of perfluoropolyether modified ester body represented by the average composition CH ₃ OCOCF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₁₆ CF ₂ CF ₂ COOCH ₃ , 1,3-bis(trifluoromethyl 5.0g of benzene and 0.17g of diethylenetriamine were put into a 100mL three-neck flask equipped with a reflux cooler, a thermometer and a stirrer, and stirred at 25°C for 1 hour under nitrogen flow. Next, after adding 0.60 g of 3-aminopropyltrimethoxysilane, the mixture was stirred at 25° C. for 1 hour. Then, the volatile matter is distilled off under reduced pressure, thereby obtaining a perfluoropolyether group-containing silane compound (M) represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCF ₂ CF ₂ O(CF ₂ CF ₂ CF ₂ O) ₁₆ CF ₂ CF ₂ CONHCH ₂ CH ₂ NHCH ₂ CH ₂ NHCOCF ₂ CF ₂ O(CF ₂ CF ₂ CF ₂ O) ₁₆ CF ₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Synthesis Example 14

10.0 g of the perfluoropolyether group-containing silane compound (M) obtained in Synthesis Example 13 and 0.24 g of 2-ethyl acrylate (Karenz (registered trademark) AOI manufactured by Showa Denko Co., Ltd.) were added to A 100 mL three-neck flask equipped with a reflux cooler, a thermometer and a stirrer was stirred at 25° C. for 1 hour under a nitrogen flow to obtain a perfluoropolyether group-containing silane compound (N) represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCF ₂ CF ₂ O(CF ₂ CF ₂ CF ₂ O) ₁₆ CF ₂ CF ₂ CONHCH ₂ CH ₂ N(X)CH ₂ CH ₂ NHCOCF ₂ CF ₂ O(CF ₂ CF ₂ CF ₂ O) ₁₆ CF ₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

-X=-CONHCH ₂ CH ₂ OCOCH=CH ₂

Example 1

The compound (B) obtained in the above Synthesis Example 2 was dissolved in Novec 7200 (manufactured by 3M Company) so that the concentration became 20 wt%, and a surface treatment agent was prepared.

The surface treatment agents prepared above were each vacuum evaporated on chemically strengthened glass ("Gorilla" glass manufactured by Corning Co., Ltd., thickness 0.7 mm). The conditions for the vacuum evaporation method: the resistance heating evaporation machine processing chamber size is 1,900mmφ, the vacuum degree is 5.0E-05, the current value is 240A, the voltage is 10V, and the substrate temperature is 40°C. Next, the evaporated chemically strengthened glass was left to stand in an environment with a temperature of 150° C. for 30 minutes, and then left to cool to room temperature. Then, in an air environment, light containing 365nm UV light is irradiated on the evaporated chemically strengthened glass at an intensity of 1000mJ/cm ² to form a surface treatment layer on the glass substrate.

Example 2

The surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1 except that the compound (C) obtained in the above Synthesis Example 3 was used instead of the compound (B).

Example 3

The surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1 except that the compound (E) obtained in Synthesis Example 5 was used instead of the compound (B).

Example 4

The surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1 except that the compound (G) obtained in Synthesis Example 7 was used instead of the compound (B).

Example 5

The surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1 except that the compound (H) obtained in the above-mentioned Synthesis Example 8 was used instead of the compound (B).

Example 6

The surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1 except that the compound (J) obtained in the above-mentioned Synthesis Example 10 was used instead of the compound (B).

Example 7

The surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1 except that the compound (L) obtained in Synthesis Example 12 was used instead of the compound (B).

Example 8

The surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1 except that the compound (N) obtained in Synthesis Example 14 was used instead of the compound (B).

Comparative example 1

The following compound (O) was dissolved in Novec 7200 (manufactured by 3M Company) so that the concentration became 20 wt%, and a surface treatment agent was prepared.

(CH ₃ O) 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 CH ₂ Si(OCH ₃ ) ₃

The surface treatment agents prepared above were each vacuum evaporated on chemically strengthened glass ("Gorilla" glass manufactured by Corning Co., Ltd., thickness 0.7 mm). The conditions for the vacuum evaporation method: the resistance heating evaporation machine processing chamber size is 1,900mmφ, the vacuum degree is 5.0E-05, the current value is 240A, the voltage is 10V, and the substrate temperature is 40°C. Then, the evaporated chemically strengthened glass is left to stand in an environment with a temperature of 150° C. for 30 minutes, and then left to cool to room temperature to form a surface treatment layer on the glass substrate.

Comparative example 2

Except that the following compound (P) was used instead of the compound (O), the same procedure as in Comparative Example 1 was performed to prepare a surface treatment agent and form a surface treatment layer.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCF ₂ CF ₂ O(CF ₂ CF ₂ CF ₂ O) ₁₆ CF ₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Comparative example 3

The surface treatment agent was prepared in the same manner as Comparative Example 1 except that the following compound (Q) was used instead of the compound (O), and a surface treatment layer was formed.

(CH ₃ O) 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 CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Comparative example 4

The surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Comparative Example 1 except that the following compound (R) was used instead of the compound (O).

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCF(CF ₃ ){OCF ₂ CF(CF ₃ )} _m OCF ₂ CF ₂ O{CF(CF ₃ )CF ₂ O} _n CF(CF ₃ )CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

<evaluate>

For the glass substrate with a surface treatment layer obtained above, the water contact angle was measured and the alkali test was evaluated in the following manner.

(alkali immersion test)

An O-ring made of PTFE with a diameter of 1 cm was placed on the surface of the surface-treated base material of Examples 1 to 8 and Comparative Examples 1 to 4, and an 8N NaOH solution (alkali aqueous solution) was dropped into the O-ring. The ring is used in the alkali immersion test to bring the surface of the surface treatment layer into contact with the alkali aqueous solution. After the alkali immersion test has elapsed for 20 to 300 minutes, the alkali aqueous solution is wiped off and washed with pure water and ethanol, and then the contact angle with respect to water is measured. The static contact angle of water is such that 2 μL of pure water Water was dropped onto the surface of the glass substrate after the alkali immersion test, and the contact angle with respect to water was measured using a contact angle meter (automatic contact angle meter DropMaster 701 manufactured by Kyowa Interface Chemical Co., Ltd.). The static contact angle of water after the alkali immersion test was measured at 5 locations. When the measured value of the static contact angle of water decreases within 300 minutes, the alkali immersion test is stopped midway. The relationship between the immersion time and the average contact angle at 5 locations is shown in the table below.

[Table 1]

(Abrasion durability test)

Arrange the sample article with the surface treatment layer horizontally, place the following friction member in contact with the surface of the surface treatment layer (the contact surface is a circle with a diameter of 1 cm), apply a load of 5N on top of it, and then apply the load to The friction part travels back and forth at a speed of 40mm/second. The friction member is allowed to travel back and forth a maximum of 4,000 times, and the static contact angle (°) of water is measured every 1,000 times (number of frictions). Stop the test when the measured value of the static contact angle of water does not reach 60°. The static contact angle of water was measured in the same manner as the above-mentioned alkali test. The results are shown in the following table.

˙Friction parts

The surface (diameter 1cm) of the silicone rubber processed product shown below is covered with cotton cloth soaked in artificial perspiration of the composition shown below and used as a friction member.

The composition of artificial sweat:

Anhydrous disodium hydrogen phosphate: 2g

Sodium chloride: 20g

85% lactic acid: 2g

Histamine hydrochloride: 5g

Distilled water: 1Kg.

Polysilicone rubber processed products:

Polysilicone rubber plug SR-51 manufactured by Tigers Polymer Co., Ltd. was processed into a cylindrical shape with a diameter of 1 cm and a thickness of 1 cm.

[Table 2]

[Industrial applicability]

The fluoropolyether-based acrylic compound disclosed in the present disclosure is suitable for use to form a surface treatment layer on the surface of various substrates, especially optical components requiring abrasion durability.

Claims (32)

A compound represented by the following formula (1), R ^b ₂ NR ^d -CO-(R ^F2 -CO-NR ^c -R ^a (R ^Ac _m )-NR ^c -CO) _x -R ^F2 -CO-R ^d -NR ^b ₂ (1) In the formula, R ^F2 are independently -Rf ² _p -R ^F -O _q -, Rf ² is a C _1-6 alkylene group which may be substituted by more than one fluorine atom, R ^F is a divalent fluoropolyether group, p is 0 or 1, q is 0 or 1, R ^a are independently (m+2)-valent organic groups, m is an integer from 1 to 4, R ^b is independently R ^Si , R ^Ac or R ^c , R ^Si are independently -X ^C -SiR ¹ _n' R ² _3-n' , X ^C is a divalent organic group with 1 to 10 carbon atoms, R ¹ are each independently a hydroxyl group or a hydrolyzable group, R ² is independently a hydrogen atom or a monovalent organic group, n’ is an integer from 1 to 3, R ^Ac are each independently -X ^D -X ^E (-X ^F -OCO-CR ⁵ =CH ₂ ) _m' , X ^D is a divalent organic radical, X ^E is a single bond or (m'+1) valence base, X ^F are each independently a divalent organic group having 1 to 10 carbon atoms, R ⁵ is a hydrogen atom or a monovalent organic group with 1 to 8 carbon atoms, m’ is an integer from 1 to 10, R ^c are each independently a hydrogen atom or a C _1-6 alkyl group, R ^d are independently single bonds or divalent organic groups, x is an integer above 1. The compound as claimed in claim 1, 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 of existence of each repeating unit enclosed in parentheses is arbitrary in the formula, but when all R ^Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1 or more. The compound according to claim 1 or 2, wherein R ^Fa is a fluorine atom. The compound according to any one of claims 1 to 3, wherein R ^F is independently represented by the following formula (f1), (f2), (f3), (f4), (f5) or (f6) The basis of expression, -(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 an integer from 0 to 2. The order of existence of each repeating unit marked with the subscript d or e and enclosed in brackets is arbitrary in the formula; -(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 existence of each repeating unit marked with the subscript c, d, e or f and enclosed in parentheses is arbitrary in the formula; -(R ⁶ -R ⁷ ) _g -R ⁹ - (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, R ⁹ is a single bond, or a group selected from OCF ₂ , OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , 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 as shown in the following chemical formula,

In the formula, * represents 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, the sum of a, b, c, d, e and f is at least 1, and then Otherwise, the order of existence of each repeating unit marked a, b, c, d, e or f and enclosed in parentheses 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, the sum of a, b, c, d, e and f is at least 1, and then Otherwise, the order of existence of each repeating unit marked a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula. The compound according to any one of claims 1 to 4, wherein ^RF2 is independently a C _1-6 perfluoroalkyl group. The compound according to any one of claims 1 to 5, wherein R ^a is 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 each independently a trivalent organic group, k is an integer from 1 to 4. The compound according to claim 6, wherein R ^a' is independently a trivalent organic group containing an N atom or an O atom. The compound as claimed in claim 6, wherein R ^a' can independently contain an amine bond, an amide bond, a urethane bond, a urea bond, an ether bond or an ester bond between carbon-carbon atoms. 3-valent organic base. The compound according to any one of claims 6 to 8, wherein R ^a' is each independently the following group,

In the formula, R ⁸ is a hydrogen atom or a C _1-6 alkyl group. The compound according to any one of claims 6 to 9, wherein R ^a' is N. The compound according to any one of claims 6 to 10, wherein k is 1. The compound according to any one of claims 6 to 10, wherein k is 2. The compound according to any one of claims 1 to 12, wherein at least one R ^b is R ^Si . The compound according to any one of claims 1 to 13, wherein one of the R ^b 's bonded to the N atom at each terminal is R ^Si and the others are R ^c . The compound according to any one of claims 1 to 13, wherein one of the R ^b 's bonded to the N atom at each terminal is R ^Si and the others are R ^Ac . The compound as described in any one of claims 1 to 15, wherein X ^C is: C _1-6 alkylene group, -(CH ₂ ) _z1 -O-(CH ₂ ) _z2 -(where 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, and z4 is an integer from 0 to 6). The compound according to any one of claims 1 to 16, wherein X ^C is C _1-6 alkylene group. The compound according to any one of claims 1 to 17, wherein n' is 2 or 3. The compound according to any one of claims 1 to 18, wherein n' is 3. The compound according to any one of claims 1 to 19, wherein X ^D is -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -OCONH-, -NHCOO -, -NH-CO-NH-, -CH ₂ CH(OH)CH ₂ - or -CH(CH ₂ OH)CH ₂ -. The compound according to any one of claims 1 to 20, wherein X ^D is -CONH-, -CH ₂ CH(OH)CH ₂ - or -CH(CH ₂ OH)CH ₂ -. The compound according to any one of claims 1 to 21, wherein X ^D is -CONH-. The compound according to any one of claims 1 to 22, wherein X ^E is a single bond. The compound according to any one of claims 1 to 23, wherein, X ^E is -X ^G -X ^H ; X ^G is: single key, C _1-6 alkylene group, -(CH ₂ ) _z9 -O-(CH ₂ ) _z10 -(where 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 shown in the following chemical formula,

R ⁸ is a hydrogen atom or a C _1-6 alkyl group. The compound as described in any one of claims 1 to 24, wherein X ^F is: C _1-6 alkylene group, -(CH ₂ ) _z5 -O-(CH ₂ ) _z6 -(where 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, and z8 is an integer from 0 to 6). The compound according to any one of claims 1 to 25, wherein R ^c is independently a hydrogen atom or a C _1-6 alkyl group. The compound according to any one of claims 1 to 26, 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 compound according to any one of claims 1 to 27, wherein x is an integer from 1 to 5. A surface treatment agent containing the compound described in any one of claims 1 to 28. The surface treatment agent as described in claim 29 further contains one or more other components selected from the group consisting of fluorine-containing oil, polysiloxane oil and catalyst. The surface treatment agent according to claim 29 or 30 is used as an antifouling coating agent or a waterproof coating agent. An article comprising a base material and a layer formed on the surface of the base material from the compound described in any one of claims 1 to 28 or the surface treatment agent described in any one of claims 29 to 31.