KR20240054382A - surface treatment agent - Google Patents

Abstract

The present invention relates to a compound represented by the following formula (1) or (2) (wherein each symbol has the same meaning as described in the specification).

Description

surface treatment agent

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

It is known that certain types of fluoropolyether group-containing silane compounds can provide excellent water repellency, oil repellency, antifouling properties, etc. when used for surface treatment of substrates. The layer obtained from a surface treatment agent containing a fluoropolyether group-containing silane compound (hereinafter also referred to as “surface treatment layer”) is a so-called functional thin film, which is used for various applications such as glass, plastic, fiber, sanitary products, and building materials. It has been implemented on various substrates (Patent Document 1).

Japanese Patent Publication No. 2003-238577

The fluoropolyether group-containing silane compound described in Patent Document 1 can provide a surface treatment layer with excellent function, but a surface treatment layer with higher durability is required.

The purpose of the present disclosure is to provide a fluoropolyether group-containing compound capable of providing a highly durable surface treatment layer.

This disclosure includes the following aspects.

[1] Equation (1) or (2) below:

[Formula:

R ^F1 is Rf ¹ -R ^F -O _q -,

R ^F2 is -Rf ² _p -R ^F -O _q -,

Rf ¹ is a C _1-16 alkyl group which may be substituted with one or more fluorine atoms,

Rf ² is a C _1-6 alkylene group which may be substituted with one or more fluorine atoms,

R ^F is each independently a divalent fluoropolyether group,

p is 0 or 1,

q is each independently 0 or 1,

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

^Each of

R ^Si is independently -X ^C -SiR ¹ _n' R ² _3-n' in each occurrence,

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

R ¹ is independently a hydroxyl group or a hydrolyzable group in each occurrence,

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

n' is an integer from 1 to 3,

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

X ^D is a single bond or a divalent organic group,

X ^E is a single bond or (m'+1) valent group,

X ^F , in each occurrence, is independently a single bond or a divalent organic group having 1 to 10 carbon atoms,

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

m' is an integer from 1 to 10,

n is each independently an integer from 1 to 10,

m is each independently an integer from 1 to 10]

Compounds represented by .

[2] R ^F is independently for each occurrence, in the equation:

-(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 is independently a hydrogen atom, a fluorine atom, or a chlorine atom in each occurrence,

a, b, c, d, e and f are each independently an integer from 0 to 200, and the sum of a, b, c, d, e and f is 1 or more, and a, b, c, d, The order of existence of each repeating unit enclosed in parentheses by adding e or f is arbitrary in the formula, provided that when all R ^Fa is a hydrogen atom or a chlorine atom, at least one of a, b, c, e and f is, [is more than 1]

The compound described in [1] above, which is a group represented by .

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

[4] R ^F , in each occurrence, is independently represented by the following formula (f1), (f2), (f3), (f4), (f5) or (f6):

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

[Wherein, d is an integer from 1 to 200, and e is 0 or 1],

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

[Wherein, c and d are each independently an integer of 0 to 30;

e and f are each independently an integer 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 enclosed in parentheses with the subscript c, d, e or f is arbitrary in the formula],

-(R ⁶ -R ⁷ ) _g -R ⁹ - (f3)

[Wherein, 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)

[Wherein, 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 and

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 two or three groups independently selected from these groups. It is a combination,

g is an integer from 2 to 100,

g' is an integer from 2 to 100,

R ^r is,

(In the formula, * indicates the binding position)

lim];

-(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 between 1 and 200, and a, b, c, d, and f are each independently integers between 0 and 200, and is the sum of a, b, c, d, e, and f. is at least 1, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f 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 between 1 and 200, and a, b, c, d, and e are each independently integers between 0 and 200, and is the sum of a, b, c, d, e, and f. is at least 1, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in the formula]

The compound according to any one of [1] to [3] above, which is a group represented by .

[5] Rf ¹ is independently a C _1-16 perfluoroalkyl group in each occurrence,

The compound according to any one of [1] to [4] above, wherein each occurrence of Rf ² is independently a C _1-6 perfluoroalkylene group.

[6] The compound according to any one of [1] to [5] above, wherein X ^A is each independently a single bond or a divalent organic group not containing a urethane bond.

[7] X ^A is, each independently, a single bond, or

-(C _α R ¹¹ _2α ) _s1 -R ¹² _t1 -

[Formula:

R ¹¹ is independently a hydrogen atom or a fluorine atom in each occurrence,

α is an integer from 1 to 10, independently for each occurrence,

R ¹² is, in each occurrence, independently -O-, -CO-, -NR ¹⁰ -, -CONR ¹⁰ -, -NR ¹⁰ CO-, -COO-, or -OCO-,

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

s1 is an integer from 0 to 3,

t1 is an integer from 0 to 3,

The sum of s1 and t1 is 1 or more,

The order of existence of each repeating unit enclosed in parentheses with s1 or t1 is arbitrary in the equation]

The compound according to any one of [1] to [6] above, which is a group represented by .

_[ ^{8 ]} _{​ ​ ​ ​ ​ ​ ​}

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

α1 is an integer from 1 to 10,

α2 is an integer from 0 to 6,

α3 is an integer from 0 to 6,

The compound described in [7] above, where α4 is an integer from 0 to 6.

[9] X ^A is -CONR ¹⁰ -C _α1 H _2α1 - The compound described in [8] above.

[10] The compound according to any one of [1] to [9] above, wherein X ^B is a trivalent group, n is 1, and m is 1.

[11 ^]

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

, n is 1, and m is 1. The compound according to any one of [1] to [10] above.

[ ¹² ]

C _1-6 alkylene group,

-(CH ₂ ) _z1 -O-(CH ₂ ) _z2 - (wherein, z1 is an integer from 0 to 6, and z2 is an integer from 0 to 6),

-(CH ₂ ) _z3 -phenylene-(CH ₂ ) _z4 - (wherein, z3 is an integer of 0 to 6, and z4 is an integer of 0 to 6), or

-(CH ₂ ) _z13 -OCONH-(CH ₂ ) _z14 - (wherein, z13 is an integer from 0 to 6, and z14 is an integer from 0 to 6), any of the above [1] to [11] Compounds described in paragraph one.

[13] The compound according to any one of [1] to [12] above, wherein X ^C is a C _1-6 alkylene group.

[14] The compound according to any one of [1] to [13] above, wherein n' is 2 or 3.

[15] The compound according to any one of [1] to [14] above, wherein n' is 3.

[16] The compound according to any one of [1] to [15] above, wherein X ^E is a single bond.

[17] X ^E is -X ^G -X ^H ,

X ^G is,

single bond,

C _1-6 alkylene group,

-(CH ₂ ) _z9 -O-(CH ₂ ) _z10 - (wherein, z9 is an integer from 0 to 6, and z10 is an integer from 0 to 6), or,

-(CH ₂ ) _z11 -phenylene-(CH ₂ ) _z12 - (wherein, z11 is an integer of 0 to 6, and z12 is an integer of 0 to 6)

and

X ^H is

and

The compound according to any one of [1] to [15] above, wherein R ⁸ is a hydrogen atom or a C _1-6 alkyl group.

[ ¹⁸ _] CH(OH)CH ₂ -, -CH(CH ₂ OH)CH ₂ -,

The compound according to any one of [1] to [17] above, wherein * and ** represent the binding position, * is bonded to X ^B , and ** is bonded ^to

[ ¹⁹ ]

single bond,

C _1-6 alkylene group,

-(CH ₂ ) _z5 -O-(CH ₂ ) _z6 - (wherein, z5 is an integer from 0 to 6, and z6 is an integer from 0 to 6), or,

-(CH ₂ ) _z7 -phenylene-(CH ₂ ) _z8 - (wherein, z7 is an integer of 0 to 6, and z8 is an integer of 0 to 6) in [1] to [18] above. The compound according to any one of the preceding paragraphs.

[20] The compound according to any one of [1] to [19] above, wherein R ⁵ is a hydrogen atom or a methyl group.

[21] A surface treatment agent containing the compound according to any one of [1] to [20] above.

[22] The surface treatment agent according to [21] above, further containing one or more other components selected from fluorine-containing oil, silicone oil, and catalyst.

[23] The surface treatment agent according to [21] or [22] above, which is used as an antifouling coating agent or a waterproof coating agent.

[24] Comprising a substrate and a layer formed on the surface of the substrate with the compound according to any one of [1] to [19] above or the surface treatment agent according to any one of [21] to [23] above. article.

According to the present disclosure, it is possible to provide an acrylic compound containing a fluoropolyether group that can provide a surface treatment layer with excellent durability.

As used herein, “monovalent organic group” means a monovalent group containing carbon. The monovalent organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. A derivative of a hydrocarbon group refers to a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the end of the hydrocarbon group or in the molecular chain. Additionally, when simply expressed as “organic group”, it means a monovalent organic group. Additionally, “divalent organic group” means a divalent group containing carbon. Such a divalent organic group is not particularly limited, but includes a divalent group in which one hydrogen atom is further removed from the organic group.

As used in this specification, “hydrocarbon group” refers to a group containing carbon and hydrogen, and means a group in which one hydrogen atom is removed from a hydrocarbon. Such hydrocarbon groups are not particularly limited, but include C _1-20 hydrocarbon groups that may be substituted with one or more substituents, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The “aliphatic hydrocarbon group” may be linear, branched, or cyclic, and may be saturated or unsaturated. Additionally, the hydrocarbon group may contain one or more ring structures.

When used in this specification, the substituent for the “hydrocarbon group” is not particularly limited, but includes, for example, a halogen atom, a C _1-6 alkyl group which may be substituted with one or more halogen atoms, and C _{2 -6} alkenyl group, C _2-6 alkynyl group, C _3-10 cycloalkyl group, C _3-10 unsaturated cycloalkyl group, 5 to 10 membered heterocyclyl group, 5 to 10 membered unsaturated heterocyclyl group, C _6- One or more groups selected from _10- membered aryl groups and 5- to 10-membered heteroaryl groups can be mentioned.

When used in this specification, “hydrolyzable group” means a group that can undergo a hydrolysis reaction, that is, a group that can be separated from the main skeleton of the compound through a hydrolysis reaction. Examples of hydrolyzable groups include -OR ^h , -OCOR ^h , -ON=CR ^h ₂ , -NR ^h ₂ , -NHR ^h , -NCO, halogen (in these formulas, R ^h is substituted or unsubstituted C _{1- 4} represents an alkyl group), and the like.

The fluoropolyether group-containing acrylic compound of the present disclosure has the following formula (1) or (2):

[Formula:

R ^F1 is Rf ¹ -R ^F -O _q -,

R ^F2 is -Rf ² _p -R ^F -O _q -,

Rf ¹ is a C _1-16 alkyl group which may be substituted with one or more fluorine atoms,

Rf ² is a C _1-6 alkylene group which may be substituted with one or more fluorine atoms,

R ^F is each independently a divalent fluoropolyether group,

p is 0 or 1,

q is each independently 0 or 1,

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

^Each of

R ^Si is independently -X ^C -SiR ¹ _n' R ² _{3 -n'} in each occurrence,

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

R ¹ is independently a hydroxyl group or a hydrolyzable group in each occurrence,

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

n' is an integer from 1 to 3,

R ^Ac is, independently in each occurrence, -X ^D -X ^E (-X ^F -OCO-CR ⁵ =CH ₂ ) _{m '} ,

X ^D is a single bond or a divalent organic group,

X ^E is a single bond or (m'+1) valent group,

X ^F , in each occurrence, is independently a single bond or an organic group,

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

m' is an integer from 1 to 10,

n is each independently an integer from 1 to 10,

m is each independently an integer from 1 to 10]

It is an acrylic compound containing a fluoropolyether group, represented by .

In the above formula (1), R ^F1 is Rf ¹ -R ^F -O _q -.

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

In the above formula, Rf ¹ is a C _1-16 alkyl group which may be substituted with one or more fluorine atoms.

The "C _1-16 alkyl group" in the C _1-16 alkyl group which may be substituted by one or more fluorine atoms may be straight chain or branched, and is preferably straight chain or branched C _1- It is a ₆ -alkyl group, especially a C _1-3 alkyl group, and more preferably a straight-chain C _1-6 alkyl group, especially a C _1-3 alkyl group.

The Rf ¹ is preferably a C _1-16 alkyl group substituted with one or more fluorine atoms, more preferably a CF ₂ HC _1-15 perfluoroalkylene group, and even more preferably a C ₁ It is a _-16 perfluoroalkyl group.

The C _1-16 perfluoroalkyl group may be straight-chain or branched, and is preferably a straight-chain or branched C _1-6 perfluoroalkyl group, especially a C _1-3 perfluoroalkyl group, and more preferably is a straight-chain C _1-6 perfluoroalkyl group, especially a C _1-3 perfluoroalkyl group, specifically -CF ₃ , -CF ₂ CF ₃ , or -CF ₂ CF ₂ CF ₃ .

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

The "C _1-6 alkylene group" in the C _1-6 alkylene group which may be substituted by one or more fluorine atoms may be straight chain or branched, and is preferably straight chain or branched C. It is a _1-3 alkylene group, and more preferably a straight chain C _1-3 alkylene group.

The Rf ² is preferably a C _1-6 alkylene group substituted with one or more fluorine atoms, more preferably a C _1-6 perfluoroalkylene group, and even more preferably a C _{1-6 alkylene} group. ₃ It is a perfluoroalkylene group.

The C _1-6 perfluoroalkylene group may be straight-chain or branched, and is preferably a straight-chain or branched C _1-3 perfluoroalkylene group, and more preferably a straight-chain C _1-3 purple group. A luoroalkyl 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 another embodiment, p is 1.

In the above formula, q is each independently 0 or 1. In one aspect, q is 0. In another embodiment, q is 1.

In the above formulas (1) and (2), R ^F each independently represents a divalent fluoropolyether group in each occurrence.

R ^F is preferably:

-(OC _h1 R ^Fa _2h1 ) _h3 -(OC _h2 R ^Fa _2h2-2 ) _h4 -

[Formula:

R ^Fa is, in each occurrence, 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 greater than or equal to 0,

h4 is an integer greater than or equal to 0,

However, the composition of h3 and h4 is 1 or more, preferably 2 or more, more preferably 5 or more, and the order of existence of each repeating unit enclosed in parentheses with h3 and h4 is arbitrary in the formula.]

It may include a group represented by .

In one aspect, R ^F may be linear or branched. R ^F is preferably expressed by the formula:

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

[Formula:

R ^Fa is, in each occurrence, independently a hydrogen atom, a fluorine atom, or a chlorine atom,

a, b, c, d, e and f are each independently an integer from 0 to 200, and the sum of a, b, c, d, e and f is 1 or more. The order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f 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]

It is a group represented by .

R ^Fa is preferably a hydrogen atom or a fluorine atom, and 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.

a, b, c, d, e and f may each independently be an integer of 0 to 100.

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

These repeating units may be linear or branched, and may contain a ring structure. For example, -(OC ₆ F ₁₂ )- is -(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 ))-, -(OC ₅ F ₁₀ )- may 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. may 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(CF ₃ ))-, -(OCF(C ₂ F ₅ CF ₂ )-, and -(OCF ₂ CF(C ₂ F ₅ ))- may be any of -(OC ₃ F ₆ )-(i.e., in the above formula, R ^Fa is a fluorine atom) is -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ CF ₂ )- and -(OCF ₂ CF(CF ₃ )) - may be any of -(OC ₂ F ₄ )- may be either -(OCF ₂ CF ₂ )- and -(OCF(CF ₃ ))-.

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

The ring structure may be the following 3-membered ring, 4-membered ring, 5-membered ring, or 6-membered ring.

[In the formula, * represents the binding position.]

The ring structure may be preferably a 4-membered ring, a 5-membered ring, or a 6-membered ring, and more preferably a 4-membered ring or a 6-membered ring.

The repeating unit having a ring structure may preferably be the following unit.

[In the formula, * represents the binding position.]

In one aspect, the repeating unit is linear. By making the repeating units linear, the surface slipperiness and wear durability of the surface treatment layer can be improved.

In one aspect, the repeating unit is branched. By making the repeating unit branched, the kinetic friction coefficient of the surface treatment layer can be increased.

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

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

[Wherein, d is an integer from 1 to 200, and e is 0 or 1, preferably 1];

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

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

The sum of c, d, e and f is at least 2,

The order of existence of each repeating unit enclosed in parentheses with the subscript c, d, e or f is arbitrary in the formula];

-(R ⁶ -R ⁷ ) _g -R ⁹ - (f3)

[Wherein, 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 and

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)

[Wherein, 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 and

R ^6' is OCF ₂ or OC ₂ F ₄ ,

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

g is an integer from 2 to 100,

g' is an integer from 2 to 100,

R ^r is,

(In the formula, * indicates the binding position)

lim];

-(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, and a, b, c, d, and f are each independently integers from 0 to 200, and a, b, c, d, e or f The order of existence of each repeating unit enclosed in parentheses is arbitrary in the equation]

-(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, and a, b, c, d, and e are each independently integers from 0 to 200, and a, b, c, d, e or f The order of existence of each repeating unit enclosed in parentheses is arbitrary in the equation]

In the above formula (f1), d is an integer of preferably 5 to 200, more preferably 10 to 100, further preferably 15 to 50, for example 25 to 35. In one aspect, e is 1. In another aspect, e is 0. (OC ₃ F ₆ ) in the formula (f1) is preferably expressed as (OCF ₂ CF ₂ CF ₂ ), (OCF ₂ CF(CF ₃ )) or (OCF(CF ₃ )CF ₂ ). It is a group, and more preferably, it is a group represented by -(OCF ₂ CF ₂ CF ₂ ) _d -. (OC ₂ F ₄ ) in the formula (f1) is preferably a group represented by (OCF ₂ CF ₂ ) or (OCF(CF ₃ )), and more preferably (OCF ₂ CF _{2 )} . It is a group represented by ).

In the above formula (f2), e and f are each independently an integer of preferably 5 to 200, more preferably 10 to 200. Additionally, the sum of c, d, e, and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. In one aspect, the 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 ) It is a group represented by _f -. In another aspect, equation (f2) also has a contribution expressed as -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f -.

In the above formula (f3), R ⁶ is preferably OC ₂ F ₄ . In (f3) above, 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, it is a group selected from OC ₃ F ₆ and OC ₄ F ₈ . The combination of two or three groups independently selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ is not particularly limited, but includes, for example, -OC ₂ F ₄ OC ₃ F ₆ -, -OC ₂ F ₄ OC ₄ F ₈ -, -OC ₃ F ₆ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₃ F ₆ -, -OC ₃ F ₆ OC ₄ F ₈ -, -OC ₄ F ₈ OC ₄ F ₈ -, -OC ₄ F ₈ OC ₃ F ₆ -, -OC ₄ F ₈ OC ₂ F ₄ -, -OC ₂ F ₄ OC ₂ F ₄ OC ₃ F ₆ -, -OC ₂ F ₄ OC ₂ F ₄ OC ₄ F ₈ -, -OC ₂ F ₄ OC ₃ F ₆ OC ₂ F ₄ -, -OC ₂ F ₄ OC ₃ F ₆ OC ₃ F ₆ -, -OC ₂ F ₄ OC ₄ F ₈ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₂ F ₄ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₂ F ₄ OC ₃ F ₆ -, -OC ₃ F ₆ OC ₃ F ₆ OC ₂ F ₄ -, and -OC ₄ F ₈ OC ₂ F ₄ OC ₂ F ₄ - and the like. In one aspect, R ⁹ is a single bond. In another aspect, 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 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 straight chain or branched, and are preferably straight chain. In this aspect, (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 formula (f4), R ⁶ , R ⁷ and g have the same meanings as those described in the formula (f3) and have similar aspects. R ^{6 '} , R ^7' and g' each have the same meaning as R ⁶ , R ⁷ and g described in the above formula (f3), and have similar aspects. R ^r is preferably

[In the formula, * indicates the binding position]

, and more preferably

[In the formula, * indicates the binding position]

am.

In the above formula (f5), e is preferably an integer of 1 to 100, more preferably 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 of 1 to 100, more preferably 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, R ^F is a group represented by the formula (f1) or (f2).

In one aspect, R ^F is a group represented by the formula (f1).

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

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

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

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

In one aspect, R ^F is a group represented by the 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, and even more preferably Typically, it is 0.2 to 1.5, and more preferably 0.2 to 0.85. By setting the e/f ratio to 10 or less, the slipperiness, 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 more improved the slipperiness and wear durability of the surface treatment layer. On the other hand, by setting the e/f ratio to 0.1 or more, the stability of the compound can be further improved. The larger the e/f ratio, the more improved the stability of the compound.

In one aspect, the 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, and more preferably 1.0 to 2.0.

In the above fluoropolyether group-containing acrylic compound, the number average molecular weight of the R ^F1 and R ^F2 portions is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 2,000. It's 10,000. In this specification, the number average molecular weight of R ^F1 and R ^F2 is the value measured by ¹⁹ F-NMR.

In the above formulas (1) and (2), X ^A is each independently a single bond or a divalent organic group.

In one aspect, X ^A is each independently a single bond or a divalent organic group not containing a urethane bond.

In a preferred embodiment, X ^A is each independently a single bond, or

-(C _α R ¹¹ _2α ) _s1 -R ¹² _t1 -

[Formula:

R ¹¹ is independently a hydrogen atom or a fluorine atom in each occurrence,

α is an integer from 1 to 10, independently for each occurrence,

R ¹² is, in each occurrence, independently -O-, -CO-, -CONH-, -NHCO-, -COO-, or -OCO-,

s1 is an integer from 0 to 3,

t1 is an integer from 0 to 3,

The sum of s1 and t1 is 1 or more,

The order of existence of each repeating unit enclosed in parentheses with s1 or t1 is arbitrary in the equation]

It is a group represented by . In addition, in the formula, the left side binds to R ^F1 or R ^F2 .

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

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

Said R ¹¹ is preferably a hydrogen atom.

The α is independently an integer in each occurrence, preferably an integer of 1 to 6, more preferably an integer of 1 to 4, and even more preferably an integer of 2 to 4.

Said R ¹² is each independently in each occurrence, preferably -O-, -CO-, -NR ¹⁰ -, -CONH-, or -COO-, more preferably -CONH-.

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

The s1 is preferably 1 or 2, and more preferably 1.

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

In a preferred embodiment,

R ¹¹ is a hydrogen atom,

α is an integer from 2 to 4,

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

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

s1 is 1 or 2,

t1 is 0 or 1.

_{In a} ^more _{preferred embodiment} ^, _{​ ​ ​ ​ ​} is -CONR ¹⁰ -C _α1 H _2α1 -. This group is bonded to R ^F1 or R ^F2 on the left side.

α1 is an integer from 1 to 10. α2 is an integer of 0 to 6, for example, 1 to 6. α3 is an integer of 0 to 6, for example, 1 to 6. α4 is an integer of 0 to 6, for example, 1 to 6.

X ^A is preferably -CONH-C _α1 H _2α1 -. This group is bonded to R ^F1 or R ^F2 on the left side.

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

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

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

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

In the above formulas (1 ⁾ and (2),

In one aspect, X ^B is a tetravalent group, preferably

am. In one aspect, in -C(-O-)=, O is bonded to R ^Si . In another embodiment, -C(-O-)=, O is bonded to R ^Ac .

In one aspect, X ^B is a trivalent group, preferably

[In the formula, R ⁸ may be a hydrogen atom or a C _1-6 alkyl group (preferably a methyl group or an ethyl group, more preferably a methyl group)]. In one aspect, in -CR ⁸ (-O-)-, O is bonded to R ^Si . In another embodiment, -CR ⁸ (-O-)-, O binds to R ^Ac .

In a preferred embodiment, X ^B is N. In this case, in the formula, m is 1 and n is 1.

In the above formulas (1) and (2), m is each independently an integer of 1 to 10, and n is each independently an integer of 1 to 10.

m is preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and particularly preferably 1.

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

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

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

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

In ^one aspect,

C _1-6 alkylene group,

-(CH ₂ ) _z1 -O-(CH ₂ ) _z2 -(Wherein, z1 is an integer of 0 to 6, for example, 1 to 6, and z2 is an integer of 0 to 6, for example. is an integer from 1 to 6),

-(CH ₂ ) _z3 -phenylene-(CH ₂ ) _z4 -(wherein, z3 is an integer of 0 to 6, for example, 1 to 6, and z4 is an integer of 0 to 6, for example For example, it is an integer from 1 to 6), or

-(CH ₂ ) _z13 -OCONH-(CH ₂ ) _z14 - (wherein, z13 is an integer from 0 to 6, and z14 is an integer from 0 to 6)

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

The C _1-6 alkylene group may be straight chain or branched, but is preferably straight chain.

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

Each occurrence of R ¹ is independently a hydroxyl group or a hydrolyzable group.

R ¹ is preferably a hydrolyzable group independently in each occurrence.

R ¹ is preferably independently in each occurrence -OR ^h , -OCOR ^h , -ON=CR ^h ₂ , -NR ^h ₂ , -NHR ^h , -NCO, or halogen (in these formulas, R ^h represents a substituted or unsubstituted C _1-4 alkyl group), and more preferably -OR ^h (i.e., an alkoxy group). Examples of R ^h include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, and isobutyl group; and substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, especially an unsubstituted alkyl group, is preferable, and a methyl group or an ethyl group is more preferable. In one aspect, R ^h is a methyl group, and in another aspect, R ^h is an ethyl group.

Each occurrence of R ² is independently a hydrogen atom or a monovalent organic group. These monovalent organic groups are monovalent organic groups excluding the hydrolyzable groups mentioned above.

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

In the above formula, n' is each independently an integer of 1 to 3 for each (SiR ¹ _n' R ² _{3 -n'} ) unit, preferably 2 or 3, and more preferably 3.

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

Said X ^D is a single bond or a divalent organic group.

X ^D is preferably -o-, -co-, -coo-, -oco-, -conh-, -nhco-, -Oconh-, _-nhcoo- CH(OH)CH ₂ -, or -CH(CH ₂ OH)CH ₂ -, more preferably -CONH-, -CH ₂ CH(OH)CH ₂ -, -CH(CH ₂ OH)CH ₂ - ,

[In the formula, * and ** represent binding positions, * binds to X ^B , and ** binds to X ^E ]

am. The left side of these groups binds to X ^B.

X ^D is more preferably -CONH-.

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

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

In one aspect, X ^E is:

-X ^G -X ^H

[Formula:

X ^G is,

single bond,

C _1-6 alkylene group,

-(CH ₂ ) _z9 -O-(CH ₂ ) _z10 -(wherein, z9 is an integer of 0 to 6, for example, an integer of 1 to 6, and z10 is an integer of 0 to 6, for example is an integer from 1 to 6), or,

-(CH ₂ ) _z11 -phenylene-(CH ₂ ) _z12 -(wherein, z11 is an integer of 0 to 6, for example, 1 to 6, and z12 is an integer of 0 to 6, for example For example, it is an integer from 1 to 6)

and

X ^H is

and

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

It is a trivalent or tetravalent group represented by .

The C _1-6 alkylene group may be straight chain or branched, but is preferably straight chain.

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

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

Each occurrence of X ^F is independently a single bond or a divalent organic group (preferably a divalent organic group having 1 to 10 carbon atoms).

In one aspect, X ^F is,

single bond,

C _1-6 alkylene group,

-(CH ₂ ) _z5 -O-(CH ₂ ) _z6 -(wherein, z5 is an integer of 0 to 6, for example, 1 to 6, and z6 is an integer of 0 to 6, for example is an integer from 1 to 6), or,

-(CH ₂ ) _z7 -phenylene-(CH ₂ ) _z8 -(wherein, z7 is an integer of 0 to 6, for example, 1 to 6, and z8 is an integer of 0 to 6, for example For example, it is an integer from 1 to 6)

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

The C _1-6 alkylene group may be straight chain or branched, but is preferably straight chain.

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

In one aspect, X ^D , X ^E , and X ^F are single bonds.

Said R ⁵ is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 8 carbon atoms.

The monovalent organic group is preferably a C _1-8 alkyl group, a C _3-8 cycloalkyl group, or a C _5-8 aryl group, more preferably a C _1-6 alkyl group or a phenyl group, and even more preferably a C 1-8 alkyl _{group. -3} It is an alkyl group, especially preferably a methyl group.

In one aspect, R ⁵ is a hydrogen atom.

In one aspect, R ⁵ is a methyl group.

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

The fluoropolyether group-containing acrylic compound represented by the formula (1) or formula (2) is not particularly limited, but may have a number average molecular weight of 5×10 ² to 1×10 ⁵ . Among these ranges, those having a number average molecular weight of 2,000 to 32,000, more preferably 2,500 to 12,000, are preferable from the viewpoint of wear durability. In addition, this “number average molecular weight” is taken as the value measured by ¹⁹ F-NMR.

In one aspect, the fluoropolyether group-containing acrylic compound of the present disclosure is a fluoropolyether group-containing acrylic compound represented by formula (1).

In one aspect, the fluoropolyether group-containing acrylic compound of the present disclosure is a fluoropolyether group-containing acrylic compound represented by formula (2).

The fluoropolyether group-containing acrylic compound represented by the above formulas (1) and (2) is prepared by first preparing a fluoropolyether group-containing silane compound having a reactive site such as -NH-, -C(OH)-, etc. Then, it can be obtained by reacting a compound having an acrylic group with the reactive site.

In one aspect, the fluoropolyether group-containing acrylic compounds represented by the formulas (1) and (2) have the following formula:

R ^F1 -COOR ²¹

R ²¹ OOC-R ^F2 -COOR ²¹

(In the formula, R ²¹ is a hydrogen atom or a methyl group, and R ^F1 and R ^F2 have the same meaning as described in formulas (1) and (2))

A compound represented by and the following formula:

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

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

R ²³ is a divalent group,

R ²⁴ is a reactive group such as NH ₂ ,

R ¹ , R ² , and n' have the same meaning as described in equations (1) and (2))

By reacting the compound represented by the following formula:

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

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

Obtain the compound represented by Then, the compound and the formula:

R ³⁴ -R ³⁵ -OCOCH=CH ₂

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

R ³⁵ is a divalent group) or

R ⁵⁶ -OCOCR ⁵⁷ =CH ₂

(Wherein, R ⁵⁶ is halogen, H, or a monovalent hydrocarbon group,

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

It can be obtained by reacting the compound represented by .

In one aspect, the fluoropolyether group-containing acrylic compounds represented by the formulas (1) and (2) have the following formula:

R ^F1 -COF

FOC-R ^F2 -COF

(In the formula, R ^F1 and R ^F2 have the same meaning as described in formulas (1) and (2))

A compound represented by

Br-Mg-CH ₂ CH=CH ₂

By reacting,

R ^F1 -C(OH)(CH ₂ CH=CH ₂ ) ₂

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

Obtain the compound represented by Then, the compound and the formula:

HSiR ¹ _n' R ² _{3 -n'}

By reacting,

R ^F1 -C(OH)(CH ₂ CH=CH ₂ ) ₂

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

Obtain the compound represented by Then, the compound and the 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 group)

It can be obtained by reacting the compound represented by .

In one aspect, the fluoropolyether group-containing acrylic compounds represented by the formulas (A1) and (A2) have the following formula:

HOCH ₂ -R ^F2 -CH ₂ OH

(In the formula, R ^F1 and R ^F2 have the same meaning as described in formulas (A1) and (A2))

A compound represented by

By reacting,

get Subsequently, the above compound,

OCN-(CH ₂ ) ₃ -SiR ¹ _n' R ² _3-n'

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

By reacting,

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

A compound represented by can be obtained.

In one aspect, the fluoropolyether group-containing acrylic compounds represented by the formulas (A1) and (A2) have the following formula:

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

A compound represented by

HOOC=CH ₂

By reacting,

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

Obtain the compound represented by Subsequently, the above compound,

OCN-(CH ₂ ) ₃ -SiR ¹ _n' R ² _3-n'

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

By reacting,

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

A compound represented by can be obtained.

The reaction conditions for each step of the above reaction can be set appropriately by a person skilled in the art.

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

The surface treatment agent of the present disclosure contains at least one fluoropolyether group-containing acrylic compound represented by formula (1) or (2).

In one aspect, among the surface treatment agents of the present disclosure, the fluoropolyether group-containing acrylic compound is a compound represented by formula (1).

In another aspect, among the surface treatment agents of the present disclosure, the fluoropolyether group-containing acrylic compound is a compound represented by formula (2).

In another aspect, among the surface treatment agents of the present disclosure, the fluoropolyether group-containing acrylic compound is a compound represented by formula (1) and a compound represented by formula (2).

Among the surface treatment agents of the present disclosure, the compound represented by formula (2) is preferably 0.1 mol% or more and 35 mol% or less relative to the total of the compound represented by formula (1) and the compound represented by formula (2). am. The lower limit of the content of the compound represented by formula (2) relative to the total of the compound represented by formula (1) and the compound represented by formula (2) is preferably 0.1 mol%, more preferably 0.2 mol%, More preferably, it is 0.5 mol%, even more preferably 1 mol%, particularly preferably 2 mol%, and especially 5 mol%. The upper limit of the content of the compound represented by formula (2) relative to the total of the compound represented by formula (1) and the compound represented by formula (2) is preferably 35 mol%, more preferably 30 mol%, More preferably, it may be 20 mol%, and even more preferably 15 mol% or 10 mol%. The compound represented by formula (2) relative to the total of the compound represented by formula (1) and the compound represented by formula (2) is preferably 0.1 mol% or more and 30 mol% or less, more preferably 0.1 mol%. 20 mol% or less, more preferably 0.2 mol% or more and 10 mol% or less, even more preferably 0.5 mol% or more and 10 mol% or less, particularly preferably 1 mol% or more and 10 mol% or less, for example 2 It is mol% or more and 10 mol% or less, or 5 mol% or more and 10 mol% or less.

The content of the compound represented by the formula (1) or (2) is preferably 0.1 to 50.0% by mass, more preferably 1.0 to 30.0% by mass, and still more preferably 5.0 to 25.0% by mass, based on the total surface treatment agent. %, particularly preferably 10.0 to 20.0 mass %. By setting the content of the fluoropolyether group-containing acrylic compound within the above range, higher water and oil repellency and friction durability can be obtained.

The surface treatment agent of the present disclosure is 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”) ), (non-reactive) silicone compounds that can be understood as silicone oil (hereinafter referred to as “silicone 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; Aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and 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-2- Ester such as hydroxybutyrate, ethyl acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, and ethyl 2-hydroxyisobutyrate. ; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methyl amino ketone, and 2-heptanone; Ethyl cellosolve, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol mono. Glycol ethers such as ethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, and ethylene glycol monoalkyl ether; Alcohols such as methanol, ethanol, iso-propanol, n-butanol, isobutanol, tert-butanol, sec-butanol, 3-pentanol, octyl alcohol, 3-methyl-3-methoxybutanol, and tert-amyl alcohol; Glycols such as ethylene glycol and propylene glycol; Cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; Amides such as N,N-dimethylformamide and N,N-dimethylacetamide; ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, and diethylene glycol monomethyl ether; diethylene glycol monoethyl ether acetate; 1,1,2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, dimethyl sulfoxide, 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 OH, (CF ₃ ) ₂ CHOH, etc. Containing solvents, etc. can be mentioned. Or a mixed solvent of two or more of these types can be mentioned.

The fluorine-containing oil is not particularly limited, but examples include compounds represented by the following general formula (3) (perfluoro(poly)ether compounds).

Rf ⁵ -(OC ₄ F ₈ ) _a' -(OC ₃ F ₆ ) _b' -(OC ₂ F ₄ ) _c' -(OCF ₂ ) _d' -Rf ⁶ … (3)

In the formula, Rf ⁵ represents an alkyl group having 1 to 16 carbon atoms (preferably a C _1-16 perfluoroalkyl group) which may be substituted with one or more fluorine atoms, and Rf ⁶ represents one or Represents an alkyl group with 1 to 16 carbon atoms (preferably a C _1-16 perfluoroalkyl group) that may be substituted with more fluorine atoms, a fluorine atom or a hydrogen atom, and Rf ⁵ and Rf ⁶ are more preferably: Each independently, is a C _1-3 perfluoroalkyl group.

a', b', c', and d' each represent the number of four types of repeating units of perfluoro(poly)ether constituting the main skeleton of the polymer, and are independently integers from 0 to 300, and a The sum of ', b', c' and d' is at least 1, preferably 1 to 300, more preferably 20 to 300. The order of existence of each repeating unit enclosed in parentheses with the subscript a', b', c', or d' is arbitrary in the formula. These repeating units may be linear or branched, and may contain a ring structure. For example, -(OCF ₄ F ₈ )- is -(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(CF ₃ ))-, -(OCF(C ₂ F ₅ )CF ₂ )- and (OCF ₂ CF(C ₂ F ₅ ))- may be any of them, but preferably -(OCF ₂ CF ₂ CF ₂ CF ₂ )-. -(OC ₃ F ₆ )- may be any of -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )-, and (OCF ₂ CF(CF ₃ ))-, and is preferred. This is -(OCF ₂ CF ₂ CF ₂ )-. -(OCF ₂ F ₄ )- may be either -(OCF ₂ CF ₂ )- or (OCF(CF ₃ ))-, but is preferably -(OCF ₂ CF ₂ )-.

The ring structure is the following 3-membered ring or 4-membered ring:

[In the formula, * indicates the binding position]

It can be.

For example, (OC ₄ F ₈ ) is:

[In the formula, * indicates the binding position]

It can be.

As an example of the perfluoro(poly)ether compound represented by the general formula (3), a compound (single type or a mixture of two or more types may be used) represented by any of the following general formulas (3a) and (3b) I can hear it.

Rf ⁵ -(OCF ₂ CF ₂ CF ₂ ) _b" -Rf ⁶ … (3a)

Rf ⁵ -(OCF ₂ CF ₂ CF ₂ CF ₂ ) _a" -(OCF ₂ CF ₂ CF ₂ ) _b" -(OCF ₂ CF ₂ ) _c" -(OCF ₂ ) _d" -Rf ⁶ ... (3b)

In these formulas, Rf ⁵ and Rf ⁶ are as defined above; In formula (3a), b" is an integer of 1 to 100; in formula (3b), a" and b" are each independently integers of 0 to 30, and c" and d" are each The order of existence of each repeating unit, which is independently an integer between 1 and 300 and enclosed in parentheses with the subscripts a", b", c", and d", is arbitrary in the formula.

Additionally, from another viewpoint, the fluorine-containing oil may be a compound represented by the general formula Rf ³ -F (wherein Rf ³ is a C _5-16 perfluoroalkyl group). Additionally, it may be a chlorotrifluoroethylene oligomer.

The fluorine-containing oil may have an average molecular weight of 500 to 10,000. The molecular weight of fluorine-containing oil can be measured using GPC.

The fluorine-containing oil may be contained in an amount of, for example, 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 5% by mass, relative to the surface treatment agent of the present disclosure. In one aspect, the surface treatment agent of the present disclosure is substantially free of fluorine-containing oil. Substantially free from fluorine-containing oil means that it does not contain fluorine-containing oil at all, or may contain a trace amount of fluorine-containing oil.

In one aspect, the average molecular weight of the fluorine-containing oil may be larger than the average molecular weight of the acrylic compound containing a fluoropolyether group. By setting such an average molecular weight, better wear durability and surface slipperiness can be obtained, especially when forming a surface treatment layer by vacuum deposition.

In one aspect, the average molecular weight of the fluorine-containing oil may be smaller than the average molecular weight of the acrylic compound containing a fluoropolyether group. By setting such an average molecular weight, a cured product having high wear durability and high surface slipperiness can be formed while suppressing a decrease in transparency of the surface treatment layer obtained from such a compound.

The fluorine-containing oil contributes to improving the surface slipperiness of the layer formed by the surface treatment agent of the present disclosure.

As the silicone oil, for example, a linear or cyclic silicone oil having a siloxane bond of 2,000 or less can be used. The linear silicone oil may be so-called straight silicone oil or modified silicone oil. Examples of straight silicone oil include dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil. Examples of modified silicone oil include straight silicone oil modified with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, etc. Examples of cyclic silicone oil include cyclic dimethylsiloxane oil.

Among the surface treatment agents of the present disclosure, such silicone oil is, for example, 0 parts by mass relative to a total of 100 parts by mass (if two or more types, the total of these, the same applies hereinafter) of the fluoropolyether group-containing acrylic compound of the present disclosure. It may be included in an amount of 50 to 300 parts by mass, preferably 50 to 200 parts by mass.

Silicone oil contributes to improving the surface slipperiness of the surface treatment layer.

Examples of the alcohols include alcohols having 1 to 6 carbon atoms that may be substituted with one or more fluorine atoms, such as methanol, ethanol, iso-propanol, 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 improved and the compatibility between the perfluoropolyether group-containing acrylic compound and the solvent is improved.

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

Examples of the catalyst include acids (e.g. acetic acid, trifluoroacetic acid, etc.), bases (e.g. ammonia, triethylamine, diethylamine, etc.), transition metals (e.g. Ti, Ni, Sn, etc.), etc. I can hear it.

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

Other components other than the above include, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and methyltriacetoxysilane. .

The surface treatment agent of the present disclosure can be made into pellets by impregnating a porous material, such as a porous ceramic material, a metal fiber, such as steel wool, hardened into a planar shape. The pellets can be used, for example, for vacuum deposition.

In addition to the above components, the surface treatment agent of the present disclosure contains impurities such as Pt, Rh, Ru, 1,3-divinyltetramethyldisiloxane, triphenylphosphine, NaCl, KCl, condensates of silane, etc. It may contain trace amounts.

Hereinafter, the article of the present disclosure will be described.

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

Substrates that can be used in the present disclosure include, for example, glass, resin (natural or synthetic resin, for example, may be a general plastic material), metal, ceramics, semiconductors (silicon, germanium, etc.), fibers (fabric, non-woven fabric, etc.) , fur, leather, wood, ceramics, stone, etc., building members, etc., sanitary products, and any suitable material.

For example, when the article to be manufactured is an optical member, the material constituting the surface of the substrate may be a material for optical members, such as glass or transparent plastic. Additionally, when the article to be manufactured is an optical member, any layer (or film), such as a hard coat layer or an anti-reflection layer, may be formed on the surface (outermost layer) of the substrate. For the anti-reflection layer, either a single-layer anti-reflection layer or a multi-layer anti-reflection layer may be used. Examples of inorganic materials that can be used in the anti-reflection 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 may be used individually or in combination of two or more types thereof (for example, as a mixture). When using a multilayer antireflection layer, it is preferable to use SiO ₂ and/or SiO as the outermost layer. When the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode, for example, indium tin oxide (ITO) or indium zinc oxide, may be formed on part of the surface of the base material (glass). . In addition, the base material has an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a higher order film, a liquid crystal display module, etc., depending on its specific specifications, etc. You can stay.

The shape of the substrate is not particularly limited, and may be, for example, plate-shaped, film, or other forms. In addition, the surface area of the substrate on which the surface treatment layer is to be formed may be at least a portion of the surface of the substrate, and can be appropriately determined depending on the purpose and specific specifications of the article to be manufactured.

In one aspect, such a substrate may have at least a surface portion made of a material that originally has hydroxyl groups. Examples of such materials include glass, and also include metals (particularly non-metals), ceramics, and semiconductors on which a natural oxide film or thermal oxidation film is formed on the surface. Alternatively, in cases where the presence of hydroxyl groups is not sufficient, such as in resins, or when the base material does not originally have hydroxyl groups, hydroxyl groups can be introduced or increased on the surface of the base material by subjecting the base material to some kind of pretreatment. Examples of such pretreatment include plasma treatment (for example, corona discharge) and ion beam irradiation. Plasma treatment can introduce or increase hydroxyl groups on the surface of a substrate, and can also be suitably used to clean the surface of the substrate (remove foreign substances, etc.). In addition, as another example of such pretreatment, an interfacial adsorbent having a carbon-carbon unsaturated bonding group is formed in the form of a monomolecular film on the surface of the substrate in advance by LB method (Langmuir-Blodget method) or chemical adsorption method, and then oxygen or nitrogen is added to the surface of the substrate. and a method of cleaving an unsaturated bond in an atmosphere containing such.

In another aspect, such a substrate may have at least a surface portion made of a material containing a silicone compound or alkoxysilane having one or more other reactive groups, for example, Si-H groups.

In a preferred embodiment, the substrate is glass. Preferred examples of such glass include sapphire glass, soda-lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass, as well as chemically strengthened soda-lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded glass. Borosilicate glass is particularly preferred.

The article of the present disclosure can be manufactured by forming a layer of the surface treatment agent of the present disclosure on the surface of the substrate, post-treating this layer as necessary, and thereby forming a layer of the surface treatment agent of the present disclosure. there is.

Layer formation of the surface treatment agent of the present disclosure can be performed by applying the surface treatment agent to the surface of the substrate so as to cover the surface. The coating method is not particularly limited. For example, wet coating and dry coating methods 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 vapor deposition (usually vacuum deposition), sputtering, CVD, and similar methods. Specific examples of the deposition method (usually vacuum deposition) include resistance heating, electron beam, high-frequency heating using microwaves, ion beam, and similar methods. Specific examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.

Additionally, coating using an atmospheric pressure plasma method is also possible.

When using a wet coating method, the surface treatment agent of the present disclosure can be diluted with a solvent and then applied to the substrate surface. In view of the stability of the composition of the present disclosure and the volatility of the solvent, the following solvents are preferably used: perfluoro aliphatic hydrocarbons having 5 to 12 carbon atoms (e.g., perfluorohexane, perfluoromethylcyclohexane and perfluoro-1,3-dimethylcyclohexane); polyfluoro aromatic hydrocarbons (e.g., bis(trifluoromethyl)benzene); Polyfluoro aliphatic hydrocarbons (e.g., C ₆ F ₁₃ CH ₂ CH ₃ (e.g., Asahi Clean (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2, 3,3,4-heptafluorocyclopentane (e.g., Zeorora (registered trademark) H manufactured by Nippon Zeon Co., Ltd.); hydrofluoroether (HFE) (e.g., perfluoropropylmethyl ether); (C ₃ F ₇ OCH ₃ ) (e.g., Novec (trademark) 7000 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutylmethyl ether (C ₄ F ₉ OCH ₃ ) (e.g., Sumitomo 3M Co., Ltd.) Novec (trademark) 7100, manufactured by Kaisha Co., Ltd.), perfluorobutyl ethyl ether (C ₄ F ₉ OC ₂ H ₅ ) (e.g., Novec (trademark) 7200, manufactured by Sumitomo 3M Co., Ltd.), perfluorohexylmethyl. Alkylperfluoroalkyl ethers such as ether (C ₂ F ₅ CF(OCH ₃ )C ₃ F ₇ ) (for example, Novec (trademark) 7300 manufactured by Sumitomo 3M Co., Ltd.) (the perfluoroalkyl group and the alkyl group are may be linear or branched), or CF ₃ CH ₂ OCF ₂ CHF ₂ (for example, Asahi Clean (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.), etc. Alternatively, it can be used as a mixture of two or more types, preferably hydrofluoroether, and perfluorobutylmethyl ether (C ₄ F ₉ OCH ₃ ) and/or perfluorobutyl ethyl ether (C ₄ F _{9 )} . OC ₂ H ₅ ) is particularly preferred.

When using the dry coating method, the surface treatment agent of the present disclosure may be subjected to the dry coating method as is, or may be diluted with the above-mentioned solvent and then subjected to the dry coating method.

The layer formation of the surface treatment agent is preferably performed so that the surface treatment agent of the present disclosure is present together with a catalyst for hydrolysis and dehydration condensation in the layer. Conveniently, in the case of using a wet coating method, the catalyst may be added to the diluted solution of the surface treatment agent of the present disclosure immediately before application to the surface of the substrate after diluting the surface treatment agent of the present disclosure with a solvent. In the case of a dry coating method, the surface treatment agent of the present disclosure to which a catalyst has been added is deposited as is (usually vacuum deposition), or a metal porous body such as iron or copper is impregnated with the surface treatment agent of the present disclosure to which a catalyst has been added. Pellets Vapor deposition (usually vacuum deposition) may be performed using the phase material.

As the catalyst, any suitable acid or base can be used. As the acid catalyst, for example, acetic acid, formic acid, trifluoroacetic acid, etc. can be used. Additionally, as a base catalyst, for example, ammonia, organic amines, etc. can be used.

The surface treatment layer included in the article of the present disclosure has both high wear durability. In addition to high abrasion durability, the surface treatment layer has water-repellency, oil-repellent properties, anti-fouling properties (prevents the adhesion of contaminants such as fingerprints), and waterproofing properties (e.g., prevents adhesion of contaminants such as fingerprints), depending on the composition of the surface treatment agent used. It can have surface slipperiness (or lubricity, such as wiping away contaminants such as fingerprints or excellent feel to the finger), chemical resistance, etc., and can be suitably used as a functional thin film. You can.

Accordingly, the present disclosure also relates to an optical material having the surface treatment layer as the outermost layer.

As optical materials, in addition to optical materials for displays and the like as exemplified later, a wide variety of optical materials are preferably used: for example, cathode ray tubes (CRTs; e.g., computer monitors), liquid crystal displays, and plasma displays. , displays such as organic EL displays, inorganic thin film EL dot matrix displays, rear projection displays, fluorescent displays (VFDs), field emission displays (FEDs), or protective plates for these displays, or anti-reflective films on their surfaces. processing was carried out.

The article of the present disclosure is not particularly limited, but may be an optical member. Examples of optical members include: lenses such as glasses; Front protection plates, anti-reflection plates, polarizers, and anti-glare plates for displays such as PDP and LCD; Touch panel sheets for devices such as mobile phones and mobile information terminals; Disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; optical fiber; Watch display, etc.

Additionally, the article of the present disclosure may be a medical device or medical material. Additionally, the article having the layer obtained by the present disclosure may be an automobile interior or exterior member. Examples of exterior materials include: windows, light covers, and external camera covers. Examples of interior materials include: instrument panel covers, navigation system touch panels, and decorative interior materials.

The thickness of the layer is not particularly limited. In the case of an optical member, the thickness of the layer is preferably in the range of 1 to 50 nm, 1 to 30 nm, and preferably 1 to 15 nm from the viewpoint of optical performance, wear durability and anti-fouling properties.

Above, the article of the present disclosure has been described in detail. In addition, the article and method for manufacturing the article of the present disclosure are not limited to those exemplified above.

Example

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

Synthesis Example 1

In a 100 mL three-necked flask equipped with a reflux condenser, thermometer and stirrer, perfluoropolyether-modified acid fluoride with an average composition CF ₃ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ COF was added. 10.0 g of sieve, 10.0 g of 1,3-bis(trifluoromethyl)benzene, and 5.0 g of tetrahydrofuran were stirred at 25°C for 30 minutes under a nitrogen stream. Subsequently, 9.6 mL of 0.7 M allyl magnesium bromide was slowly added dropwise, and then heated at 60°C for 4 hours. After that, it was cooled to 5°C, and 10.0 g of 3.0 M hydrochloric acid aqueous solution was added dropwise to stop the reaction. The lower fluorose phase was recovered through a liquid separation operation and then washed with methanol. Thereafter, the volatile matter was distilled off under reduced pressure to obtain a perfluoropolyether group-containing allyl compound (A) represented by the following formula.

CF ₃ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ C(OH)(CH ₂ CH=CH ₂ ) ₂

Synthesis Example 2

In a 100 mL three-necked flask equipped with a reflux condenser, thermometer, and stirrer, 10.0 g of the perfluoropolyether group-containing allyl compound (A) obtained in Synthesis Example 1 and 10.0 g of 1,3-bis(trifluoromethyl)benzene were added. , 0.020 g of triacetoxymethylsilane, and 1.21 g of trichlorosilane were added, and stirred for 30 minutes at 5°C under a nitrogen stream. Subsequently, 0.20 g of a xylene solution containing 2% of the Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added, and then stirred at 60°C for 5 hours. Thereafter, the volatile matter was distilled off under reduced pressure to obtain a perfluoropolyether group-containing trichlorosilane compound (B) represented by the following formula.

CF ₃ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ C(OH)(CH ₂ CH ₂ CH ₂ SiCl ₃ ) ₂

Synthesis Example 3

In a 100 mL three-necked flask equipped with a reflux condenser, thermometer, and stirrer, 10.0 g of the perfluoropolyether group-containing trichlorosilane compound (B) obtained in Synthesis Example 2, and 1,3-bis(trifluoromethyl) 10.0 g of benzene was added and stirred at 50°C for 30 minutes under a nitrogen stream. Subsequently, a mixed solution of 0.13 g of methanol and 1.42 g of methyl orthoformate was added, and then stirred at 65°C for 2 hours. Thereafter, the volatile matter was distilled off under reduced pressure to obtain a perfluoropolyether group-containing silane compound (C) represented by the following formula.

CF ₃ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ C(OH){CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ } ₂

Synthesis Example 4

In a 100 mL three-necked flask equipped with a reflux condenser, thermometer, and stirrer, 10.0 g of the perfluoropolyether group-containing silane compound (C) obtained in Synthesis Example 3 and 2-isocyanatoethyl acrylate (Showa Denko Co., Ltd.) 0.32 g of Kaisha Karenz (registered trademark) AOI) and 0.0014 g of dibutyltin dilaurate were added and stirred at 50°C for 2 hours under a nitrogen stream to obtain a perfluoropolyether group represented by the following formula. Silane compound (D) was obtained.

CF ₃ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ C(OX){CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ } ₂

X=-CONHCH ₂ CH ₂ OCOCH=CH ₂

Synthesis Example 5

In a 100 mL three-necked flask equipped with a reflux condenser, thermometer and stirrer, modified perfluoropolyether with an average composition CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₂₄ CF ₂ CF ₂ COOCH ₃ was added. 10.0 g of ester, 5.0 g of 1,3-bis(trifluoromethyl)benzene, and 0.51 g of 3-(2-aminoethylamino)propyltrimethoxysilane were added, and incubated at 25°C for 1 hour under a nitrogen stream. It was stirred. Thereafter, the volatile matter was distilled off under reduced pressure to obtain a perfluoropolyether group-containing silane compound (E) represented by the following formula.

CF ₃ CF ₂ CF ₂ O(CF ₂ CF ₂ CF ₂ O) ₂₄ CF ₂ CF ₂ CONHCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Synthesis Example 6

In a 100 mL three-necked flask equipped with a reflux condenser, thermometer, and stirrer, 10.0 g of the perfluoropolyether group-containing silane compound (E) obtained in Synthesis Example 5 and 2-isocyanatoethyl acrylate (Showa Denko Co., Ltd.) 0.32 g of Kaisha Karenz (registered trademark) AOI) was added and stirred at 25°C for 1 hour under a nitrogen stream to obtain a perfluoropolyether group-containing silane compound (F) represented by the following formula.

CF ₃ CF ₂ CF ₂ O(CF ₂ CF ₂ CF ₂ O) ₂₄ CF ₂ 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 7

In a 100 mL three-necked flask equipped with a reflux condenser, thermometer, and stirrer, a perfluoropolyether modified ester with an average composition CF ₃ O (CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ COOCH ₃ was added. 10.0 g, 5.0 g of 1,3-bis(trifluoromethyl)benzene, and 0.50 g of 3-(2-aminoethylamino)propyltrimethoxysilane were added, and stirred at 25°C for 1 hour under a nitrogen stream. . Thereafter, the volatile matter was distilled off under reduced pressure to obtain a perfluoropolyether group-containing silane compound (G) represented by the following formula.

CF ₃ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ CONHCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Synthesis Example 8

In a 100 mL three-necked flask equipped with a reflux condenser, thermometer, and stirrer, 10.0 g of the perfluoropolyether group-containing silane compound (G) obtained in Synthesis Example 7, and 2-isocyanatoethyl acrylate (Showa Denko Co., Ltd.) 0.31 g of Karenz (registered trademark) AOI) manufactured by Shiki Kaisha was added and stirred at 25°C for 1 hour under a nitrogen stream to obtain a perfluoropolyether group-containing silane compound (H) represented by the following formula.

CF ₃ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ CONHCH ₂ CH ₂ N(X)CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

X=-CONHCH ₂ CH ₂ OCOCH=CH ₂

Synthesis Example 9

In a 100 mL three-necked flask equipped with a reflux condenser, thermometer, and stirrer, perfluoropoly with an average composition CF ₃ CF ₂ CF ₂ O{CF(CF ₃ )CF ₂ O} ₁₁ CF(CF ₃ )COOCH ₃ was added. 10.0 g of ether-modified ester, 5.0 g of 1,3-bis(trifluoromethyl)benzene, and 1.02 g of 3-(2-aminoethylamino)propyltrimethoxysilane were added, and the mixture was heated at 70°C under a nitrogen stream. It was stirred for 10 hours. Thereafter, the volatile matter was distilled off under reduced pressure to obtain a perfluoropolyether group-containing silane compound (I) represented by the following formula.

CF ₃ CF ₂ CF ₂ O{CF(CF ₃ )CF ₂ O} ₁₁ CF(CF ₃ )CONHCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Synthesis Example 10

In a 100 mL three-necked flask equipped with a reflux condenser, thermometer, and stirrer, 10.0 g of the perfluoropolyether group-containing silane compound (I) obtained in Synthesis Example 9, and 2-isocyanatoethyl acrylate (Showa Denko Co., Ltd.) 0.65 g of Karenz (registered trademark) AOI) manufactured by Shiki Kaisha was added and stirred at 25°C for 1 hour under a nitrogen stream to obtain a perfluoropolyether group-containing silane compound (J) represented by the following formula.

CF ₃ CF ₂ CF ₂ O{CF(CF ₃ )CF ₂ O} ₁₁ CF(CF ₃ )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 11

In a 100 mL three-necked flask equipped with a reflux condenser, thermometer, and stirrer, the average composition CF ₃ O (CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) ₁₃ CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ COOCH ₃ 10.0 g of the indicated perfluoropolyether modified ester, 5.0 g of 1,3-bis(trifluoromethyl)benzene, and 0.47 g of 3-(2-aminoethylamino)propyltrimethoxysilane were added, and nitrogen was added. It was stirred for 1 hour at 25°C under air flow. Thereafter, the volatile matter was distilled off under reduced pressure to obtain a perfluoropolyether group-containing silane compound (K) represented by the following formula.

CF ₃ O(CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) ₁₃ CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CONHCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Synthesis Example 12

In a 100 mL three-necked flask equipped with a reflux condenser, thermometer, and stirrer, 10.0 g of the perfluoropolyether group-containing silane compound (K) obtained in Synthesis Example 11, and 2-isocyanatoethyl acrylate (Showa Denko Co., Ltd.) 0.30 g of Karen's (registered trademark) AOI) manufactured by Shiki Kaisha was added and stirred at 25°C for 1 hour under a nitrogen stream to obtain a perfluoropolyether group-containing silane compound (L) represented by the following formula.

CF ₃ O(CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) ₁₃ CF ₂ CF ₂ OCF ₂ CF ₂ 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

In a 100 mL three-necked flask equipped with a reflux condenser, thermometer, and stirrer, 10.0 g of the perfluoropolyether group-containing silane compound (G) obtained in Synthesis Example 7, and 1,1-(bisacryloyloxymethyl)ethyl 0.53 g of isocyanate (Kalens (registered trademark) BEI, manufactured by Showa Denko Co., Ltd.) was added, stirred for 1 hour at 25°C under a nitrogen stream, and a perfluoropolyether group-containing silane compound represented by the following formula ( M) was obtained.

CF ₃ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ CONHCH ₂ CH ₂ N(X)CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

X=-CONHC(CH ₃ )(CH ₂ OCOCH=CH ₂ ) ₂

Synthesis Example 14

In a 100 mL three-necked flask equipped with a reflux condenser, thermometer, and stirrer, 10.0 g of the perfluoropolyether group-containing silane compound (G) obtained in Synthesis Example 7, and 4-hydroxybutylacrylate glycidyl ether (Mitsubishi 0.45 g of (4HBAGE) manufactured by Chemical Co., Ltd. was added and stirred at 50°C for 2 hours under a nitrogen stream to obtain a perfluoropolyether group-containing silane compound (N) represented by the following formula.

CF ₃ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ CONHCH ₂ CH ₂ N(X)CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

^{X is ​ ​}

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 15

In a 100 mL three-necked flask equipped with a reflux condenser, thermometer and stirrer, modified perfluoropolyether with an average composition CH ₃ OCOCF ₂ O(CF ₂ O) ₁₂ (CF ₂ CF ₂ O) ₁₂ CF ₂ COOCH ₃ was added. 10.0 g of ester, 5.0 g of 1,3-bis(trifluoromethyl)benzene, and 1.69 g of 3-(2-aminoethylamino)propyltrimethoxysilane were added, and incubated at 25°C for 1 hour under a nitrogen stream. It was stirred. Thereafter, the volatile matter was distilled off under reduced pressure to obtain a perfluoropolyether group-containing silane compound (O) 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 CH ₂ Si(OCH ₃ ) ₃

Synthesis Example 16

In a 100 mL three-necked flask equipped with a reflux condenser, thermometer, and stirrer, 10.0 g of the perfluoropolyether group-containing silane compound (O) obtained in Synthesis Example 15, and 2-isocyanatoethyl acrylate (Showa Denko Co., Ltd.) 1.08 g of Karen's (registered trademark) AOI) manufactured by Shiki Kaisha was added and stirred at 25°C for 1 hour under a nitrogen stream to obtain a perfluoropolyether group-containing silane compound (P) 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 CH ₂ Si(OCH ₃ ) ₃

X=-CONHCH ₂ CH ₂ OCOCH=CH ₂

Synthesis Example 17

In a 100 mL three-necked flask equipped with a reflux condenser, thermometer, and stirrer, the average composition CH ₃ OCOCF(CF ₃ ){OCF ₂ CF(CF ₃ )} _m OCF ₂ CF ₂ O{CF(CF ₃ )CF ₂ O} 10.0 g of perfluoropolyether modified ester represented by _n CF(CF ₃ )COOCH ₃ (m+n≒34), 5.0 g of hexafluorobenzene, and 3-(2-aminoethylamino)propyltrimethoxy 0.73 g of silane was added, and stirred at 70°C for 12 hours under a nitrogen stream. Thereafter, volatile matter was distilled off under reduced pressure to obtain a perfluoropolyether group-containing silane compound (Q) represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH 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 NHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Synthesis Example 18

In a 100 mL three-necked flask equipped with a reflux condenser, thermometer, and stirrer, 10.0 g of the perfluoropolyether group-containing silane compound (Q) obtained in Synthesis Example 17, and 2-isocyanatoethyl acrylate (Showa Denko Co., Ltd.) 0.46 g of Karen's (registered trademark) AOI) manufactured by Shiki Kaisha was added and stirred at 25°C for 1 hour under a nitrogen stream to obtain a perfluoropolyether group-containing silane compound (R) represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH 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 N(X)CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

X=-CONHCH ₂ CH ₂ OCOCH=CH ₂

Synthesis Example 19

In a 100 mL three-necked flask equipped with a reflux condenser, thermometer, and stirrer, 10.0 g of the perfluoropolyether group-containing silane compound (O) obtained in Synthesis Example 15, and 2-(2-methacryloyloxyethyloxy) 1.52 g of ethyl isocyanato (Karenz (registered trademark) MOI-EG, manufactured by Showa Denko Co., Ltd.) was added, stirred for 1 hour at 25°C under a nitrogen stream, and perfluoropolyether represented by the following formula was obtained. A group-containing silane compound (S) was obtained.

(CH ₃ O) ₂ (CH 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 CH ₂ Si(CH ₃ )(OCH ₃ ) ₂

X=-CONHCH ₂ CH ₂ OCH ₂ CH ₂ OCOC(CH ₃ )=CH ₂

Example 1

Compound (D) obtained in Synthesis Example 4 was dissolved in Novec 7200 (manufactured by 3M) to a concentration of 20 mass% to prepare Surface Treatment Agent 1.

Surface treatment agent 1 prepared above was vacuum deposited on chemically strengthened glass (“Gorilla” glass manufactured by Corning, thickness 0.7 mm). The conditions for the vacuum deposition method were a resistance heating type evaporator chamber size of 1,900 mmϕ, a vacuum degree of 5.0E-05, a current value of 240 A, a voltage of 10 V, and a substrate temperature of 40°C. Next, the vapor-deposited chemically strengthened glass was left to stand in an atmosphere at a temperature of 150°C for 30 minutes, and then allowed to cool to room temperature. Subsequently, the vapor-deposited chemically strengthened glass was irradiated with a ray containing 365 nm UV light in an air atmosphere at an intensity of 1000 mJ/cm 2 to form a surface treatment layer on the glass substrate.

Example 2

A surface treatment agent was prepared in the same manner as in Example 1, except that the compound (F) obtained in Synthesis Example 6 was used instead of the compound (D), and a surface treatment layer was formed.

Example 3

A surface treatment agent was prepared in the same manner as in Example 1, except that compound (H) obtained in Synthesis Example 8 was used instead of compound (D), and a surface treatment layer was formed.

Example 4

A surface treatment agent was prepared in the same manner as in Example 1, except that compound (J) obtained in Synthesis Example 10 was used instead of compound (D), and a surface treatment layer was formed.

Example 5

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

Example 6

A surface treatment agent was prepared in the same manner as in Example 1, except that compound (M) obtained in Synthesis Example 13 was used instead of compound (D), and a surface treatment layer was formed.

Example 7

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

Example 8

A surface treatment agent was prepared in the same manner as in Example 1, except that the compound (P) obtained in Synthesis Example 16 was used instead of the compound (D), and a surface treatment layer was formed.

Example 9

A surface treatment agent was prepared in the same manner as in Example 1, except that the compound (R) obtained in Synthesis Example 18 was used instead of the compound (D), and a surface treatment layer was formed.

Example 10

A surface treatment agent was prepared in the same manner as in Example 1, except that the compound (S) obtained in Synthesis Example 19 was used instead of the compound (D), and a surface treatment layer was formed.

Comparative Example 1

Surface treatment agent 2 was prepared by dissolving the following compound (T) in Novec 7200 (manufactured by 3M) at a concentration of 20% by mass.

CF ₃ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ CON{CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ } ₂

The surface treatment agent 2 prepared above was vacuum deposited on chemically strengthened glass (“Gorilla” glass manufactured by Corning, thickness 0.7 mm). The conditions for the vacuum deposition method were a resistance heating type evaporator chamber size of 1,900 mmϕ, a vacuum degree of 5.0E-05, a current value of 240 A, a voltage of 10 V, and a substrate temperature of 40°C. Next, the vapor-deposited chemically strengthened glass was left to stand in an atmosphere at a temperature of 150°C for 30 minutes, and then allowed to cool to room temperature to form a surface treatment layer on the glass substrate.

Comparative Example 2

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

CF ₃ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Comparative Example 3

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

CF ₃ CF ₂ CF ₂ O{CF(CF ₃ )CF ₂ O} ₁₁ CF(CF ₃ )CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Comparative Example 4

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

CF ₃ CF ₂ CF ₂ O(CF ₂ CF ₂ CF ₂ CF ₂ O) ₂₅ CF ₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Comparative Example 5

A surface treatment agent was prepared in the same manner as in Comparative Example 1, except that the following compound (X) was used instead of compound (T), 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 Si(OCH ₃ ) ₃

Comparative Example 6

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

(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

<Evaluation>

For each of the glass substrates with a surface treatment layer obtained above, the water contact angle was measured and the alkaline test was evaluated as follows.

(Alkali immersion test)

A PTFE O-ring with a diameter of 1 cm was installed on the surface of the substrate surface-treated in Examples 1 to 10 and Comparative Examples 1 to 6, and an 8N NaOH solution (alkaline aqueous solution) was dropped into the O-ring to form a surface. The surface of the treated layer was brought into contact with an aqueous alkaline solution and subjected to an alkali immersion test. After 20 to 300 minutes of the alkali immersion test, the aqueous alkaline solution was wiped off, washed with pure water and ethanol, and then the contact angle with water was measured. In addition, the static contact angle of water was measured by depositing 2 μL of pure water on the surface of the glass substrate after the above-described alkali immersion test and using a contact angle meter (Kyowa Kaimen Chemical Co., Ltd.: Automatic contact angle meter DropMaster701). The contact angle was measured. The static contact angle of water after the alkali immersion test was measured at five locations. If the measured value of the static contact angle of water decreased within 300 minutes, the alkali immersion test was stopped midway. The relationship between the immersion time and the average value of the contact angles at five locations is shown in the table below.

(Abrasion durability test)

The sample article on which the surface treatment layer was formed is placed horizontally, the friction element shown below is brought into contact with the surface of the surface treatment layer (the contact surface is a circle with a diameter of 1 cm), and a load of 5 N is applied thereon. After that, the load is applied. The friction element was reciprocated at a speed of 40 mm/sec. The friction element was reciprocated up to 4000 times, and the static contact angle (°) of water was measured for every 1000 reciprocations (number of frictions). The test was stopped when the measured static contact angle of water became less than 60°. In addition, the static contact angle of water was measured in the same manner as the alkaline test described above. The results are shown in the table below.

·Frictioner

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

Composition of artificial sweat:

Disodium hydrogen phosphate anhydrous: 2g

Sodium chloride: 20g

85% lactic acid: 2g

Histidine hydrochloride: 5g

Distilled water: 1Kg

Silicone rubber processed products:

Silicone rubber stopper SR-51 made by Tigers Polymer was processed into a column shape with a diameter of 1 cm and a thickness of 1 cm.

The fluoropolyether group-containing acrylic compound of the present disclosure can be suitably used to form a surface treatment layer on a variety of substrates, especially on the surface of an optical member requiring friction durability.

Claims (24)

Equation (1) or (2) below:

[Formula:
R ^F1 is Rf ¹ -R ^F -O _q -,
R ^F2 is -Rf ² _p -R ^F -O _q -,
Rf ¹ is a C _1-16 alkyl group which may be substituted with one or more fluorine atoms,
Rf ² is a C _1-6 alkylene group which may be substituted with one or more fluorine atoms,
R ^F is each independently a divalent fluoropolyether group,
p is 0 or 1,
q is each independently 0 or 1,
X ^A is each independently a single bond or a divalent organic group,
^Each of
R ^Si is independently -X ^C -SiR ¹ _n' R ² _3-n' in each occurrence,
X ^C is a divalent organic group having 1 to 10 carbon atoms,
R ¹ is independently a hydroxyl group or a hydrolyzable group in each occurrence,
R ² is independently a hydrogen atom or a monovalent organic group in each occurrence,
n' is an integer from 1 to 3,
R ^Ac is, independently in each occurrence, -X ^D -X ^E (-X ^F -OCO-CR ⁵ =CH ₂ ) _m' ,
X ^D is a single bond or a divalent organic group,
X ^E is a single bond or a (m'+1) valent group,
X ^F is, in each occurrence, independently a single bond or a divalent organic group,
R ⁵ is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 8 carbon atoms,
m' is an integer from 1 to 10,
n is each independently an integer from 1 to 10,
m is each independently an integer from 1 to 10]
Compounds represented by . According to paragraph 1,
R ^F is independently for each occurrence, in the equation:
-(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 is independently a hydrogen atom, a fluorine atom, or a chlorine atom in each occurrence,
a, b, c, d, e and f are each independently an integer from 0 to 200, and the sum of a, b, c, d, e and f is 1 or more, and a, b, c, d, The order of existence of each repeating unit enclosed in parentheses by adding e or f is arbitrary in the formula, provided that when all R ^Fa is a hydrogen atom or a chlorine atom, at least one of a, b, c, e and f is, [is more than 1]
A radical, a compound, denoted by . According to claim 1 or 2,
R ^Fa is a fluorine atom. According to any one of claims 1 to 3,
R ^F is, at each occurrence, independently of the following formula (f1), (f2), (f3), (f4), (f5) or (f6):
-(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1)
[Wherein, d is an integer from 1 to 200, and e is 0 or 1],
-(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f2)
[Wherein, c and d are each independently an integer of 0 to 30;
e and f are each independently an integer 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 enclosed in parentheses with the subscript c, d, e or f is arbitrary in the formula],
-(R ⁶ -R ⁷ ) _g -R ⁹ - (f3)
[Wherein, 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 and
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 two or three groups independently selected from these groups. It is a combination,
g is an integer from 2 to 100,
g' is an integer from 2 to 100,
R ^r is,

(In the formula, * indicates the binding position)
lim];
-(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 between 1 and 200, and a, b, c, d, and f are each independently integers between 0 and 200, and is the sum of a, b, c, d, e, and f. is at least 1, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f 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 between 1 and 200, and a, b, c, d, and e are each independently integers between 0 and 200, and is the sum of a, b, c, d, e, and f. is at least 1, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in the formula]
A radical, a compound, denoted by . According to any one of claims 1 to 4,
Each occurrence of Rf ¹ is independently a C _1-16 perfluoroalkyl group,
A compound in which Rf ² is independently a C _1-6 perfluoroalkylene group in each occurrence. According to any one of claims 1 to 5,
X ^A is each independently a single bond or a divalent organic group not containing a urethane bond. According to any one of claims 1 to 6,
X ^A is, each independently, a single bond, or
-(C _α R ¹¹ _2α ) _s1 -R ¹² _t1 -
[Formula:
R ¹¹ is independently a hydrogen atom or a fluorine atom in each occurrence,
α is an integer from 1 to 10, independently for each occurrence,
R ¹² is, in each occurrence, independently -O-, -CO-, -NR ¹⁰ -, -CONR ¹⁰ -, -NR ¹⁰ CO-, -COO-, or -OCO-,
R ¹⁰ is a hydrogen atom or a C _1-6 alkyl group,
s1 is an integer from 0 to 3,
t1 is an integer from 0 to 3,
The sum of s1 and t1 is 1 or more,
The order of existence of each repeating unit enclosed in parentheses with s1 or t1 is arbitrary in the equation]
A radical, a compound, denoted by . In clause 7,
^{and ​} _{​ ​ ​ ​ ​ ​ ​ ​}
R ¹⁰ is a hydrogen atom or a C _1-6 alkyl group,
α1 is an integer from 1 to 10,
α2 is an integer from 0 to 6,
α3 is an integer from 0 to 6,
α4 is an integer from 0 to 6. According to clause 8,
X ^A is -CONR ¹⁰ -C _α1 H _2α1 -, a compound. According to any one of claims 1 to 9,
X ^B is a trivalent group, n is 1, and m is 1. According to any one of claims 1 to 10,
X ^B is,

[Wherein, R ⁸ is a hydrogen atom or a C _1-6 alkyl group]
, n is 1, and m is 1. According to any one of claims 1 to 11,
X ^C is,
C _1-6 alkylene group,
-(CH ₂ ) _z1 -O-(CH ₂ ) _z2 - (wherein, z1 is an integer from 0 to 6, and z2 is an integer from 0 to 6),
-(CH ₂ ) _z3 -phenylene-(CH ₂ ) _z4 - (wherein, z3 is an integer of 0 to 6, and z4 is an integer of 0 to 6), or
-(CH ₂ ) _z13 -OCONH-(CH ₂ ) _z14 - (wherein, z13 is an integer of 0 to 6, and z14 is an integer of 0 to 6). According to any one of claims 1 to 12,
X ^C is a C _1-6 alkylene group. According to any one of claims 1 to 13,
n' is 2 or 3, compound. According to any one of claims 1 to 14,
n' is 3, compound. According to any one of claims 1 to 15,
X ^E is a single bond compound. According to any one of claims 1 to 15,
X ^E is -X ^G -X ^H ,
X ^G is,
single bond,
C _1-6 alkylene group,
-(CH ₂ ) _z9 -O-(CH ₂ ) _z10 - (wherein, z9 is an integer from 0 to 6, and z10 is an integer from 0 to 6), or,
-(CH ₂ ) _z11 -phenylene-(CH ₂ ) _z12 - (wherein, z11 is an integer of 0 to 6, and z12 is an integer of 0 to 6)
and
X ^H is

and
A compound in which R ⁸ is a hydrogen atom or a C _1-6 alkyl group. According to any one of claims 1 to 17,
X ^D is -o-, -co-, -coo-, -oco-, -conh-, -nhco-, -Oconh-, -nhcoo-, -nh-co-nh-, -CH ₂ ch )CH ₂ -, -CH(CH ₂ OH)CH ₂ -,

[Wherein, * and ** represent the binding position, * is bonded to X ^B , and ** is bonded to X ^E ]. According to any one of claims 1 to 18,
X ^F is,
single bond,
C _1-6 alkylene group,
-(CH ₂ ) _z5 -O-(CH ₂ ) _z6 - (wherein, z5 is an integer from 0 to 6, and z6 is an integer from 0 to 6), or,
-(CH ₂ ) _z7 -phenylene-(CH ₂ ) _z8 - (wherein, z7 is an integer of 0 to 6, and z8 is an integer of 0 to 6). According to any one of claims 1 to 19,
A compound in which R ⁵ is a hydrogen atom or a methyl group. A surface treatment agent containing the compound according to any one of claims 1 to 20. According to clause 21,
A surface treatment agent further containing one or more other components selected from fluorine-containing oil, silicone oil, and catalyst. According to claim 21 or 22,
A surface treatment agent used as an antifouling or waterproof coating. A substrate and a compound according to any one of claims 1 to 20 on the surface of the substrate, or
An article comprising a layer formed with the surface treatment agent according to any one of claims 21 to 23.