CN118201984A - Surface treatment agent - Google Patents

Abstract

The present invention provides a compound represented by the following formula (1) or (2) (wherein each symbol has the same meaning as described in the specification.) .R^F1-X^A-X^BR^Si _nR^Ac _m (1)R^Ac _mR^Si _nX^B-X^A-R^F2-X^A-X^BR^Si _nR^Ac _m (2).

Description

Surface treating agent

Technical Field

The present invention relates to novel fluorinated polyether group-containing acrylic compounds and surface treatment agents containing such compounds.

Background

It is known that a certain fluorinated polyether-based silane compound can provide excellent water repellency, oil repellency, stain resistance, and the like when used for the surface treatment of a substrate. A layer obtained from a surface treatment agent containing a fluorinated polyether group-containing silane compound (hereinafter also referred to as "surface treatment layer") has been used as a so-called functional film for various substrates such as glass, plastic, fiber, sanitary products, and building materials (patent document 1).

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open publication No. 2003-238577

Disclosure of Invention

Technical problem to be solved by the invention

The fluorinated polyether group-containing silane compound described in patent document 1 can provide a surface-treated layer having an excellent function, but a surface-treated layer having higher durability is required.

The purpose of the present invention is to provide a fluorinated polyether-based compound that can form a surface-treated layer that has excellent durability.

Technical scheme for solving technical problems

The present invention includes the following means.

[1] A compound represented by the following formula (1) or (2):

R^F1-X^A-X^B R^Si _nR^AC _m (1)

R^Ac _mR^Si _nX^B-X^A-R^F2-X^A-X^B R^Si _nR^Ac _m (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 1 or more fluorine atoms,

Rf ² is a C _1-6 alkylene group which may be substituted with 1 or more fluorine atoms,

R ^F are each independently a divalent fluoropolyether group,

P is either 0 or 1 and,

Q is each independently 0 or 1,

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

X ^B is a group having a valence of (m+n+1) and having 1 to 10 carbon atoms and not containing Si atom,

R ^Si is independently at each occurrence-X ^C-SiR¹ _n,R² _3-n',

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

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

R ² is independently at each occurrence a hydrogen atom or a 1-valent organic group,

N' is an integer of 1 to 3,

R ^Ac is independently at each occurrence-X ^D-X^E(-X^F-OCO-CR⁵＝CH₂)_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 independently a single bond or a divalent organic group having 1 to 10 carbon atoms at each occurrence,

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

M' is an integer of 1 to 10,

N is each independently an integer of 1 to 10,

M is each independently an integer of 1 to 10. ].

[2] The compound according to the above item [1], wherein R ^F is each independently a group represented by the following formula:

－(OC₆F₁₂)_a－(OC₅F₁₀)_b－(OC₄F₈)_c－(OC₃R^Fa ₆)_d－(OC₂F₄)_e－(OCF₂)_f－

[ wherein R ^Fa is independently a hydrogen atom, a fluorine atom or a chlorine atom at each occurrence, a, b, c, d, e and f are each independently integers of 0 to 200, and the sum of a, b, c, d, e and f is 1 or more, the order of presence of the repeating units indicated by a, b, c, d, e or f and bracketed is arbitrary in the formula, wherein at least 1 of a, b, c, e and f is 1 or more in the case where all R ^Fa are hydrogen atoms or chlorine atoms. ].

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

[4] The compound according to any one of the above [1] to [3], wherein R ^F is independently a group represented by the following formula (f 1), (f 2), (f 3), (f 4), (f 5) or (f 6) at each occurrence:

－(OC₃F₆)_d－(OC₂F₄)_e－ (f1)

In the formula (f 1), d is an integer of 1 to 200, and e is 0 or 1. The ];

－(OC₄F₈)_c－(OC₃F₆)_d－(OC₂F₄)_e－(OCF₂)_f－ (f2)

[ in the formula (f 2), c and d are each independently an integer of 0 to 30;

e and f are each independently integers from 1 to 200;

c. d, e and f are integers from 10 to 200;

the order of presence of the repeating units indicated by subscripts c, d, e, or f and bracketed is arbitrary in the formula. The ];

－(R⁶－R⁷)_g－R⁹－ (f3)

[ in formula (f 3), R ⁶ is OCF ₂ or OC ₂F₄;

R ⁷ is a group selected from OC ₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀ and OC ₆F₁₂, or a combination of 2 or 3 groups selected from these groups;

R ⁹ is a single bond or a group selected from OCF₂、OC₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀ and OC ₆F₁₂;

g is an integer of 2 to 100. The ];

－(R⁶－R⁷)_g－R^r－(R^7'－R^6')_g'－ (f4)

[ in formula (f 4), R ⁶ is OCF ₂ or OC ₂F₄;

r ⁷ is a group selected from OC ₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀ and OC ₆F₁₂, or a combination of 2 or 3 groups independently selected from these groups;

R ^6' is OCF ₂ or OC ₂F₄;

R ^7' is a group selected from OC ₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀ and OC ₆F₁₂, or a combination of 2 or 3 groups independently selected from these groups;

g is an integer of 2 to 100;

g' is an integer of 2 to 100;

R ^r is

(Wherein, the term "represents a bonding position"). The ];

－(OC₆F₁₂)_a－(OC₅F₁₀)_b－(OC₄F₈)_c－(OC₃F₆)_d－(OC₂F₄)_e－(OCF₂)_f－(f5)

[ in formula (f 5), e is an integer of 1 to 200, a, b, c, d and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is at least 1, and the order of presence of the repeating units denoted by a, b, c, d, e or f and bracketed is arbitrary in the formula. The ];

－(OC₆F₁₂)_a－(OC₅F₁₀)_b－(OC₄F₈)_c－(OC₃F₆)_d－(OC₂F₄)_e－(OCF₂)_f－(f6)

[ in formula (f 6), f is an integer of 1 to 200, a, b, c, d and e are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is at least 1, and the order of presence of the repeating units denoted by a, b, c, d, e or f and bracketed is arbitrary in the formula. ].

[5] The compound according to any one of the above [1] to [4], wherein Rf ¹ is independently a C _1－16 perfluoroalkyl group at each occurrence,

Rf ² is independently at each occurrence 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 containing no urethane bond.

[7] The compound according to any one of the above [1] to [6], wherein X ^A is each independently a single bond or a group represented by the following formula:

－(C_αR¹¹ _2α)_s1－R¹² _t1－

[ formula:

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

Alpha is independently an integer of 1 to 10 for each occurrence,

R ¹² is independently at each occurrence-O-; -CO-, -NR ¹⁰－、－CONR¹⁰－、－NR¹⁰ CO-, -COO-or-OCO-,

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

S1 is an integer of 0 to 3,

T1 is an integer of 0 to 3,

The total of s1 and t1 is 1 or more,

The order of presence of the repeating units denoted by s1 or t1 and bracketed is arbitrary in the formula. ].

[8] The compound according to the above [7], wherein X ^A is-CONR ¹⁰－C_α1H_2α1－、－(C_α2H_2α2)－O－(C_{α 3}H_2α3) -or-C _α4H_2α4 -,

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

Alpha 1 is an integer of 1 to 10,

Alpha 2 is an integer of 0 to 6,

Alpha 3 is an integer of 0 to 6,

Alpha 4 is an integer of 0 to 6.

[9] The compound according to the above [8], wherein X ^A is-CONR ¹⁰－C_α1H_2α1 -.

[10] The compound according to any one of [1] to [9], wherein X ^B is a 3-valent group, n is 1, and m is 1.

[11] The compound according to any one of the above [1] to [10], wherein X ^B is the following group:

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

N is 1 and m is 1.

[12] The compound according to any one of the above [1] to [11], wherein X ^C is a C _1－6 alkylene group, - (CH ₂)_z1－O－(CH₂)_z2 - (wherein z1 is an integer of 0 to 6), z2 is an integer of 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－(CH₂)_z14 - (wherein z13 is an integer of 0 to 6, and z14 is an integer of 0 to 6).

[13] The compound according to any one of the above [1] to [12], 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], wherein X ^E is a single bond.

[17] The compound according to any one of the above [1] to [15], wherein X ^E is-X ^G－X^H,

X ^G is a single bond, C _1－6 alkylene, - (CH ₂)_z9－O－(CH₂)_z10 - (wherein z9 is an integer of 0 to 6, z10 is an integer of 0 to 6), or- (CH ₂)_z11 -phenylene- (CH ₂)_z12 - (wherein z11 is an integer of 0 to 6, z12 is an integer of 0 to 6)), a catalyst for the preparation of a pharmaceutical composition,

X ^H is the following group:

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

[18] The compound according to any one of the above [1] to [17], wherein X ^D is －O－、－CO－、－COO－、－OCO－、－CONH－、－NHCO－、－OCONH－、－NHCOO－、－NH－CO－NH－、－CH₂CH(OH)CH₂－、－CH(CH₂OH)CH₂－、

Wherein < CHEM > represents a bonding position, is bonded to X ^B, and is bonded to X ^E. ].

[19] The compound according to any one of the above [1] to [18], wherein X ^F is a single bond, C _1－6 alkylene, - (CH ₂)_z5－O－(CH₂)_z6 - (wherein z5 is an integer of 0 to 6, and z6 is an integer of 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).

[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 treating agent comprising the compound of any one of the above [1] to [20 ].

[22] The surface treatment agent according to the above [21], which further contains 1 or more other components selected from fluorine-containing oil, silicone oil and catalyst.

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

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

Effects of the invention

The present invention can provide a fluorinated polyether-based acrylic compound capable of forming a surface-treated layer having excellent durability.

Detailed Description

As used herein, "1-valent organic group" refers to a 1-valent group that contains carbon. The 1-valent organic group is not particularly limited, and may be a hydrocarbon group or a derivative thereof. The derivative of the hydrocarbon group means a group having 1 or more N, O, S, si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, or the like at the end of the hydrocarbon group or in the molecular chain. In addition, in the case of simply referred to as "organic group", it means an organic group having 1 valence. In addition, "2-valent organic group" means a 2-valent group containing carbon. The organic group having a valence of 2 is not particularly limited, and examples thereof include a valence-2 group in which 1 hydrogen atom is removed from the organic group.

As used herein, "hydrocarbyl" is a group containing carbon and hydrogen, and refers to a group that has 1 hydrogen atom removed from a hydrocarbon. Examples of the hydrocarbon group include, but are not particularly limited to, a C _1-20 hydrocarbon group which may be substituted with 1 or more substituents, for example, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and the like. The "aliphatic hydrocarbon group" may be any of linear, branched, and cyclic, or may be any of saturated or unsaturated. The hydrocarbon group may further contain 1 or more ring structures.

As used in the present specification, the substituent of the "hydrocarbon group" is not particularly limited, and examples thereof include: a halogen atom; 1 or more groups selected from the group consisting of C _1-6 alkyl, C _2-6 alkenyl, C _2-6 alkynyl, C _3-10 cycloalkyl, C _3-10 unsaturated cycloalkyl, 5-10 membered heterocyclic group, 5-10 membered unsaturated heterocyclic group, C _6-10 aryl and 5-10 membered heteroaryl which may be substituted with 1 or more halogen atoms.

As used herein, "hydrolyzable group" refers to a group capable of undergoing a hydrolysis reaction, that is, a group capable of being detached from the main skeleton of a compound by a hydrolysis reaction. Examples of the hydrolyzable group include-OR ^h、-OCOR^h、-O-N＝CR^h ₂、-NR^h ₂、-NHR^h, -NCO, and halogen (in these formulae, R ^h represents a substituted OR unsubstituted C _1-4 alkyl group).

The fluorinated polyether group-containing acrylic compound of the present invention is a fluorinated polyether group-containing acrylic compound represented by the following formula (1) or (2):

R^F1-X^A-X^B R^Si _nR^Ac _m (1)

R^AC _mR^Si _nX^B-X^A-R^F2-X^A-X^B R^Si _nR^Ac _m (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 1 or more fluorine atoms,

Rf ² is a C _1-6 alkylene group which may be substituted with 1 or more fluorine atoms,

R ^F are each independently a divalent fluoropolyether group,

P is either 0 or 1 and,

Q is each independently 0 or 1,

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

X ^B is a group having a valence of (m+n+1) and having 1 to 10 carbon atoms and not containing Si atom,

R ^Si is independently at each occurrence-X ^C－SiR¹ _n'R² _3－n',

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

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

R ² is independently at each occurrence a hydrogen atom or a 1-valent organic group,

N' is an integer of 1 to 3,

R ^Ac is independently at each occurrence-X ^D－X^E(－X^F－OCO－CR⁵＝CH₂)_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 independently a single bond or an organic group at each occurrence,

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

M' is an integer of 1 to 10,

N is each independently an integer of 1 to 10,

M is each independently an integer of 1 to 10. ].

In formula (1), R ^F1 is Rf ¹－R^F－O_q -.

In 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 1 or more fluorine atoms.

The "C _1－16 alkyl group" in the above-mentioned C _1－16 alkyl group which may be substituted with 1 or more fluorine atoms may be a straight chain or branched, preferably a straight chain or branched C _1－6 alkyl group, particularly a C _1－3 alkyl group, more preferably a straight chain C _1－6 alkyl group, particularly a C _1－3 alkyl group.

The above-mentioned Rf ¹ is preferably a C _1－16 alkyl group which may be substituted with 1 or more fluorine atoms, more preferably a CF ₂H－C_1－15 perfluoroalkylene group, and still more preferably a C _1－16 perfluoroalkyl group.

The abovementioned C _1－16 perfluoroalkyl group may be straight-chain or branched, preferably straight-chain or branched, C _1－6 perfluoroalkyl, in particular C _1－3 perfluoroalkyl, more preferably straight-chain, C _1－6 perfluoroalkyl, in particular C _1－3 perfluoroalkyl, in particular-CF ₃、－CF₂CF₃ or-CF ₂CF₂CF₃.

In the above formula, rf ² is a C _1－6 alkylene group which may be substituted with 1 or more fluorine atoms.

The "C _1－6 alkylene group" in the above-mentioned C _1－6 alkylene group which may be substituted with 1 or more fluorine atoms may be a straight chain or a branched chain, and is preferably a straight chain or branched C _1－3 alkylene group, and more preferably a straight chain C _1－3 alkylene group.

The above-mentioned Rf ² is preferably a C _1－6 alkylene group which may be substituted with 1 or more fluorine atoms, more preferably a C _1－6 perfluoroalkylene group, and still more preferably a C _1－3 perfluoroalkylene group.

The C _1－6 perfluoroalkylene group may be a linear or branched C _1－3 perfluoroalkylene group, preferably a linear or branched C _1－3 perfluoroalkyl group, more preferably-CF ₂－、－CF₂CF₂ -or-CF ₂CF₂CF₂ -.

In the above formula, p is 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.

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

In the above formulas (1) and (2), R ^F is independently a 2-valent fluoropolyether group at each occurrence.

R ^F may preferably comprise the following groups:

－(OC_h1R^Fa _2h1)_h3－(OC_h2R^Fa _2h2－2)_h4－

[ formula:

r ^Fa is independently at each occurrence a hydrogen atom, a fluorine atom or a chlorine atom,

H1 is an integer of 1 to 6,

H2 is an integer of 4 to 8,

H3 is an integer of 0 or more,

H4 is an integer of 0 or more,

Wherein the total of h3 and h4 is 1 or more, preferably 2 or more, more preferably 5 or more, and the order of the presence of the repeating units denoted by h3 and h4 and bracketed is arbitrary in the formula. ].

In one embodiment, R ^F may be linear or branched. R ^F is preferably a group of the formula:

－(OC₆F₁₂)_a－(OC₅F₁₀)_b－(OC₄F₈)_c－(OC₃R^Fa ₆)_d－(OC₂F₄)_e－(OCF₂)_f－

[ formula:

r ^Fa is independently at each occurrence a hydrogen atom, a fluorine atom or a chlorine atom,

A. b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is 1 or more. The order of presence of the repeating units labeled a, b, c, d, e or f and bracketed is arbitrary in the formula. Wherein, when all R ^Fa are hydrogen atoms or chlorine atoms, at least 1 of a, b, c, e and f is 1 or more. ].

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

A. b, c, d, e and f may preferably each independently be an integer from 0 to 100.

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

These repeating units may be linear or branched, or may include a ring structure. For example, - (OC ₆F₁₂) -may be －(OCF₂CF₂CF₂CF₂CF₂CF₂)－、－(OCF(CF₃)CF₂CF₂CF₂CF₂)－、－(OCF₂CF(CF₃)CF₂CF₂CF₂)－、－(OCF₂CF₂CF(CF₃)CF₂CF₂)－、－(OCF₂CF₂CF₂CF(CF₃)CF₂)－、－(OCF₂CF₂CF₂CF₂CF(CF₃))－ or the like. - (OC ₅F₁₀) -may be －(OCF₂CF₂CF₂CF₂CF₂)－、－(OCF(CF₃)CF₂CF₂CF₂)－、－(OCF₂CF(CF₃)CF₂CF₂)－、－(OCF₂CF₂CF(CF₃)CF₂)－、－(OCF₂CF₂CF₂CF(CF₃))－, etc. - (OC ₄F₈) -can be any of －(OCF₂CF₂CF₂CF₂)－、－(OCF(CF₃)CF₂CF₂)－、－(OCF₂CF(CF₃)CF₂)－、－(OCF₂CF₂CF(CF₃))－、－(OC(CF₃)₂CF₂)－、－(OCF₂C(CF₃)₂)－、－(OCF(CF₃)CF(CF₃))－、－(OCF(C₂F₅)CF₂)－ and- (OCF ₂CF(C₂F₅)) -. - (OC ₃F₆) - (i.e. in the above formula, R ^Fa is a fluorine atom) may be any of- (OCF ₂CF₂CF₂)－、－(OCF(CF₃)CF₂) -and- (OCF ₂CF(CF₃)) -. - (OC ₂F₄) -can be any of- (OCF ₂CF₂) -and- (OCF (CF ₃)) -.

In one embodiment, R ^F may comprise a ring structure.

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

[ Wherein, the formula (I) represents a bonding position. ]

The above-mentioned ring structure may be preferably a four-membered ring, a five-membered ring or a six-membered ring, more preferably a four-membered ring or a six-membered ring.

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

[ Wherein, the formula (I) represents a bonding position. ]

In one embodiment, the repeating unit is linear. By making the repeating unit linear, the surface smoothness, wear durability, and the like of the surface treatment layer can be improved.

In one embodiment, the repeating unit is branched. By forming the repeating unit into a branched chain, the coefficient of dynamic friction of the surface treatment layer can be increased.

In one embodiment, each occurrence of R ^F is independently a group represented by any of the following formulas (f 1) to (f 6).

－(OC₃F₆)_d－(OC₂F₄)_e－ (f1)

In the formula (f 1), d is an integer of 1 to 200, and e is 0 or 1, preferably 1.]

－(OC₄F₈)_c－(OC₃F₆)_d－(OC₂F₄)_e－(OCF₂)_f－ (f2)

[ In formula (f 2), c and d are each independently an integer of 0 to 30, e and f are each independently an integer of 1 to 200,

C. d, e and f are added to 2 or more,

The order of presence of the repeating units indicated by subscripts c, d, e, or f and bracketed is arbitrary in the formula. ]

－(R⁶－R⁷)_g－R⁹－ (f3)

[ In formula (f 3), R ⁶ is OCF ₂ or OC ₂F₄,

R ⁷ is a group selected from OC ₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀ and OC ₆F₁₂, or a combination of 2 or 3 groups independently selected from these groups,

R ⁹ is a single bond or a group selected from OCF₂、OC₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀ and OC ₆F₁₂;

g is an integer of 2 to 100. ]

－(R⁶－R⁷)_g－R^r－(R^7'－R^6')_g'－ (f4)

[ In formula (f 4), R ⁶ is OCF ₂ or OC ₂F₄,

R ⁷ is a group selected from OC ₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀ and OC ₆F₁₂, or a combination of 2 or 3 groups independently selected from these groups,

R ^6' is OCF ₂ or OC ₂F₄,

R ^7' is a group selected from OC ₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀ and OC ₆F₁₂, or a combination of 2 or 3 groups independently selected from these groups,

G is an integer of 2 to 100,

G' is an integer of 2 to 100,

R ^r is

(Wherein, the term "represents a bonding position"). ]

－(OC₆F₁₂)_a－(OC₅F₁₀)_b－(OC₄F₈)_c－(OC₃F₆)_d－(OC₂F₄)_e－(OCF₂)_f－ (f5)

In the formula (f 5), e is an integer of 1 to 200, a, b, c, d and f are each independently an integer of 0 to 200, and the order of presence of the repeating units denoted by a, b, c, d, e or f and bracketed is arbitrary in the formula. ]

－(OC₆F₁₂)_a－(OC₅F₁₀)_b－(OC₄F₈)_c－(OC₃F₆)_d－(OC₂F₄)_e－(OCF₂)_f－ (f6)

In the formula (f 6), f is an integer of 1 to 200, a, b, c, d and e are each independently an integer of 0 to 200, and the order of presence of the repeating units denoted by a, b, c, d, e or f and bracketed is arbitrary in the formula. ]

In the above formula (f 1), d is an integer of preferably 5 to 200, more preferably 10 to 100, still more preferably 15 to 50, for example 25 to 35. In one embodiment, e is 1. In another embodiment, e is 0. (OC ₃F₆) in the above formula (f 1) is preferably a group represented by (OCF ₂CF₂CF₂)、(OCF₂CF(CF₃)) or (OCF (CF ₃)CF₂), more preferably a group represented by- (OCF ₂CF₂CF₂)_d) -and (OC ₂F₄) in the above formula (f 1) is preferably a group represented by (OCF ₂CF₂) or (OCF (CF ₃)), more preferably a group represented by (OCF ₂CF₂).

In the above formula (f 2), e and f are each independently an integer of preferably 5 to 200, more preferably 10 to 200. The sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be 15 or more or 20 or more, for example. In one embodiment, the formula (f 2) is preferably a group represented by －(OCF₂CF₂CF₂CF₂)_c－(OCF₂CF₂CF₂)_d－(OCF₂CF₂)_e－(OCF₂)_f－. In another embodiment, formula (f 2) may be a group represented by- (OC ₂F₄)_e－(OCF₂)_f -).

In the above formula (f 3), R ⁶ is preferably OC ₂F₄. In the above (f 3), R ⁷ is preferably a group selected from OC ₂F₄、OC₃F₆ and OC ₄F₈, or a combination of 2 or 3 groups independently selected from these groups, more preferably a group selected from OC ₃F₆ and OC ₄F₈. The combination of 2 or 3 groups independently selected from OC ₂F₄、OC₃F₆ and OC ₄F₈ is not particularly limited, and examples thereof include －OC₂F₄OC₃F₆－、－OC₂F₄OC₄F₈－、－OC₃F₆OC₂F₄－、－OC₃F₆OC₃F₆－、－OC₃F₆OC₄F₈－、－OC₄F₈OC₄F₈－、－OC₄F₈OC₃F₆－、－OC₄F₈OC₂F₄－、－OC₂F₄OC₂F₄OC₃F₆－、－OC₂F₄OC₂F₄OC₄F₈－、－OC₂F₄OC₃F₆OC₂F₄－、－OC₂F₄OC₃F₆OC₃F₆－、－OC₂F₄OC₄F₈OC₂F₄－、－OC₃F₆OC₂F₄OC₂F₄－、－OC₃F₆OC₂F₄OC₃F₆－、－OC₃F₆OC₃F₆OC₂F₄－ and-OC ₄F₈OC₂F₄OC₂F₄ -. In one embodiment, R ⁹ is a single bond. In another embodiment, R ⁹ is a group selected from OCF₂、OC₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀ and OC ₆F₁₂. In the above formula (f 3), g is an integer of preferably 3 or more, more preferably 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f 3), OC ₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀ and OC ₆F₁₂ may be any of linear or branched chains, and are preferably linear. In this embodiment, R ⁶－R⁷)_g is preferably- (OC ₂F₄－OC₃F₆)_g -or- (OC ₂F₄－OC₄F₈)_g -).

In the above formula (f 4), R ⁶、R⁷ and g have the same meanings as those described in the above formula (f 3). R ^6'、R^7' and g' have the same meanings as R ⁶、R⁷ and g described in formula (f 3) above, respectively. R ^r is preferably

[ Wherein, the formula (I) represents a bonding position. More preferably ]

[ Wherein, the formula (I) represents a bonding position. ].

In the above formula (f 5), e is an integer of preferably 1 to 100, more preferably 5 to 100. a. The sum of 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 (f 6), f is an integer of preferably 1 to 100, more preferably 5 to 100. a. The sum of 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 embodiment, R ^F is a group represented by the formula (f 1) or (f 2).

In one embodiment, R ^F is a group represented by the formula (f 1).

In one embodiment, R ^F is a group represented by the formula (f 2).

In one embodiment, R ^F is a group represented by the formula (f 3).

In one embodiment, R ^F is a group represented by the formula (f 4).

In one embodiment, R ^F is a group represented by the formula (f 5).

In one embodiment, R ^F is a group represented by the formula (f 6).

In R ^F, the ratio of e to f (hereinafter referred to as "e/f ratio") is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, still more preferably 0.2 to 1.5, and still more preferably 0.2 to 0.85. By setting the e/f ratio to 10 or less, the smoothness, abrasion durability, and chemical resistance (e.g., durability against artificial sweat) of the surface-treated layer obtained from the compound are further improved. The smaller the e/f ratio, the higher the smoothness 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 greater the e/f ratio, the greater the stability of the compound.

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

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

In the above-mentioned fluoropolyether group-containing acrylic compound, the number average molecular weight of the R ^F1 and R ^F2 portions is not particularly limited, and is, for example, 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 10,000. In the present specification, the number average molecular weights of R ^F1 and R ^F2 are values measured by ¹⁹ F-NMR.

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

In one embodiment, each X ^A is independently a single bond or a divalent organic group that does not contain urethane linkages.

In a preferred embodiment, each X ^A is independently a single bond or a group of the formula:

－(C_αR¹¹ _2α)_s1－R¹² _t1－

[ formula:

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

Alpha is independently an integer of 1 to 10 for each occurrence,

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

S1 is an integer of 0 to 3,

T1 is an integer of 0 to 3,

The total of s1 and t1 is 1 or more,

The order of presence of the repeating units denoted by s1 or t1 and bracketed is arbitrary in the formula. ]. Wherein, the left side is bonded with R ^F1 or R ^F2.

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

In one embodiment, X ^A is each independently- (C _αR¹¹ _2α)_s1－R¹² _t1) -as described above.

R ¹¹ is preferably a hydrogen atom.

The above α is each independently an integer of preferably 1 to 6, more preferably an integer of 1 to 4, and still more preferably an integer of 2 to 4 at each occurrence.

R ¹² is, independently of one another, preferably-O-, -CO-, -NR ¹⁰ -, -CONH-or-COO-, more preferably-CONH-.

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

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 still more preferably 1.

In a preferred mode of use, the method comprises,

R ¹¹ is a hydrogen atom,

Alpha is an integer of 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, and the number of the groups is 1,

T1 is 0 or 1.

In a more preferred embodiment, X ^A is-CONR ¹⁰－C_α1H_2α1－、－(C_α2H_2α2)－O－(C_α3H_2α3) -or-C _{α 4}H_2α4 -, preferably-CONR ¹⁰－C_α1H_2α1 -. The left side of such a group is bonded to R ^F1 or R ^F2.

Α1 is an integer of 1 to 10.α2 is an integer of 0to 6, for example, an integer of 1 to 6.α3 is an integer of 0to 6, for example, an integer of 1 to 6.α4 is an integer of 0to 6, for example, an integer of 1 to 6.

X ^A is preferably-CONH-C _α1H_2α1 -. The left side of such a group is bonded to R ^F1 or R ^F2.

The above C _α1H_2α1 is preferably (CH ₂)_α1).

The above C _α2H_2α2 is preferably (CH ₂)_α2).

The above C _α3H_2α3 is preferably (CH ₂)_α3).

The above C _α4H_2α4 is preferably (CH ₂)_α4).

In the above formulas (1) and (2), X ^B are each independently a group having a valence of (n+n+1) of 1 to 10 containing no Si atom.

In one embodiment, the above X ^B is a 4-valent group, preferably

In one embodiment, O of-C (-O-) =described above is bonded to R ^Si. In another embodiment, -C (-O-) =o is bonded to R ^Ac.

In one embodiment, X ^B may be a 3-valent group, and may be preferably

[ Wherein R ⁸ is a hydrogen atom or a C _1－6 alkyl group (preferably methyl or ethyl, more preferably methyl). ]. In one embodiment, the-CR ⁸ (-O-) -O is bonded to R ^Si. In another embodiment, -CR ⁸ (-O-) -O is bonded 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 formulae (1) and (2), m is an integer of 1 to 10, and n is an integer of 1 to 10, respectively.

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 formulas (1) and (2) above, R ^Si is independently at each occurrence-X ^C－SiR¹ _n'R² _3－n'.

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

In one embodiment, X ^C is

C _1－6 alkylene,

- (CH ₂)_z1－O－(CH₂)_z2 - (wherein, z1 is an integer of 0 to 6, for example, an integer of 1 to 6, and z2 is an integer of 0 to 6, for example, an integer of 1 to 6)), a catalyst comprising a catalyst having a functional group of the formula (I),

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

- (CH ₂)_z13－OCONH－(CH₂)_z14 - (wherein, z13 is an integer of 0 to 6) and z14 is an integer of 0 to 6).

These groups may be substituted, preferably unsubstituted, with 1 or more substituents selected from the group consisting of a fluorine atom, a C _1－6 alkyl group, a C _2－6 alkenyl group and a C _2－6 alkynyl group, for example. The left side of these groups is bonded to X ^B.

The C _1－6 alkylene group may be linear or branched, and is preferably linear.

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

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

R ¹ is preferably, independently at each occurrence, a hydrolyzable group.

R ¹ is preferably-OR ^h、－OCOR^h、－O－N＝CR^h ₂、－NR^h ₂、－NHR^h, -NCO, OR halogen (in these formulae, R ^h represents a substituted OR unsubstituted C _1－4 alkyl group), more preferably-OR ^h (i.e., alkoxy group), each independently at each occurrence. As R ^h, there may be mentioned: unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, etc.; chloromethyl and the like. Of these, alkyl groups are preferable, and unsubstituted alkyl groups are more preferable. In one embodiment, R ^h is methyl, and in another embodiment, R ^h is ethyl.

Each occurrence of R ² is independently a hydrogen atom or a 1-valent organic group. Such a 1-valent organic group is a 1-valent organic group excluding the above-mentioned hydrolyzable group.

In R ², the organic group having valence 1 is preferably a C _1－20 alkyl group, more preferably a C _1－6 alkyl group, and further preferably a methyl group.

In the above formula, n' is an integer of 1 to 3, preferably 2 or 3, more preferably 3, independently for each (SiR ¹ _n'R² _3－n') unit.

In formulas (1) and (2) above, R ^Ac is independently at each occurrence-X ^D－X^E(－X^F－OCO－CR⁵＝CH₂)_m'.

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

X ^D is preferably-O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -OCONH-, -NHCOO-, -NH-CO-NH-, -CH ₂CH(OH)CH₂ -, or-CH (CH ₂OH)CH₂ -, more preferably-CONH-, -CH ₂CH(OH)CH₂－、－CH(CH₂OH)CH₂ -

Wherein < CHEM > represents a bonding position, is bonded to X ^B, and is bonded to X ^E. ]. The left side of these groups is bonded 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 embodiment, X ^E is a single bond.

In one embodiment, X ^E is a trivalent or tetravalent group of the formula:

－X^G－X^H

[ formula:

X ^G is

A single bond,

C _1－6 alkylene,

- (CH ₂)_z9－O－(CH₂)_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, an integer of 1 to 6), or

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

X ^H is as follows

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

The C _1－6 alkylene group may be linear or branched, and is preferably linear.

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

The above-mentioned C _1－6 alkyl group is preferably a C _1－3 alkyl group, 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 embodiment, X ^F is

A single bond,

C _1－6 alkylene,

- (CH ₂)_z5－O－(CH₂)_z6 - (wherein z5 is an integer of 0 to 6, for example, an integer of 1 to 6, and z6 is an integer of 0 to 6, for example, an integer of 1 to 6)), or

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

These groups may be substituted, preferably unsubstituted, with 1 or more substituents selected from the group consisting of a fluorine atom, a C _1－6 alkyl group, a C _2－6 alkenyl group and a C _2－6 alkynyl group, for example. The left side of these groups is bonded to X ^B.

The C _1－6 alkylene group may be linear or branched, and is preferably linear.

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

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

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, further preferably a C _1－3 alkyl group, and particularly preferably a methyl group.

In one embodiment, R ⁵ is a hydrogen atom.

In one embodiment, R ⁵ is methyl.

The above 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 above formula (1) or (2) is not particularly limited, and may have a number average molecular weight of 5×10 ²～1×10⁵. Within such a range, it is preferable to have a number average molecular weight of 2,000 to 32,000, more preferably 2,500 to 12,000, from the viewpoint of wear durability. The "number average molecular weight" is a value obtained by measurement by ¹⁹ F-NMR.

In one embodiment, the fluorinated polyether group-containing acrylic compound of the present invention is a fluorinated polyether group-containing acrylic compound represented by the formula (1).

In one embodiment, the fluorinated polyether group-containing acrylic compound of the present invention is a fluorinated polyether group-containing acrylic compound represented by the formula (2).

The fluoropolyether group-containing acrylic compound represented by the above formulas (1) and (2) can be obtained by: first, a fluorinated polyether group-containing silane compound having a reactive site such as-NH-, -C (OH) -is prepared, and then, an acrylic compound having an acrylic group is reacted with the reactive site, whereby the fluorinated polyether group-containing acrylic compounds represented by the above formulas (1) and (2) can be obtained.

In one embodiment, the following formula is used: compounds represented by R ^F1－COOR²¹、R²¹OOC－R^F2－COOR²¹ (wherein R ²¹ is a hydrogen atom or a methyl group, and R ^F1 and R ^F2 have the same meanings as described in relation to formulas (1) and (2)) are represented by the following formulas: r ²⁴－R²³－NH－R²²－SiR¹ _n'R² _3－n' (wherein R ²² is a divalent group, R ²³ is a divalent group, R ²⁴ is a reactive group such as NH ₂, and the like, and R ¹、R² and n' have the same meanings as described in relation to formulas (1) and (2)). ) The compound shown in the following formula ：R^F1－R²⁵－R²³－NH－R²²－SiR¹ _n'R² _3－n'、R² _3－n'R¹ _n'Si－R²²－HN－R²³－R²⁵－R^F2－R²⁵－R²³－NH－R²²－SiR¹ _n'R² _3－n' is obtained by reacting the compound shown in the following formula. Next, the above compound is reacted with the following formula: the fluorinated polyether group-containing acrylic compound represented by the above-mentioned formulas (1) and (2) can be obtained by reacting a compound represented by R ³⁴－R³⁵－OCOCH＝CH₂ (wherein R ³⁴ is a reactive group such as-NCO, -COOH or-COOCl, and R ³⁵ is a divalent group) or R ⁵⁶－OCOCR⁵⁷＝CH₂ (wherein R ⁵⁶ is a halogen, H or monovalent hydrocarbon group, and R ⁵⁷ is a hydrogen atom or a C _1－3 alkyl group).

In one embodiment, the following formula is used: the compound represented by R ^F1－COF、FOC－R^F2 -COF (wherein R ^F1 and R ^F2 have the same meanings as described in relation to formulas (1) and (2)) is reacted with Br-Mg-CH ₂CH＝CH₂ to give a compound represented by R^F1－C(OH)(CH₂CH＝CH₂)₂、(CH₂＝CHCH₂)₂(HO)C－R^F2－C(OH)(CH₂CH＝CH₂)₂. Next, the above compound is reacted with the following formula: HSiR ¹ _n'R² _3－n' reacted to give the compound shown in R^F1－C(OH)(CH₂CH＝CH₂)₂、(R² _3－n'R¹ _n'Si－CH₂CH₂CH₂)₂(HO)C－R^F2－C(OH)(CH₂CH₂CH₂－SiR¹ _n'R² _3－n')₂. Next, the above compound is reacted with the following formula: the fluorinated polyether group-containing acrylic compounds represented by the above formulas (1) and (2) can be obtained by reacting a compound represented by R ³⁴－R³⁵－OCOCH＝CH₂ (wherein R ³⁴ is a reactive group such as-NCO, -COOH, or the like, and R ³⁵ is a divalent group).

In one embodiment, the fluorinated polyether group-containing acrylic compound represented by the above formulas (A1) and (A2) is represented by the following formula: HOCH ₂－R^F2－CH₂ OH (wherein R ^F1 and R ^F2 have the same meanings as described for formulas (A1) and (A2)), and a compound represented by the formula (A2)

Reacting to obtain

Next, the above compound is reacted with OCN- (CH ₂)₃－SiR¹ _n'R² _3－n') (wherein each symbol has the same meaning as described above) to obtain

(Wherein each symbol has the same meaning as described above).

In one embodiment, the fluorinated polyether group-containing acrylic compound represented by the above formulas (A1) and (A2) is represented by the following formula:

(wherein each symbol has the same meaning as described above.) and hooc=ch ₂ to give

(Wherein each symbol has the same meaning as described above). Next, the above compound is reacted with OCN- (CH ₂)₃－SiR¹ _n'R² _3－n') (wherein each symbol has the same meaning as described above) to obtain

(Wherein each symbol has the same meaning as described above).

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

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

The surface treatment agent of the present invention contains at least 1 kind of fluorinated polyether group-containing acrylic compound represented by the formula (1) or (2).

In one embodiment, in the surface treatment agent of the present invention, the fluoropolyether group-containing acrylic compound is a compound represented by formula (1).

In another embodiment, in the surface treatment agent of the present invention, the fluoropolyether group-containing acrylic compound is a compound represented by formula (2).

In another embodiment, in the surface treatment agent of the present invention, the fluoropolyether group-containing acrylic compound is a compound represented by formula (1) or a compound represented by formula (2).

In the surface treatment agent of the present invention, the compound represented by the formula (2) is preferably 0.1 mol% or more and 35 mol% or less relative to the total of the compound represented by the formula (1) and the compound represented by the formula (2). The lower limit of the content of the compound represented by the formula (2) is preferably 0.1 mol%, more preferably 0.2 mol%, further preferably 0.5 mol%, further more preferably 1 mol%, particularly preferably 2 mol%, and particularly preferably 5 mol%, based on the total of the compound represented by the formula (1) and the compound represented by the formula (2). The upper limit of the content of the compound represented by the formula (2) may be preferably 35 mol%, more preferably 30 mol%, further preferably 20 mol%, further more preferably 15 mol% or 10 mol% with respect to the total of the compound represented by the formula (1) and the compound represented by the formula (2). The compound represented by the formula (2) is preferably 0.1 to 30 mol%, more preferably 0.1 to 20 mol%, still more preferably 0.2 to 10 mol%, still more preferably 0.5 to 10 mol%, particularly preferably 1 to 10 mol%, for example 2 to 10 mol%, or 5 to 10 mol%, based on the total of the compound represented by the formula (1) and the compound represented by the formula (2).

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

The surface treatment agent of the present invention may contain a solvent, a (non-reactive) fluoropolyether compound which can be understood to be a fluorine-containing oil, preferably a perfluoro (poly) ether compound (hereinafter, collectively referred to as "fluorine-containing oil"), a (non-reactive) organosilicon compound which can be understood to be a silicone oil (hereinafter, referred to as "silicone oil"), an alcohol, a catalyst, a surfactant, a polymerization inhibitor, a sensitizer, and the like.

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; esters such as 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-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, methylaminoketone, and 2-heptanone; glycol ethers such as ethyl 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 monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, and ethylene glycol monoalkyl ether; alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, t-butanol, sec-butanol, 3-pentanol, octanol, 3-methyl-3-methoxybutanol, t-pentanol, and the like; 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, isopropyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, and the like; diethylene glycol monoethyl ether acetate; 1, 2-trichloro-1, 2-trifluoroethane, 1, 2-dichloro-1, 2-tetrafluoroethane fluorine-containing solvents such as dimethyl sulfoxide and 1, 1-dichloro-1, 2, 3-pentafluoropropane (HCFC225)、ZEORORA H、HFE7100、HFE7200、HFE7300、CF₃CH₂OH、CF₃CF₂CH₂OH、(CF₃)₂CHOH. Or a mixed solvent of 2 or more of them.

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

Rf⁵－(OC₄F₈)_a'－(OC₃F₆)_b'－(OC₂F₄)_c'－(OCF₂)_d'－Rf⁶···(3)

In formula (3), rf ⁵ represents a C1-16 alkyl group (preferably a perfluoroalkyl group of C _1－16) which may be substituted with 1 or more fluorine atoms, rf ⁶ represents a C1-16 alkyl group (preferably a C _1－16 perfluoroalkyl group) which may be substituted with 1 or more fluorine atoms, a fluorine atom or a hydrogen atom, and Rf ⁵ and Rf ⁶ are more preferably each independently a C _1－3 perfluoroalkyl group.

A ', b', c 'and d' each represent the number of 4 kinds of repeating units of perfluoro (poly) ether constituting the main polymer skeleton, and are each independently an integer of 0 to 300, and the sum of a ', b', c 'and d' is at least 1, preferably 1 to 300, more preferably 20 to 300. The order of presence of the repeating units indicated by subscripts a ', b', c 'or d' and bracketed is arbitrary in the formula. These repeating units may be linear or branched, and may include a ring structure. For example, - (OC ₄F₈) -can be any of －(OCF₂CF₂CF₂CF₂)－、－(OCF(CF₃)CF₂CF₂)－、－(OCF₂CF(CF₃)CF₂)－、－(OCF₂CF₂CF(CF₃))－、－(OC(CF₃)₂CF₂)－、－(OCF₂C(CF₃)₂)－、－(OCF(CF₃)CF(CF₃))－、－(OCF(C₂F₅)CF₂)－ and (OCF ₂CF(C₂F₅)) -, preferably- (OCF ₂CF₂CF₂CF₂)－.－(OC₃F₆) -can be any of- (OCF ₂CF₂CF₂)－、－(OCF(CF₃)CF₂) -and (OCF ₂CF(CF₃)) -, preferably- (OCF ₂CF₂CF₂)－.－(OC₂F₄) -can be any of- (OCF ₂CF₂) -and (OCF (CF ₃)) -, preferably- (OCF ₂CF₂) -.

The above-mentioned ring structure may be the following three-membered ring or four-membered ring:

[ wherein, the formula (I) represents a bonding position. ]

For example, (OC ₄F₈) may be

[ Wherein, the formula (I) represents a bonding position. ].

Examples of the perfluoro (poly) ether compound represented by the above general formula (3) include compounds represented by any of the following general formulae (3 a) and (3 b) (which may be a mixture of 1 or 2 or more).

Rf⁵－(OCF₂CF₂CF₂)_b"－Rf⁶···(3a)

Rf⁵－(OCF₂CF₂CF₂CF₂)_a"－(OCF₂CF₂CF₂)_b"－(OCF₂CF₂)_c"－(OCF₂)_d"－Rf⁶···(3b)

In these formulae, rf ⁵ and Rf ⁶ are as described above; in the formula (3 a), b' is an integer of 1 to 100 inclusive; in formula (3 b), a "and b" are each independently an integer of 0 to 30, and c "and d" are each independently an integer of 1 to 300. The order of presence of the repeating units indicated by subscripts a ", b", c ", d" and bracketed is arbitrary in the formula.

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). In addition, chlorotrifluoroethylene oligomer may be used.

The fluorine-containing oil may have an average molecular weight of 500 to 10000. The molecular weight of the fluorine-containing oil can be measured by GPC.

The surface treatment agent of the present invention may contain, for example, 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 5% by mass of a fluorine-containing oil. In one embodiment, the surface treatment agent of the present invention is substantially free of fluorine-containing oil. Substantially free of fluorine-containing oil means that the oil is completely free of fluorine-containing oil, or may contain an extremely small amount of fluorine-containing oil.

In one embodiment, the average molecular weight of the fluorine-containing oil may be made larger than the average molecular weight of the fluorinated polyether group-containing acrylic compound. By having such an average molecular weight, particularly when the surface treatment layer is formed by a vacuum vapor deposition method, more excellent wear durability and surface smoothness can be obtained.

In one embodiment, the average molecular weight of the fluorine-containing oil may be made smaller than the average molecular weight of the fluorinated polyether group-containing acrylic compound. By having such an average molecular weight, it is possible to form a cured product having high wear durability and high surface smoothness while suppressing a decrease in the transparency of a surface-treated layer obtained from such a compound.

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

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 ordinary silicone oil (straight silicon oil) or modified silicone oil. Examples of the general silicone oil include dimethyl silicone oil, methyl phenyl silicone oil, and methyl hydrogen silicone oil. Examples of the modified silicone oil include silicone oils obtained by modifying ordinary silicone oils with alkyl groups, aralkyl groups, polyethers, higher fatty acid esters, fluoroalkyl groups, amino groups, epoxy groups, carboxyl groups, alcohols, and the like. Examples of the cyclic silicone oil include cyclic dimethylsiloxane oil and the like.

The surface treating agent of the present invention may contain, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass, based on 100 parts by mass (the sum of 2 or more kinds is the same in the case of the above-mentioned fluorinated polyether-based acrylic compound of the present invention) of such silicone oil.

The silicone oil helps to improve the surface smoothness of the surface treatment layer.

Examples of the alcohols include alcohols having 1 to 6 carbon atoms which may be substituted with 1 or more fluorine atoms, such as methanol, ethanol, isopropanol, t-butanol, and CF ₃CH₂OH、CF₃CF₂CH₂OH、(CF₃)₂ CHOH. The addition of these alcohols to the surface treatment agent can improve the stability of the surface treatment agent and can also improve the compatibility of the perfluoropolyether group-containing acrylic compound with the solvent.

The above alcohol is preferably 2, 3-pentafluoro-1-propanol or 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.), and the like.

The catalyst promotes the hydrolysis, dehydration condensation or polymerization of the fluoropolyether-based acrylic compound of the present invention, and promotes the formation of a layer formed from the surface treating agent of the present invention.

Examples of the other components include tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyl trimethoxysilane, 3-glycidoxypropyl trimethoxysilane, and methyltriacetoxysilane, in addition to the above.

The surface treatment agent of the present invention may be impregnated into a substance obtained by fixing a porous substance such as a porous ceramic material or a metal fiber such as steel wool in a cotton-like state to prepare a pellet. The pellets can be used for vacuum evaporation, for example.

The surface treatment agent of the present invention may contain, as an impurity, a trace amount of, for example, pt, rh, ru, 1, 3-divinyl tetramethyl disiloxane, triphenylphosphine, naCl, KCl, a condensate of silane, or the like, in addition to the above-described components.

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

The article of the present invention comprises a substrate and a layer (surface-treated layer) formed on the surface of the substrate by the surface-treating agent of the present invention.

The substrate that can be used in the present invention may be made of, for example, glass, resin (natural or synthetic resin, for example, a common plastic material), metal, ceramic, semiconductor (silicon, germanium, etc.), fiber (fabric, nonwoven fabric, etc.), fur, leather, wood, ceramic, stone, etc., building materials, etc., sanitary products, or any suitable material.

For example, in the case where the article to be manufactured is an optical member, the material constituting the surface of the base material may be a material for an optical member, such as glass or transparent plastic. In addition, in the case where the article to be manufactured is an optical member, a layer (or film) such as a hard coat layer, an antireflection layer, or the like may be formed on the surface (outermost layer) of the substrate. The antireflection layer may use any of a single antireflection layer and a multilayer antireflection layer. Examples of the inorganic substance that can be used for the antireflection layer include SiO₂、SiO、ZrO₂、TiO₂、TiO、Ti₂O₃、Ti₂O₅、Al₂O₃、Ta₂O₅、Ta₃O₅、Nb₂O₅、HfO₂、Si₃N₄、CeO₂、MgO、Y₂O₃、SnO₂、MgF₂、WO₃. These inorganic substances may be used alone or in combination of 2 or more (for example, in the form of a mixture). In the case of forming a multilayer antireflection layer, siO ₂ and/or SiO is preferably used in the outermost layer thereof. When the object to be manufactured is an optical glass member for a touch panel, a transparent electrode, for example, a thin film of Indium Tin Oxide (ITO) or indium zinc oxide may be provided on a part of the surface of a substrate (glass). The substrate may further include an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coat film layer, a polarizing film, a retardation film, a liquid crystal display module, and the like, according to its specific specifications and the like.

The shape of the substrate is not particularly limited, and may be, for example, a plate, a film, or other forms. The surface area of the substrate on which the surface treatment layer is to be formed may be at least a part of the surface of the substrate, and may be appropriately determined according to the purpose of the article to be manufactured, the specific specification, and the like.

In one embodiment, the substrate may be a substrate having at least a surface portion formed of a material having a hydroxyl group. Examples of such a material include glass, and metals (particularly, base metals), ceramics, semiconductors, and the like, on the surface of which a natural oxide film or a thermal oxide film can be formed. Or, in the case where the hydroxyl group is not sufficiently present, such as a resin, or in the case where the hydroxyl group is not present in the original state, the hydroxyl group can be introduced or added to the surface of the substrate by performing a certain pretreatment on the substrate. Examples of such pretreatment include plasma treatment (e.g., corona discharge) and ion beam irradiation. In order to introduce or add hydroxyl groups to the surface of the substrate and to clean the surface of the substrate (remove foreign matter, etc.), plasma treatment may be suitably used. Further, as other examples of such pretreatment, the following methods are listed: a surface adsorbent having a carbon-carbon unsaturated bond group is formed in advance as a monolayer on the surface of a substrate by LB method (Langmuir-Blodgett method), chemisorption method or the like, and then the unsaturated bond is broken in an atmosphere containing oxygen, nitrogen or the like.

In another embodiment, the substrate may be a substrate having at least a surface portion formed of an organosilicon compound having 1 or more other reactive groups, for example, si—h groups, or a material containing an alkoxysilane.

In a preferred embodiment, the substrate is glass. As such glass, sapphire glass, soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, quartz glass are preferable, and soda lime glass after chemical strengthening, alkali aluminosilicate glass after chemical strengthening, and borosilicate glass after chemical bonding are particularly preferable.

The article of the present invention can be produced by forming the above-described layer of the surface treatment agent of the present invention on the surface of the base material, and if necessary, post-treating the layer to form a layer from the surface treatment agent of the present invention.

The layer formation of the surface treatment agent of the present invention can be carried out by applying the surface treatment agent described above to the surface of the substrate so as to cover the surface. The covering method is not particularly limited. For example, a wet coverage method and a dry coverage method may be used.

As examples of the wet coverage method, dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, and the like can be cited.

Examples of the dry coating method include vapor deposition (usually vacuum vapor deposition), sputtering, CVD, and the like. Specific examples of the vapor deposition method (typically, vacuum vapor deposition method) include resistance heating, electron beam, high-frequency heating using microwaves or the like, ion beam, and the like. Specific examples of the CVD method include plasma CVD, optical CVD, thermal CVD, and the like.

In addition, the coating may be performed by an atmospheric pressure plasma method.

In the case of using the wet coverage method, the surface treatment agent of the present invention may be diluted with a solvent and applied to the surface of a substrate. From the viewpoints of the stability of the composition of the present invention and the volatility of the solvent, the following solvents are preferably used: perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (e.g., perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1, 3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (e.g., bis (trifluoromethyl) benzene); alkyl perfluoroalkyl ethers (perfluoroalkyl and alkyl groups may be linear or branched) such as polyfluoroaliphatic hydrocarbons (e.g., C ₆F₁₃CH₂CH₃ (e.g., ASAHIKLIN (registered trademark) AC-6000 manufactured by Asahi Kao 3M Co., ltd.), 1,2, 3, 4-heptafluorocyclopentane (e.g., ZEORORA (registered trademark) H manufactured by Sumitomo Weng Zhushi Co., ltd.), hydrofluoroethers (HFEs) (e.g., perfluoropropyl methyl ether (C ₃F₇OCH₃) (e.g., novec (trademark) 7000 manufactured by Sumitomo 3M Co., ltd.), perfluorobutyl methyl ether (C ₄F₉OCH₃) (e.g., novec (trademark) 7100 manufactured by Sumitomo 3M Co., ltd.), perfluorobutyl ethyl ether (C ₄F₉OC₂H₅) (e.g., novec (trademark) 7200 manufactured by Sumitomo 3M Co., ltd.), perfluorohexyl methyl ether (C ₂F₅CF(OCH₃)C₃F₇) (e.g., novec (trademark) 7300) alkyl groups may be linear or branched), or CF ₃CH₂OCF₂CHF₂ (e.g., AE (manufactured by Sumitomo 3M Co., ltd.) may be used alone or as a mixture of these compounds may be used in particular preference to form of perfluorobutyl ether (C. ₄F₉OCH₃).

In the case of using the dry coating method, the surface treatment agent of the present invention may be directly supplied to the dry coating method, or may be supplied to the dry coating method after being diluted with the above-mentioned solvent.

The layer formation of the surface treatment agent is preferably carried out in such a manner that the surface treatment agent of the present invention and a catalyst for hydrolysis and dehydration condensation coexist in the layer. For simplicity, in the case of using the wet coverage method, the catalyst may be added to the diluted solution of the surface treatment agent of the present invention immediately before the surface treatment agent is diluted with the solvent. In the case of using the dry coating method, the surface treatment agent of the present invention after the addition of the catalyst may be directly subjected to vapor deposition (usually vacuum vapor deposition), or the surface treatment agent of the present invention after the addition of the catalyst may be impregnated into a metal porous body such as iron or copper to obtain a particulate material, and vapor deposition (usually vacuum vapor deposition) may be performed using the obtained particulate material.

Any suitable acid or base may be used as the catalyst. As the acid catalyst, for example, acetic acid, formic acid, trifluoroacetic acid, and the like can be used. As the base catalyst, ammonia, organic amines, and the like can be used, for example.

The surface treatment layer included in the article of the present invention has both high wear durability. In addition to high abrasion durability, the surface treatment layer may have water repellency, oil repellency, stain resistance (for example, prevention of adhesion of stains such as fingerprints), water repellency (prevention of penetration of water into electronic parts and the like), surface smoothness (or lubricity, for example, wiping property of stains such as fingerprints, excellent finger touch), chemical resistance, and the like, depending on the composition of the surface treatment agent used, and may be suitably used as a functional film.

The invention therefore also relates to an optical material having an outermost layer with the surface treatment layer described above.

As the optical material, various optical materials can be preferably cited, in addition to the optical materials related to a display or the like as exemplified below, for example: a display such as a cathode ray tube (CRT; for example, a computer display), a liquid crystal display, a plasma display, an organic EL display, an inorganic thin film EL dot matrix display, a rear projection display, a fluorescent display tube (VFD), a field emission display (FED; field Emission Display), a protective plate for these displays, or a material obtained by subjecting the surfaces of these to an antireflection film treatment.

The article of the present invention is not particularly limited, and may be an optical member. Examples of the optical member are as follows: lenses such as spectacles; front protection plates, antireflection plates, polarizing plates, antiglare plates for displays such as PDP, LCD, etc.; touch panel sheets for mobile phones, portable information terminals, and the like; disc surfaces of optical discs such as Blu-ray discs, DVD discs, CD-R, MO, etc.; an optical fiber; a display surface of a timepiece, and the like.

In addition, the article of the present invention may be a medical device or a medical material. The article having the layer obtained by the present invention may be an automobile interior or exterior material. Examples of the exterior material include the following: window, lamp shade, external camera lid. Examples of the interior material are as follows: an instrument panel cover, a navigation system touch panel, and a decorative interior material.

The thickness of the above layer is not particularly limited. In the case of the optical member, the thickness of the layer is preferably in the range of 1 to 50nm, 1 to 30nm, preferably 1 to 15nm, from the viewpoints of optical performance, abrasion durability and stain resistance.

The article of the present invention is described in detail above. The article, the method of manufacturing the article, and the like of the present invention are not limited to the above-described examples.

Examples

The compounds of the present invention will be described below in examples, but the present invention is not limited to the examples below. In this example, the order of presence of the repeating units constituting the perfluoropolyether is arbitrary, and the chemical formula shown below represents the average composition.

Synthesis example 1

To a 100mL 3-neck flask equipped with a reflux condenser, a thermometer and a stirrer were added 10.0g of a perfluoropolyether-modified acyl fluoride represented by average composition CF ₃O(CF₂CF₂O)₂₂(CF₂O)₂₆CF₂ COF, 10.0g of 1, 3-bis (trifluoromethyl) benzene and 5.0g of tetrahydrofuran, and the mixture was stirred under a nitrogen stream at 25℃for 30 minutes. Then, 9.6mL of 0.7M allylmagnesium bromide was slowly added dropwise thereto, followed by heating at 60℃for 4 hours. Thereafter, the reaction mixture was cooled to 5℃and 10.0g of a 3.0M aqueous hydrochloric acid solution was added dropwise thereto to stop the reaction. After recovering the lower fluorine phase by liquid separation, the lower fluorine phase was washed with methanol. Thereafter, the volatile component is distilled off under reduced pressure, whereby the perfluoropolyether group-containing allyl compound (a) represented by the following formula is obtained.

CF₃O(CF₂CF₂O)₂₂(CF₂O)₂₆CF₂C(OH)(CH₂CH＝CH₂)₂

Synthesis example 2

10.0G of the perfluoropolyether group-containing allyl compound (A) obtained in Synthesis example 1, 10.0g of 1, 3-bis (trifluoromethyl) benzene, 0.020g of triacetoxymethylsilane and 1.21g of trichlorosilane were charged into a 100mL 3-neck flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred under a nitrogen stream at 5℃for 30 minutes. Next, 0.20g of a 2% xylene solution of Pt complex compound containing 1, 3-divinyl-1, 3-tetramethyldisiloxane was added thereto, and the mixture was stirred at 60℃for 5 hours. Thereafter, volatile components were distilled off under reduced pressure, whereby a perfluoropolyether group-containing trichlorosilane compound (B) represented by the following formula was obtained.

CF₃O(CF₂CF₂O)₂₂(CF₂O)₂₆CF₂C(OH)(CH₂CH₂CH₂SiCl₃)₂ Synthesis example 3

10.0G of the perfluoropolyether group-containing trichlorosilane compound (B) obtained in Synthesis example 2 and 10.0g of 1, 3-bis (trifluoromethyl) benzene were charged into a 100mL 3-necked flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred under a nitrogen flow at 50℃for 30 minutes. Next, a mixed solution of 0.13g of methanol and 1.42g of methyl orthoformate was added thereto, and the mixture was stirred at 65℃for 2 hours. Thereafter, volatile components were distilled off under reduced pressure, whereby a perfluoropolyether group-containing silane compound (C) represented by the following formula was obtained.

CF₃O(CF₂CF₂O)₂₂(CF₂O)₂₆CF₂C(OH){CH₂CH₂CH₂Si(OCH₃)₃}₂

Synthesis example 4

To a 100mL 3-neck flask equipped with a reflux condenser, a thermometer and a stirrer were charged 10.0g of the perfluoropolyether group-containing silane compound (C) obtained in Synthesis example 3, 0.32g of 2-isocyanatoethyl acrylate (KARENZ (registered trademark) AOI manufactured by Showa Denko Co., ltd.) and 0.0014g of dibutyltin dilaurate, and the mixture was stirred under a nitrogen flow at 50℃for 2 hours to obtain a perfluoropolyether group-containing silane compound (D) shown below.

CF₃O(CF₂CF₂O)₂₂(CF₂O)₂₆CF₂C(OX){CH₂CH₂CH₂Si(OCH₃)₃}₂

X＝－CONHCH₂CH₂OCOCH＝CH₂

Synthesis example 5

10.0G of a perfluoropolyether-modified ester having an average composition of CF₃CF₂CF₂O(CF₂CF₂CF₂O)₂₄CF₂CF₂COOCH₃ g, 5.0g of 1, 3-bis (trifluoromethyl) benzene, and 0.51g of 3- (2-aminoethylamino) propyltrimethoxysilane were charged into a 100mL 3-necked flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred under a nitrogen stream at 25℃for 1 hour. Thereafter, volatile components were distilled off under reduced pressure, whereby a perfluoropolyether group-containing silane compound (E) represented by the following formula was obtained.

CF₃CF₂CF₂O(CF₂CF₂CF₂O)₂₄CF₂CF₂CONHCH₂CH₂NHCH₂CH₂CH₂Si(OCH₃)₃

Synthesis example 6

10.0G of the perfluoropolyether group-containing silane compound (E) obtained in Synthesis example 5 and 0.32g of 2-isocyanatoethyl acrylate (KARENZ (registered trademark) AOI manufactured by Showa Denko Co., ltd.) were charged into a 100mL 3-neck flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred under a nitrogen stream at 25℃for 1 hour to obtain a perfluoropolyether group-containing silane compound (F) represented by the following formula.

CF₃CF₂CF₂O(CF₂CF₂CF₂O)₂₄CF₂CF₂CONHCH₂CH₂N(X)CH₂CH₂CH₂Si(OCH₃)₃

X＝－CONHCH₂CH₂OCOCH＝CH₂

Synthesis example 7

10.0G of a perfluoropolyether-modified ester having an average composition of CF ₃O(CF₂CF₂O)₂₂(CF₂O)₂₆CF₂COOCH₃ g, 5.0g of 1, 3-bis (trifluoromethyl) benzene and 0.50g of 3- (2-aminoethylamino) propyltrimethoxysilane were charged into a 100mL 3-necked flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred under a nitrogen stream at 25℃for 1 hour. Thereafter, volatile components were distilled off under reduced pressure, whereby a perfluoropolyether group-containing silane compound (G) represented by the following formula was obtained.

CF₃O(CF₂CF₂O)₂₂(CF₂O)₂₆CF₂CONHCH₂CH₂NHCH₂CH₂CH₂Si(OCH₃)₃

Synthesis example 8

10.0G of the perfluoropolyether group-containing silane compound (G) obtained in Synthesis example 7 and 0.31G of 2-isocyanatoethyl acrylate (KARENZ (registered trademark) AOI manufactured by Showa Denko Co., ltd.) were charged into a 100mL 3-neck flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred under a nitrogen stream at 25℃for 1 hour to obtain a perfluoropolyether group-containing silane compound (H) represented by the following formula.

CF₃O(CF₂CF₂O)₂₂(CF₂O)₂₆CF₂CONHCH₂CH₂N(X)CH₂CH₂CH₂Si(OCH₃)₃

X＝－CONHCH₂CH₂OCOCH＝CH₂

Synthesis example 9

10.0G of a perfluoropolyether-modified ester having an average composition of CF₃CF₂CF₂O{CF(CF₃)CF₂O}₁₁CF(CF₃)COOCH₃ g, 5.0g of 1, 3-bis (trifluoromethyl) benzene and 1.02g of 3- (2-aminoethylamino) propyltrimethoxysilane were charged into a 100mL 3-necked flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred under a nitrogen stream at 70℃for 10 hours. Thereafter, volatile components were distilled off under reduced pressure, whereby a perfluoropolyether group-containing silane compound (I) represented by the following formula was obtained.

CF₃CF₂CF₂O{CF(CF₃)CF₂O}₁₁CF(CF₃)CONHCH₂CH₂NHCH₂CH₂CH₂Si(OCH₃)₃

Synthesis example 10

10.0G of the perfluoropolyether group-containing silane compound (I) obtained in Synthesis example 9 and 0.65g of 2-isocyanatoethyl acrylate (KARENZ (registered trademark) AOI manufactured by Showa Denko Co., ltd.) were charged into a 100mL 3-neck flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred under a nitrogen stream at 25℃for 1 hour to obtain a perfluoropolyether group-containing silane compound (J) represented by the following formula.

CF₃CF₂CF₂O{CF(CF₃)CF₂O}₁₁CF(CF₃)CONHCH₂CH₂N(X)CH₂CH₂CH₂Si(OCH₃)₃

X＝－CONHCH₂CH₂OCOCH＝CH₂

Synthesis example 11

10.0G of a perfluoropolyether-modified ester having an average composition of CF₃O(CF₂CF₂OCF₂CF₂CF₂CF₂O)₁₃CF₂CF₂OCF₂CF₂CF₂COOCH₃ g, 5.0g of 1, 3-bis (trifluoromethyl) benzene and 0.47g of 3- (2-aminoethylamino) propyltrimethoxysilane were charged into a 100mL 3-necked flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred under a nitrogen stream at 25℃for 1 hour. Thereafter, volatile components were distilled off under reduced pressure, whereby a perfluoropolyether group-containing silane compound (K) represented by the following formula was obtained.

CF₃O(CF₂CF₂OCF₂CF₂CF₂CF₂O)₁₃CF₂CF₂OCF₂CF₂CF₂CONHCH₂CH₂NHCH₂CH₂CH₂Si(OCH₃)₃

Synthesis example 12

10.0G of the perfluoropolyether group-containing silane compound (K) obtained in Synthesis example 11 and 0.30g of 2-isocyanatoethyl acrylate (KARENZ (registered trademark) AOI manufactured by Showa Denko Co., ltd.) were charged into a 100mL 3-neck flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred under a nitrogen stream at 25℃for 1 hour to obtain a perfluoropolyether group-containing silane compound (L) represented by the following formula.

CF₃O(CF₂CF₂OCF₂CF₂CF₂CF₂O)₁₃CF₂CF₂OCF₂CF₂CF₂CONHCH₂CH₂N(X)CH₂CH₂CH₂Si(OCH₃)₃

X＝－CONHCH₂CH₂OCOCH＝CH₂

Synthesis example 13

10.0G of the perfluoropolyether group-containing silane compound (G) obtained in Synthesis example 7 and 0.53G of 1,1- (bisacryloxymethyl) ethyl isocyanate (KARENZ (registered trademark) BEI manufactured by Showa Denko Co., ltd.) were charged into a 100mL 3-neck flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred under a nitrogen flow at 25℃for 1 hour to obtain a perfluoropolyether group-containing silane compound (M) represented by the following formula.

CF₃O(CF₂CF₂O)₂₂(CF₂O)₂₆CF₂CONHCH₂CH₂N(X)CH₂CH₂CH₂Si(OCH₃)₃

X＝－CONHC(CH₃)(CH₂OCOCH＝CH₂)₂

Synthesis example 14

10.0G of the perfluoropolyether group-containing silane compound (G) obtained in Synthesis example 7 and 0.45G of 4-hydroxybutyl acrylate glycidyl ether (4 HBAGE manufactured by Mitsubishi chemical corporation) were charged into a 100mL 3-neck flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred under a nitrogen flow at 50℃for 2 hours to obtain a perfluoropolyether group-containing silane compound (N) represented by the following formula.

CF₃O(CF₂CF₂O)₂₂(CF₂O)₂₆CF₂CONHCH₂CH₂N(X)CH₂CH₂CH₂Si(OCH₃)₃

X is X ¹ or X ²(X¹:X² =73:27 described below).

X¹＝－CH₂CH(OH)CH₂OCH₂CH₂CH₂CH₂OCOCH＝CH₂

X²＝－CH(CH₂OH)CH₂OCH₂CH₂CH₂CH₂OCOCH＝CH₂

Synthesis example 15

10.0G of a perfluoropolyether-modified ester having an average composition of CH₃OCOCF₂O(CF₂O)₁₂(CF₂CF₂O)₁₂CF₂COOCH₃ g, 5.0g of 1, 3-bis (trifluoromethyl) benzene and 1.69g of 3- (2-aminoethylamino) propyltrimethoxysilane were charged into a 100mL 3-necked flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred under a nitrogen stream at 25℃for 1 hour. Thereafter, volatile components were distilled off under reduced pressure, whereby a perfluoropolyether group-containing silane compound (O) represented by the following formula was obtained.

(CH₃O)₃SiCH₂CH₂CH₂NHCH₂CH₂NHCOCF₂O(CF₂CF₂O)₁₂(CF₂O)₁₂CF₂CONHCH₂CH₂NHCH₂CH₂CH₂Si(OCH₃)₃

Synthesis example 16

10.0G of the perfluoropolyether group-containing silane compound (O) obtained in Synthesis example 15 and 1.08g of 2-isocyanatoethyl acrylate (KARENZ (registered trademark) AOI manufactured by Showa Denko Co., ltd.) were charged into a 100mL 3-neck flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred under a nitrogen stream at 25℃for 1 hour to obtain a perfluoropolyether group-containing silane compound (P) represented by the following formula.

(CH₃O)₃SiCH₂CH₂CH₂N(X)CH₂CH₂NHCOCF₂O(CF₂CF₂O)₁₂(CF₂O)₁₂CF₂CONHCH₂CH₂N(X)CH₂CH₂CH₂Si(OCH₃)₃

X＝－CONHCH₂CH₂OCOCH＝CH₂

Synthesis example 17

10.0G of a perfluoropolyether-modified ester having an average composition CH₃OCOCF(CF₃){OCF₂CF(CF₃)}_mOCF₂CF₂O{CF(CF₃)CF₂O}_nCF(CF₃)COOCH₃(m+n≈34) g, 5.0g of hexafluorobenzene and 0.73g of 3- (2-aminoethylamino) propyltrimethoxysilane were charged into a 100mL 3-neck flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred under a nitrogen stream at 70℃for 12 hours. Thereafter, volatile components were distilled off under reduced pressure, whereby a perfluoropolyether group-containing silane compound (Q) represented by the following formula was obtained.

(CH₃O)₃SiCH₂CH₂CH₂NHCH₂CH₂NHCOCF(CF₃){OCF₂CF(CF₃)}_mOCF₂CF₂O{CF(CF₃)CF₂O}_nCF(CF₃)CONHCH₂CH₂NHCH₂CH₂CH₂Si(OCH₃)₃

Synthesis example 18

10.0G of the perfluoropolyether group-containing silane compound (Q) obtained in Synthesis example 17 and 0.46g of 2-isocyanatoethyl acrylate (KARENZ (registered trademark) AOI manufactured by Showa Denko Co., ltd.) were charged into a 100mL 3-neck flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred under a nitrogen stream at 25℃for 1 hour to obtain a perfluoropolyether group-containing silane compound (R) represented by the following formula.

(CH₃O)₃SiCH₂CH₂CH₂N(X)CH₂CH₂NHCOCF(CF₃){OCF₂CF(CF₃)}_mOCF₂CF₂O{CF(CF₃)CF₂O}_nCF(CF₃)CONHCH₂CH₂N(X)CH₂CH₂CH₂Si(OCH₃)₃

X＝－CONHCH₂CH₂OCOCH＝CH₂

Synthesis example 19

10.0G of the perfluoropolyether group-containing silane compound (O) obtained in Synthesis example 15 and 1.52g of 2- (2-methacryloyloxyethyl) ethyl isocyanate (KARENZ (registered trademark) MOI-EG manufactured by Showa Denko Co., ltd.) were charged into a 100mL 3-neck flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred under a nitrogen flow at 25℃for 1 hour to obtain a perfluoropolyether group-containing silane compound (S) represented by the following formula.

(CH₃O)₂(CH₃)SiCH₂CH₂CH₂N(X)CH₂CH₂NHCOCF₂O(CF₂CF₂O)₁₂(CF₂O)₁₂CF₂CONHCH₂CH₂N(X)CH₂CH₂CH₂Si(CH₃)(OCH₃)₂

X＝－CONHCH₂CH₂OCH₂CH₂OCOC(CH₃)＝CH₂

Example 1

The compound (D) obtained in synthesis example 4 was dissolved in Novec7200 (manufactured by 3M corporation) to a concentration of 20 mass%, to prepare a surface treatment agent 1.

The surface treatment agent 1 prepared above was vacuum-deposited on chemically strengthened glass (manufactured by Corning, inc., "Gorilla" glass, thickness 0.7 mm). The vacuum evaporation method is carried out under the condition that the size of the chamber of the resistance heating type evaporatorVacuum degree 5.0E-05, current value 240A, voltage 10V, substrate temperature 40 ℃. Then, the vapor-deposited chemically strengthened glass was allowed to stand in an atmosphere at 150℃for 30 minutes, and then cooled to room temperature. Then, the vapor-deposited chemically strengthened glass was irradiated with light containing 365nm UV light at an intensity of 1000mJ/cm ² under an air atmosphere to form a surface-treated layer on the glass substrate.

Example 2

A surface treatment agent was prepared and a surface treatment layer was formed 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).

Example 3

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

Example 4

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

Example 5

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

Example 6

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

Example 7

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

Example 8

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

Example 9

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

Example 10

A surface treatment agent was prepared and a surface treatment layer was formed 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).

Comparative example 1

The following compound (T) was dissolved in Novec7200 (manufactured by 3M corporation) to a concentration of 20 mass%, to prepare a surface treatment agent 2.

CF₃O(CF₂CF₂O)₂₂(CF₂O)₂₆CF₂CON{CH₂CH₂CH₂Si(OCH₃)₃}₂

The surface treatment agent 2 prepared above was vacuum-deposited on chemically strengthened glass (produced by Corning, "Gorilla" glass, thickness 0.7 mm). The vacuum evaporation method is carried out under the condition that the size of the chamber of the resistance heating type evaporatorVacuum degree 5.0E-05, current value 240A, voltage 10V, substrate temperature 40 ℃. Then, the vapor-deposited chemically strengthened glass was allowed to stand in an atmosphere at 150℃for 30 minutes, and then cooled to room temperature to form a surface-treated layer on the glass substrate.

Comparative example 2

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

CF₃O(CF₂CF₂O)₂₂(CF₂O)₂₆CF₂CONHCH₂CH₂CH₂Si(OCH₃)₃

Comparative example 3

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

CF₃CF₂CF₂O{CF(CF₃)CF₂O}₁₁CF(CF₃)CONHCH₂CH₂CH₂Si(OCH₃)₃ Comparative example 4

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

CF₃CF₂CF₂O(CF₂CF₂CF₂CF₂O)₂₅CF₂CF₂CONHCH₂CH₂CH₂Si(OCH₃)₃

Comparative example 5

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

(CH₃O)₃SiCH₂CH₂CH₂NHCOCF₂O(CF₂CF₂O)₁₂(CF₂O)₁₂CF₂CONHC H₂CH₂CH₂Si(OCH₃)₃

Comparative example 6

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

(CH₃O)₃SiCH₂CH₂CH₂NHCOCF(CF₃){OCF₂CF(CF₃)}_mOCF₂CF₂O{CF(CF₃)CF₂O}_nCF(CF₃)CONHCH₂CH₂CH₂Si(OCH₃)₃

< Evaluation >

The glass substrate with the surface-treated layer obtained above was subjected to measurement of water contact angle and evaluation of alkali test as follows.

(Alkali impregnation test)

An O-ring made of PTFE having a diameter of 1cm was placed on the surface of the substrate surface-treated in examples 1 to 10 and comparative examples 1 to 6, and an 8N NaOH solution (aqueous alkali solution) was dropped into the O-ring to bring the surface of the surface-treated layer into contact with an aqueous alkali solution, and the surface was subjected to an alkali impregnation test. After the alkali impregnation test was performed for 20 to 300 minutes, the alkali aqueous solution was wiped off, and the aqueous solution was washed with pure water and ethanol, and then the contact angle with water was measured. Further, as to the static contact angle of water, 2. Mu.L of a water drop of pure water was dropped onto the surface of the glass substrate after the alkali impregnation test, and the contact angle with water was measured using a contact angle meter (manufactured by Kyowa Kagaku chemical Co., ltd.: automatic contact angle meter, dropMaster701,701). The static contact angle of water after the alkali impregnation test was measured with 5 measurement sites. When the measured value of the static contact angle of water was lowered within 300 minutes, the alkali impregnation test was stopped halfway. The relationship between the immersion time and the average contact angle of 5 sites is shown in the following table.

TABLE 1

(Wear durability test)

The sample article having the surface-treated layer formed thereon was placed horizontally, and the friction material described below was brought into contact with the surface of the surface-treated layer (the contact surface was a circle having a diameter of 1 cm), a load of 5N was applied thereto, and then the friction material was reciprocated at a speed of 40 mm/sec in a state where the load was applied. The friction piece was reciprocated 4000 times at most, and the static contact angle (°) of water was measured every 1000 reciprocation times (number of rubs). The test was stopped at a time when the measured value of the static contact angle of water was less than 60 °. The static contact angle of water was measured in the same manner as in the alkali test described above. The results are shown in the following table.

Friction piece

The surface (diameter: 1 cm) of a silicone rubber processed product shown below was covered with cotton impregnated with artificial sweat having the composition shown below to obtain a cotton cover, and the obtained cotton cover was used as a rubbing member.

Composition of artificial sweat:

Anhydrous disodium hydrogen phosphate: 2g;

sodium chloride: 20g;

85% lactic acid: 2g;

Histidine hydrochloride: 5g;

Distilled water: 1Kg;

Silicone rubber processed product: the TIGERS POLYMER is obtained by processing a silica gel plug SR-51 into a cylinder with a diameter of 1cm and a thickness of 1 cm.

TABLE 2

Industrial applicability

The fluoropolyether-based acrylic compound of the present invention can be suitably used for forming a surface treatment layer on the surface of various substrates, particularly optical members requiring friction durability.

Claims (24)

1. A compound represented by the following formula (1) or (2), characterized by:

R^F1-X^A-X^B R^Si _nR^Ac _m (1)

R^Ac _mR^Si _nX^B-X^A-R^F2-X^A-X^B R^Si _nR^Ac _m (2)

In the formulas (1) and (2):

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 1 or more fluorine atoms,

Rf ² is a C _1-6 alkylene group which may be substituted with 1 or more fluorine atoms,

R ^F are each independently a divalent fluoropolyether group,

P is either 0 or 1 and,

Q is each independently 0 or 1,

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

X ^B is a group having a valence of (m+n+1) and having 1 to 10 carbon atoms and not containing Si atom,

R ^Si is independently at each occurrence-X ^C-SiR¹ _n'R² _3-n',

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

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

R ² is independently at each occurrence a hydrogen atom or a 1-valent organic group,

N' is an integer of 1 to 3,

R ^Ac is independently at each occurrence-X ^D-X^E(-X^F-OCO-CR⁵＝CH₂)_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 independently in each occurrence 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 of 1 to 10,

N is each independently an integer of 1 to 10,

M is each independently an integer of 1 to 10.

2. A compound according to claim 1, wherein:

R ^F is independently at each occurrence a group of the formula:

－(OC₆F₁₂)_a－(OC₅F₁₀)_b－(OC₄F₈)_c－(OC₃R^Fa ₆)_d－(OC₂F₄)_e－(OCF₂)_f－

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

A. b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is 1 or more, and the order in which the repeating units are each represented by a, b, c, d, e or f and bracketed is arbitrary in the formula, wherein at least 1 of a, b, c, e and f is 1 or more in the case where all R ^Fa are hydrogen atoms or chlorine atoms.

3. A compound according to claim 1 or 2, wherein:

R ^Fa is a fluorine atom.

4. A compound according to any one of claims 1 to 3, wherein:

r ^F is independently at each occurrence a group of the formula (f 1), (f 2), (f 3), (f 4), (f 5) or (f 6):

－(OC₃F₆)_d－(OC₂F₄)_e－(f1)

in the formula (f 1), d is an integer of 1 to 200, and e is 0 or 1;

－(OC₄F₈)_c－(OC₃F₆)_d－(OC₂F₄)_e－(OCF₂)_f－(f2)

in the formula (f 2), c and d are each independently an integer of 0 to 30,

E and f are each independently integers of 1 to 200,

C. d, e and f are integers from 10 to 200,

The order of presence of the repeating units noted under subscripts c, d, e, or f and bracketed is arbitrary in the formula;

－(R⁶－R⁷)_g－R⁹－(f3)

In the formula (f 3), R ⁶ is OCF ₂ or OC ₂F₄,

R ⁷ is a group selected from OC ₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀ and OC ₆F₁₂, or a combination of 2 or 3 groups selected from these groups,

R ⁹ is a single bond or a group selected from OCF₂、OC₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀ and OC ₆F₁₂,

G is an integer of 2 to 100;

－(R⁶－R⁷)_g－R^r－(R^7'－R^6')_g'－(f4)

In the formula (f 4), R ⁶ is OCF ₂ or OC ₂F₄,

R ⁷ is a group selected from OC ₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀ and OC ₆F₁₂, or a combination of 2 or 3 groups independently selected from these groups,

R ^6' is OCF ₂ or OC ₂F₄,

R ^7' is a group selected from OC ₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀ and OC ₆F₁₂, or a combination of 2 or 3 groups independently selected from these groups,

G is an integer of 2 to 100,

G' is an integer of 2 to 100,

R ^r is

Wherein, represents a bonding position;

－(OC₆F₁₂)_a－(OC₅F₁₀)_b－(OC₄F₈)_c－(OC₃F₆)_d－(OC₂F₄)_e－(OCF₂)_f－(f5)

in the formula (f 5), e is an integer of 1 to 200, a, b, c, d and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is at least 1, and the order of the presence of the repeating units denoted by a, b, c, d, e or f and bracketed is arbitrary in the formula;

－(OC₆F₁₂)_a－(OC₅F₁₀)_b－(OC₄F₈)_c－(OC₃F₆)_d－(OC₂F₄)_e－(OCF₂)_f－(f6)

In the formula (f 6), f is an integer of 1 to 200, a, b, c, d and e are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is at least 1, and the order of the presence of the repeating units denoted by a, b, c, d, e or f and bracketed is arbitrary in the formula.

5. A compound according to any one of claims 1 to 4, wherein:

rf ¹ is independently at each occurrence a C _1－16 perfluoroalkyl group,

Rf ² is independently at each occurrence a C _1－6 perfluoroalkylene group.

6. A compound according to any one of claims 1 to 5, wherein:

X ^A are each independently a single bond or a divalent organic group that is free of urethane bonds.

7. A compound according to any one of claims 1 to 6, wherein:

X ^A is each independently a single bond or a group of the formula:

－(C_αR¹¹ _2α)_s1－R¹² _t1－

Wherein:

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

Alpha is independently an integer of 1 to 10 for each occurrence,

R ¹² is independently at each occurrence-O-; -CO-, -NR ¹⁰－、－CONR¹⁰－、－NR¹⁰ CO-, -COO-or-OCO-,

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

S1 is an integer of 0 to 3,

T1 is an integer of 0 to 3,

The total of s1 and t1 is 1 or more,

The order of presence of the repeating units denoted by s1 or t1 and bracketed is arbitrary in the formula.

8. The compound of claim 7, wherein:

X ^A is-CONR ¹⁰－C_α1H_2α1－、－(C_α2H_2α2)－O－(C_α3H_2α3) -or-C _α4H_2α4 -,

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

Alpha 1 is an integer of 1 to 10,

Alpha 2 is an integer of 0 to 6,

Alpha 3 is an integer of 0 to 6,

Alpha 4 is an integer of 0 to 6.

9. The compound of claim 8, wherein:

X ^A is-CONR ¹⁰－C_α1H_2α1 -.

10. A compound according to any one of claims 1 to 9, wherein:

X ^B is a 3-valent group, n is 1, and m is 1.

11. A compound according to any one of claims 1 to 10, wherein:

X ^B is the following group:

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

N is 1 and m is 1.

12. A compound according to any one of claims 1 to 11, wherein:

X ^C is C _1－6 alkylene, - (CH ₂)_z1－O－(CH₂)_z2－、－(CH₂)_z3 -phenylene- (CH ₂)_z4 -or- (CH ₂)_z13－OCONH－(CH₂)_z14 -),

In the formula- (CH ₂)_z1－O－(CH₂)_z2 -, z1 is an integer of 0 to 6, and z2 is an integer of 0 to 6;

In the formula- (CH ₂)_z3 -phenylene- (CH ₂)_z4 -, z3 is an integer of 0 to 6, and z4 is an integer of 0 to 6);

In the formula- (CH ₂)_z13－OCONH－(CH₂)_z14) -z 13 is an integer of 0 to 6, and z14 is an integer of 0 to 6.

13. A compound according to any one of claims 1 to 12, wherein:

X ^C is C _1－6 alkylene.

14. A compound according to any one of claims 1 to 13, wherein:

n' is 2 or 3.

15. A compound according to any one of claims 1 to 14, wherein:

n' is 3.

16. A compound according to any one of claims 1 to 15, wherein:

x ^E is a single bond.

17. A compound according to any one of claims 1 to 15, wherein:

X ^E is-X ^G－X^H,

X ^G is a single bond, C _1－6 alkylene, - (CH ₂)_z9－O－(CH₂)_z10 -or- (CH ₂)_z11 -phenylene- (CH ₂)_z12 -),

In the formula- (CH ₂)_z9－O－(CH₂)_z10 -, z9 is an integer of 0 to 6, z10 is an integer of 0 to 6,

In the formula- (CH ₂)_z11 -phenylene- (CH ₂)_z12 -, z11 is an integer of 0 to 6, z12 is an integer of 0 to 6),

X ^H is the following group:

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

18. A compound according to any one of claims 1 to 17, wherein:

X ^D is －O－、－CO－、－COO－、－OCO－、－CONH－、－NHCO－、－OCONH－、－NHCOO－、－NH－CO－NH－、－CH₂CH(OH)CH₂－、－CH(CH₂OH)CH₂－、

Wherein X and X denote bonding positions, X is bonded to X ^B, and X ^E is bonded to X.

19. A compound according to any one of claims 1 to 18, wherein:

X ^F is a single bond, C _1－6 alkylene, - (CH ₂)_z5－O－(CH₂)_z6 -or- (CH ₂)_z7 -phenylene- (CH ₂)_z8 -),

In the formula- (CH ₂)_z5－O－(CH₂)_z6 -, z5 is an integer of 0 to 6, z6 is an integer of 0 to 6,

In the formula- (CH ₂)_z7 -phenylene- (CH ₂)_z8), z7 is an integer of 0 to 6, and z8 is an integer of 0 to 6.

20. A compound according to any one of claims 1 to 19, wherein:

R ⁵ is a hydrogen atom or a methyl group.

21. A surface treating agent characterized by:

A compound according to any one of claims 1 to 20.

22. The surface treatment agent according to claim 21, wherein:

And further comprises 1 or more other components selected from fluorine-containing oil, silicone oil and catalyst.

23. The surface treatment agent according to claim 21 or 22, wherein:

It is used as an antifouling coating agent or a water-repellent coating agent.

24. An article, characterized in that:

A layer comprising a substrate and a surface of the substrate formed of the compound according to any one of claims 1 to 20 or the surface treatment agent according to any one of claims 21 to 23.