KR20240096851A - Fluorine-containing coating agent composition, surface treatment agent and article - Google Patents

Abstract

(A) silanes and/or partial hydrolysis condensates thereof having alkoxysilyl groups and/or aryloxysilyl groups modified with a fluoropolyether group-containing polymer, and (B) acyl modified with a fluoropolyether group-containing polymer. It contains silane having an oxysilyl group and/or aroyloxysilyl group and/or a partially hydrolyzed condensate thereof, and this mass ratio is (A)/(B)=99.9/0.1 to 80/20 (total is 100). By setting the range, especially in vacuum vapor deposition coating, the curing speed after coating is improved, and a fluorine-containing coating composition that can form a stable, uniform film in a short time is obtained.

Description

Fluorine-containing coating composition, surface treatment agent and article {FLUORINE-CONTAINING COATING AGENT COMPOSITION, SURFACE TREATMENT AGENT AND ARTICLE}

The present invention relates to a coating agent containing a hydrolyzable alkoxy group- or aryloxy group-containing silane modified with a fluoropolyether group-containing polymer and/or a partially hydrolyzed condensate thereof, and in particular, even in vacuum deposition coating, the curing speed after coating. A fluorine-containing coating composition capable of forming a stable film in a short time, a surface treatment agent comprising the coating composition, and an article treated with the surface treatment agent are provided.

Recently, the conversion of screens into touch panels, including displays of mobile phones, is accelerating. However, the screen of the touch panel is often exposed and there are many opportunities for direct contact with fingers or cheeks, so it is easy for dirt such as sebum to accumulate, which is a problem. Therefore, in order to improve appearance and visibility, the demand for technology that makes it difficult for fingerprints to get on the surface of the display or technology that makes it easy to remove dirt is increasing every year.

In general, fluoropolyether group-containing compounds have very low surface free energy, so they have water and oil repellency, chemical resistance, lubricity, release properties, antifouling properties, etc. Taking advantage of its properties, it is widely used industrially as a water and oil repellant for paper and textiles, a lubricant for magnetic recording media, an oil repellent for precision equipment, a mold release agent, cosmetics, and a protective film. However, its properties mean that it is non-adhesive and non-adhesive to other substrates, and although it can be applied to the surface of a substrate, it is difficult to bring the film into close contact with the substrate.

On the other hand, silane coupling agents are well known for bonding organic compounds to the surface of a substrate such as glass or cloth, and are widely used as a coating agent for the surface of various substrates. Silane coupling agents have an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule. Hydrolyzable silyl groups undergo a self-condensation reaction due to moisture in the air, forming a film. This film becomes a strong, durable film by combining hydrolyzable silyl groups chemically and physically with the surface of glass or metal.

Therefore, by introducing a hydrolyzable silyl group into a fluoropolyether group-containing compound, it is easy to adhere to the surface of the substrate and can also form a film having water and oil repellency, chemical resistance, lubricity, release property, and antifouling properties on the surface of the substrate. Compositions have been disclosed (Patent Documents 1 to 8: Japanese Patent Application Laid-Open No. 2003-238577, Japanese Patent No. 2860979, Japanese Patent No. 4672095, Japanese Patent Application No. 2008-534696, Japanese Patent Application No. 2008-537557, Japanese Patent Application No. 2012-072272 , Japanese Patent Laid-open No. 2012-157856, Japanese Patent Laid-open No. 2013-136833).

These compositions are generally used by diluting them with a solvent that can dissolve the fluoropolyether group-containing silane compound. The dilution concentration varies depending on the application method, but in the case of vapor deposition coating, it is often used in the range of 10 to 50 mass%, and in the case of spray coating or dipping coating, it is often used in the range of 0.03 to 5 mass%. . The fluoropolyether group-containing polymer used in these compositions is mainly a hydrolyzable silyl group, and compounds containing an alkoxysilyl group such as a methoxy group or an ethoxy group are used. When applied to the surface of a substrate such as glass, it is hydrolyzed by moisture in the air or water adsorbed on the substrate, and crosslinks and reacts between polymers or with active groups on the surface of the substrate to form chemical bonds. If this crosslinking reaction is fast, the formation of the coating film can proceed quickly and a durable film can be formed, but the alkoxysilyl group does not have a sufficient reaction rate from the viewpoint of hydrolyzability, and faster curing is required.

Therefore, the above prior art document describes a method of adding basic compounds such as various inorganic acids, organic acids, and amines as catalysts for the purpose of speeding up the curing speed. However, if these catalyst components remain after coating, they may cause re-decomposition of the cross-linked portion or may adversely affect surface properties such as contact angle and friction coefficient. In addition, in the case of use on the surface of a touch panel such as a smartphone, since it is directly contacted with the finger, from these viewpoints, a compound that gradually volatilizes over time and does not remain on the surface is preferable.

On the other hand, vapor deposition coating involves heating and evaporating the polymer component in a vacuum and attaching it to the substrate. However, if the additive is prone to volatilization, it evaporates before the polymer, and it is also easy to be drawn into the vacuum line and settle on the substrate. Because it was difficult to do, there was a problem that sufficient effect was not obtained.

Japanese Patent Laid-open No. 2003-238577 Japanese Patent No. 2860979 Japanese Patent No. 4672095 Japan Special Patent No. 2008-534696 Japan Special Patent No. 2008-537557 Japanese Patent Laid-open No. 2012-072272 Japanese Patent Laid-open No. 2012-157856 Japanese Patent Application No. 2013-136833

The present invention has been made in consideration of the above circumstances, particularly in vacuum deposition coating, by improving the curing speed after coating, the development of performance such as wear durability is accelerated, and a fluorine-containing coating composition that can form a stable film in a short time, and The object is to provide a surface treatment agent containing this coating composition, and an article treated with this surface treatment agent.

The present inventors have conducted extensive studies to achieve the above object and have found that (A) a silane and/or a partially hydrolyzed condensate thereof having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer, wherein the hydrolyzable silyl group is A compound having an alkoxysilyl group and/or an aryloxysilyl group, (B) a silane having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer, and/or a partially hydrolyzed condensate thereof, wherein the hydrolyzable silyl group is an acyloxysilyl group. In the coating composition containing a compound that is a group and/or an aroyloxysilyl group, the mass ratio of component (A) and component (B) is (A)/(B) = 99.9/0.1 to 80/20 ((A) component and (B) the sum of the masses of the components is 100), specifically, a small amount of a compound having the same molecular weight distribution as the main component and having a hydrolyzable silyl group from which a catalytically active compound is released by hydrolysis. By adding it, it became possible to improve the curing speed after coating, especially in vacuum deposition coating, and it was discovered that a fluorine-containing coating composition capable of forming a stable film in a short time could be obtained, leading to the present invention.

Accordingly, the present invention provides the following fluorine-containing coating composition, a surface treatment agent comprising the coating composition, and an article treated with the surface treatment agent.

[One]

It contains the following components (A) and (B), and the mass ratio of component (A) and component (B) is (A)/(B) = 99.9/0.1 to 80/20 (component (A) and (B)) A fluorine-containing coating composition, characterized in that the sum of the masses of the components is 100.

(A) A compound that is a silane and/or a partially hydrolyzed condensate thereof having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer, wherein the hydrolyzable silyl group is an alkoxysilyl group and/or an aryloxysilyl group,

(B) A compound that is a silane and/or a partially hydrolyzed condensate thereof having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer, wherein the hydrolyzable silyl group is an acyloxysilyl group and/or an aroyloxysilyl group.

[2]

The silane having a hydrolyzable silyl group modified with the fluoropolyether group-containing polymer of component (A) has the following general formula (1)

-C _g F _2g O- (1)

(In the formula, g is an integer of 1 to 6 independently for each unit.)

The molecule contains 10 to 200 repeating units, and at least one terminal of the fluoropolyether group-containing polymer has the following general formula (2a):

(Wherein, R ¹ is an alkyl group having 1 to 4 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R is a monovalent hydrocarbon group having 1 to 6 carbon atoms in which part of the hydrogen atoms may be replaced with halogen atoms, , a is 2 or 3.)

The fluorine-containing coating composition according to [1], which has at least one hydrolyzable alkoxysilyl group and/or aryloxysilyl group represented by .

[3]

In the formula (2a), R ¹ is a methyl group or an ethyl group. The fluorine-containing coating composition according to [2].

[4]

The silane having a hydrolyzable silyl group modified with the fluoropolyether group-containing polymer of component (B) has the following general formula (1)

-C _g F _2g O- (1)

(In the formula, g is an integer of 1 to 6 independently for each unit.)

A polymer containing 10 to 200 repeating units represented by , and also containing a fluoropolyether group, has the following general formula (2b) at at least one terminal:

(Wherein, R ² is an alkyl group having 1 to 4 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R is a monovalent hydrocarbon group having 1 to 6 carbon atoms in which part of the hydrogen atoms may be replaced with halogen atoms, , a' is 1, 2 or 3.)

The fluorinated coating composition according to any one of [1] to [3], which has at least one hydrolyzable acyloxysilyl group and/or aroyloxysilyl group represented by .

[5]

In the formula (2b), R ² is a methyl group or an ethyl group, and a' is 1 or 2. The fluorine-containing coating composition according to [4].

[6]

The silane having a hydrolyzable silyl group modified with the fluoropolyether group-containing polymer of component (A) and component (B) is fluorocarbon represented by the following general formulas (3), (4), (5) and (6). The fluorine-containing coating composition according to any one of [1] to [5], wherein the fluorine-containing coating composition is at least one selected from polymer-modified hydrolyzable silanes containing a polyether group.

A-Rf-QZ(W) _α (3)

Rf-(QZ(W) _α ) ₂ (4)

A-Rf-Q-(Y) _β B (5)

Rf - (Q - (Y) _β B) ₂ (6)

[In the formula, Rf is

-(CF ₂ ) _d -O-(CF ₂ O) _p (CF ₂ CF ₂ O) _q (CF ₂ CF ₂ CF ₂ O) _r (CF ₂ CF ₂ CF ₂ CF ₂ O) _s (CF(CF ₃ )CF ₂ O) _t -(CF ₂ ) _d -, and p, q, r, s, and t are each independently integers of 0 to 200, and p+q+r+s+t=10 to 200 is an integer, each unit displayed within these parentheses may be randomly combined, and d is independently an integer from 0 to 5. A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a -CF ₃ group, -CF ₂ H group, or -CFH ₂ group, and Q is a single bond or a divalent organic group that may be fluorine substituted, Z is a single bond, a diorganosilylene group, -JC=[J is an alkyl group, a hydroxyl group, or K ₃ SiO-(K is a silyl ether group independently represented by a hydrogen atom, an alkyl group, an aryl group, or an alkoxy group)] Selected from the trivalent group indicated, the trivalent group indicated by -LSi=(L is an alkyl group), the tetravalent group indicated by -C≡, the tetravalent group indicated by -Si≡, and the 2 to 8 valent siloxane residues. W is a group having the following general formulas (7a) to (7d):

[In the formula, X is the following general formula (2a) or general formula (2b)

(In the formula, R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R is an alkyl group having 1 to 6 carbon atoms in which some of the hydrogen atoms may be substituted with halogen atoms. is a monovalent hydrocarbon group, a is 2 or 3, and a' is 1, 2, or 3.)

is a group represented by , f is an integer of 1 to 10, D is a single bond or a divalent organic group having 1 to 20 carbon atoms that may be fluorine-substituted, m is an integer of 2 to 6, and Me is a methyl group. ]

It is a group selected from groups having a hydrolyzable silyl group represented by , and α is an integer of 1 to 7. Y is a divalent group having an alkoxysilyl group, aryloxysilyl group, acyloxysilyl group, or aroyloxysilyl group, β is an integer of 1 to 10, and B is a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or a halogen. It is an atom.]

[7]

The fluorine-containing coating composition according to [6], wherein Y is at least one selected from groups represented by the following general formulas (8) to (10).

(Wherein, It is a divalent organic group that may be substituted with ~10 fluorine atoms, R ³ is a monovalent hydrocarbon group with 1 to 20 carbon atoms, and e is 1 or 2.)

[8]

A fluorine-containing coating composition according to [6] or [7], wherein Q is selected from a single bond or a divalent group represented by the following formula.

(In the formula, b is an integer of 2 to 4, c is an integer of 2 to 4, and Me is a methyl group.)

[9]

The fluorine-containing coating composition according to any one of [6] to [8], wherein Z is a single bond or a group represented by the following formula.

(In the formula, h is an integer of 2 to 4, and Me is a methyl group.)

[10]

Additionally, the fluorine-containing coating composition according to any one of [1] to [9], which contains a fluoropolyether group-containing polymer (C) represented by the following general formula (11).

(In the formula, Rf' is a polymer residue containing a divalent fluoroxyalkylene group. A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a -CF ₃ group, -CF ₂ H group, or -CFH ₂ group. am.)

[11]

A surface treatment agent comprising the fluorine-containing coating composition according to any one of [1] to [10].

[12]

Additionally, the surface treatment agent according to [11], which is diluted with a solvent containing a fluorine atom.

[13]

An article treated with a surface treatment agent according to [11] or [12].

[14]

A touch panel treated with a surface treatment agent according to [11] or [12].

[15]

An anti-reflection treated article treated with a surface treatment agent according to [11] or [12].

[16]

[11] or [12] Glass, tempered glass, sapphire glass, quartz glass, or SiO ₂ treated substrate treated with the surface treatment agent of the substrate.

The fluorinated coating composition of the present invention is basically a coating composition containing a silane containing a hydrolyzable alkoxysilyl group and/or an aryloxysilyl group modified with a fluoropolyether group-containing polymer and/or a partial hydrolysis condensate thereof. By adding a small amount of a compound having a molecular weight distribution similar to that of the polymer and having a hydrolyzable acyloxysilyl group and/or an aroyloxysilyl group from which an acetic acid compound having catalytic activity is released by hydrolysis, vacuum vapor deposition coating. When two types of polymers evaporate at the same time, they are uniformly dispersed and applied onto the substrate, and then hydrolyzed to generate a catalyst compound uniformly, thereby improving the curing speed after application and forming a stable, uniform film in a short period of time. . In addition, it exhibits a curing acceleration effect not only in vacuum evaporation coating but also in wet coating (spray coating, dipping coating).

(Form for carrying out the invention)

The fluorinated coating composition of the present invention is (A) a silane and/or a partially hydrolyzed condensate thereof having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer, and the hydrolyzable silyl group is an alkoxysilyl group and/or an aryl group. A compound having an oxysilyl group, (B) a silane having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer, and/or a partially hydrolyzed condensate thereof, wherein the hydrolyzable silyl group is an acyloxysilyl group and/or an aroyl group. In the coating composition containing a compound that is an oxysilyl group, the mass ratio of component (A) and component (B) is (A)/(B) = 99.9/0.1 to 80/20 (component (A) and component (B) The total mass is 100).

The mass ratio of component (A) and component (B) is (A)/(B)=99.9/0.1 to 80/20, preferably 99.8/0.2 to 85/15, and more preferably 99.5/0.5 to 90. /10 (the sum of the masses of component (A) and component (B) is 100). If the component (B) is less than the above ratio, the effect of accelerating curing may be difficult to exert, and if the component (B) is more than the above ratio, the storage stability of the uncured polymer may decrease.

In addition, component (A) and component (B) have different hydrolyzable silyl groups bonded to silicon atoms (component (A) is an alkoxysilyl group and/or aryloxysilyl group, component (B) is an acyloxysilyl group and / or aroyloxysilyl group), the structure of the silane modified with other fluoropolyether group-containing polymers may have the same molecular weight distribution, and even if those with the same structure are used, those with different structures can be used. You may use it.

As a silane having a hydrolyzable silyl group modified with the fluoropolyether group-containing polymer of component (A), the fluoropolyether group of component (A) has the following general formula (1)

-C _g F _2g O- (1)

(In the formula, g is an integer of 1 to 6 independently for each unit.)

Contains 10 to 200 repeating units, preferably 20 to 100, in the molecule, and also contains at least one terminal of the fluoropolyether group-containing polymer, preferably one or two terminals, more preferably has the following general formula (2a) at one end:

(Wherein, R ¹ is an alkyl group having 1 to 4 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R is a monovalent hydrocarbon group having 1 to 6 carbon atoms in which part of the hydrogen atoms may be replaced with halogen atoms, , a is 2 or 3.)

Those having at least one hydrolyzable alkoxysilyl group and/or aryloxysilyl group represented by are suitably used.

In addition, component (A) has at least one hydrolyzable alkoxysilyl group and/or aryloxysilyl group represented by the formula (2a), preferably 1 to 12, more preferably 1 to 6. Having a dog is desirable.

As a silane having a hydrolyzable silyl group modified with the fluoropolyether group-containing polymer of component (B), the fluoropolyether group of component (B) has the following general formula (1)

-C _g F _2g O- (1)

(In the formula, g is an integer of 1 to 6 independently for each unit.)

Contains 10 to 200 repeating units, preferably 20 to 100, in the molecule, and also contains at least one terminal of the fluoropolyether group-containing polymer, preferably one or two terminals, more preferably has the following general formula (2b) at one end:

(Wherein, R ² is an alkyl group having 1 to 4 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R is a monovalent hydrocarbon group having 1 to 6 carbon atoms in which part of the hydrogen atoms may be replaced with halogen atoms, , a' is 1, 2 or 3.)

Those having at least one hydrolyzable acyloxysilyl group and/or aroyloxysilyl group represented by are suitably used.

In addition, component (B) has at least one hydrolyzable acyloxysilyl group and/or aroyloxysilyl group represented by the formula (2b), preferably 1 to 12, more preferably 1 to 6. Having a dog is desirable.

Examples of the repeating unit represented by the general formula (1), which is a fluoropolyether group, include the following units. Additionally, the fluoropolyether group may be composed of one type of these repeating units alone, or may be a combination of two or more types, and each repeating unit may be randomly combined.

In the formula (2a), R ¹ is an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl, or an alkyl group having 2 to 4 carbon atoms. It is an alkoxy-substituted alkyl group such as methoxymethyl group, methoxyethyl group, ethoxymethyl group, and ethoxyethyl group of 4, or a phenyl group, and among them, methyl group and ethyl group are suitable.

R is a monovalent hydrocarbon group having 1 to 6 carbon atoms in which part of the hydrogen atom may be replaced with a halogen atom, and is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl. group, unsubstituted or halogen-substituted alkyl groups such as trifluoroethyl group and trichloroethyl group, and unsubstituted or halogen-substituted aryl groups such as phenyl group. Among them, methyl group and ethyl group are suitable.

In the formula (2b), R ² is an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl, or an alkyl group having 2 to 4 carbon atoms. It is an alkoxy-substituted alkyl group such as methoxymethyl group, methoxyethyl group, ethoxymethyl group, and ethoxyethyl group of 4, or a phenyl group, and among them, methyl group and ethyl group are suitable.

R is a monovalent hydrocarbon group having 1 to 6 carbon atoms in which part of the hydrogen atom may be replaced with a halogen atom, and is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl. group, unsubstituted or halogen-substituted alkyl groups such as trifluoroethyl group and trichloroethyl group, and unsubstituted or halogen-substituted aryl groups such as phenyl group. Among them, methyl group and ethyl group are suitable.

A silane containing a hydrolyzable alkoxysilyl group and/or an aryloxysilyl group modified with a fluoropolyether group-containing polymer of component (A) and a hydrolyzable acyloxysilyl modified with a fluoropolyether group-containing polymer of component (B). As the silane containing a group and/or an aroyloxysilyl group, at least one selected from polymer-modified hydrolyzable silanes containing a fluoropolyether group represented by the following general formulas (3), (4), (5) and (6) Paper is more suitable.

A-Rf-QZ(W) _α (3)

Rf-(QZ(W) _α ) ₂ (4)

A-Rf-Q-(Y) _β B (5)

Rf - (Q - (Y) _β B) ₂ (6)

[In the formula, Rf is

-(CF ₂ ) _d -O-(CF ₂ O) _p (CF ₂ CF ₂ O) _q (CF ₂ CF ₂ CF ₂ O) _r (CF ₂ CF ₂ CF ₂ CF ₂ O) _s (CF(CF ₃ )CF ₂ O) _t -(CF ₂ ) _d -, and p, q, r, s, and t are each independently integers of 0 to 200, and p+q+r+s+t=10 to 200 is an integer, each unit displayed within these parentheses may be randomly combined, and d is independently an integer from 0 to 5. A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a -CF ₃ group, -CF ₂ H group, or -CFH ₂ group, and Q is a single bond or a divalent organic group that may be fluorine substituted, Z is a single bond, a diorganosilylene group, -JC=[J is an alkyl group, a hydroxyl group, or K ₃ SiO-(K is a silyl ether group independently represented by a hydrogen atom, an alkyl group, an aryl group, or an alkoxy group)] Selected from the trivalent group indicated, the trivalent group indicated by -LSi=(L is an alkyl group), the tetravalent group indicated by -C≡, the tetravalent group indicated by -Si≡, and the 2 to 8 valent siloxane residues. W is a group having the following general formulas (7a) to (7d):

(Wherein, , m is an integer from 2 to 6, and Me is a methyl group.)

It is a group selected from groups having a hydrolyzable silyl group represented by , and α is an integer of 1 to 7. Y is a divalent group having a hydrolyzable silyl group selected from alkoxysilyl group, aryloxysilyl group, acyloxysilyl group and aroyloxysilyl group, β is an integer of 1 to 10, and B is a hydrogen atom, carbon number 1 It is an alkyl group of ~4, or a halogen atom.]

In the above equations (3) to (6), Rf is

-(CF ₂ ) _d -O-(CF ₂ O) _p (CF ₂ CF ₂ O) _q (CF ₂ CF ₂ CF ₂ O) _r (CF ₂ CF ₂ CF ₂ CF ₂ O) _s (CF(CF ₃ )CF ₂ O) _t -(CF ₂ ) _d -.

Here, p, q, r, s, and t are each independently an integer of 0 to 200, preferably p is an integer of 5 to 100, q is an integer of 5 to 100, R is an integer of 0 to 100, s is an integer from 0 to 50, t is an integer from 0 to 100, and p+q+r+s+t is an integer from 10 to 200, preferably an integer from 20 to 100, and each indicated in these parentheses Units may be randomly combined. d is independently an integer of 0 to 5, preferably an integer of 0 to 2, and more preferably 1 or 2.

As Rf, what is specifically shown below can be exemplified.

(In the formula, d' is the same as d above, p', q', r', s', and t' are each integers of 1 or more, and their upper limit is the same as the upper limit of p, q, r, s, and t above. In addition, the sum of p', q', r', s', and t' is 1 to 200, u is an integer of 1 or more, v is an integer of 1 or more, and u+v=2 to 100. Each repeating unit may be randomly combined.)

In the above formulas (3) and (5), A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a -CF ₃ group, -CF ₂ H group, or -CFH ₂ group, and is a monovalent fluorine-containing group. Specifically, what is shown below can be exemplified.

-CF ₃

-CF ₂ CF ₃

-CF ₂ CF ₂ CF ₃

_-CF2H

-CFH ₂

In the above formulas (3) to (6), Q is a single bond or a divalent organic group that may be fluorine substituted, and is a linking group between the Rf group and the terminal group. Q is preferably an amide bond, an ether bond, an ester bond, or a diorganosilylene group such as a dimethylsilylene group, -Si[OH][(CH ₂ ) _b Si(CH ₃ ) ₃ ]-(b is 2 to It is an unsubstituted or substituted divalent organic group having 2 to 12 carbon atoms that may contain one or two or more structures selected from the group consisting of groups represented by (an integer of 4), and more preferably may contain the above structures. It is an unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms.

Here, the unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms includes ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), hexamethylene group, and octamethylene group. An alkylene group such as a methylene group, an arylene group such as a phenylene group, or a combination of two or more of these groups (alkylene, arylene group, etc.) may be used, and some or all of the hydrogen atoms of these groups may be replaced with a halogen such as fluorine or iodine. and those substituted with atoms, and among them, unsubstituted or substituted alkyl groups and phenyl groups having 2 to 4 carbon atoms are preferable.

Examples of such Q include the following groups.

(In the formula, b is an integer of 2 to 4, c is an integer of 2 to 4, and Me is a methyl group.)

In each of the above formulas (3) and (4), Z is a single bond, preferably a diorganosilylene group such as a dialkyl silylene group having 1 to 3 carbon atoms, and -JC=[J is preferably 1 to 3 carbon atoms. Silyl represented by an alkyl group, a hydroxyl group, or K ₃ SiO- (K is independently a hydrogen atom, preferably an alkyl group with 1 to 3 carbon atoms, an aryl group such as a phenyl group, or an alkoxy group preferably with 1 to 3 carbon atoms) ether group], a trivalent group represented by -LSi=(L is preferably an alkyl group having 1 to 3 carbon atoms), a tetravalent group represented by -C≡, and 4 represented by -Si≡ It is a group selected from a valent group and a siloxane residue of 2 to 8 valence, preferably 2 to 4 valence, and when it contains a siloxane bond, it has 2 to 13 silicon atoms, preferably 2 to 5 silicon atoms. Preferred are chain, branched or cyclic organopolysiloxane residues. In addition, it may include a silalkylene structure in which two silicon atoms are bonded to an alkylene group, that is, Si-(CH ₂ ) _n -Si (in the above formula, n is an integer of 2 to 6).

This organopolysiloxane residue preferably has an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group, or a phenyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Additionally, the alkylene group in the real alkylene bond preferably has 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.

Examples of such Z include those shown below.

(In the formula, h is an integer of 2 to 4, and Me is a methyl group.)

In the above formulas (3) and (4), W is a group selected from groups having a hydrolyzable silyl group represented by the following general formulas (7a) to (7d).

(Wherein, ~6, preferably an integer of 2 to 4, and Me is a methyl group.)

Here, X is as above.

D is a single bond or a divalent organic group having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms, which may be substituted with fluorine, preferably a divalent hydrocarbon group, and examples of the divalent hydrocarbon group include methylene group, ethylene group and propylene. Groups (trimethylene group, methyl ethylene group), butylene groups (tetramethylene group, methylpropylene group), alkylene groups such as hexamethylene group and octamethylene group, arylene groups such as phenylene group, or a combination of two or more of these groups. (alkylene, arylene groups, etc.), and those in which some or all of the hydrogen atoms of these groups are substituted with fluorine atoms. As D, an ethylene group, a propylene group, and a phenylene group are preferable.

As W, specifically, those shown below can be exemplified.

(In the formula, f is the same as above.)

In the above formulas (3) and (4), α is an integer of 1 to 7, preferably an integer of 1 to 3.

In the above formulas (5) and (6), Y is a divalent group having a hydrolyzable silyl group selected from alkoxysilyl group, aryloxysilyl group, acyloxysilyl group and aroyloxysilyl group, preferably It is a group represented by general formula (8), (9), or (10).

(Wherein ^, am.)

Here, X and D are the same as above.

D' is a divalent organic group having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, which may be fluorine-substituted, preferably a divalent hydrocarbon group, and examples of the divalent hydrocarbon group include methylene group, ethylene group, and propylene group (tri methylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), alkylene group such as hexamethylene group, octamethylene group, arylene group such as phenylene group, or a combination of two or more of these groups (alkylene group) ·Arylene group, etc.), and those in which some or all of the hydrogen atoms of these groups are substituted with fluorine atoms. As D', an ethylene group or a propylene group is preferable.

In addition, R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group include methyl, ethyl, propyl, isopropyl, butyl, and isobutyl. Alkyl groups such as tert-butyl group, pentyl group, neopentyl group, hexyl group, and octyl group, cycloalkyl groups such as cyclohexyl group, alkenyl groups such as vinyl group, allyl group, and propenyl group, phenyl group, tolyl group, etc. Aralkyl groups such as aryl group, benzyl group, phenylethyl group, and phenylpropyl group can be mentioned. Among these, a methyl group is preferable.

Specifically as Y, the following groups can be mentioned.

(Wherein, X is the same as above, and Me is a methyl group.)

In the above formulas (5) and (6), β is an integer of 1 to 10, preferably an integer of 1 to 4.

In addition, in the above formulas (5) and (6), B is a hydrogen atom, an alkyl group with 1 to 4 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, or a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. is a halogen atom.

A fluoropolyether group-containing polymer-modified hydrolyzable silane represented by the above formulas (3) and (4), with a linking group Q.

and press Z

and a W group containing a hydrolyzable silyl group.

-(CH ₂ ) ₂ -Xa (where -Xa is -Si-(OCH ₃ ) ₃ or am.)

What is displayed as is exemplified below. The combination of Q, Z, and W is not limited to these, and several fluoropolyether group-containing polymer-modified hydrolyzable silanes can be obtained by simply changing Q, Z, and W. The effect of the present invention can be achieved with any fluoropolyether group-containing polymer-modified hydrolyzable silane.

(In the formula, t1 and r1 are the same as t' and r', respectively.)

(In the formula, p1 and q1 are the same as p' and q', respectively.)

(In the formula, p1 and q1 are the same as p' and q', respectively.)

(In the formula, u1 and v1 are integers greater than 1, u1+v1=t1, and t1 is equal to t'.)

In addition, as fluoropolyether group-containing polymer-modified hydrolyzable silanes represented by the above formulas (3) and (4) using those other than Q, Z, and W, and combining them, those having the following structures can be further mentioned. there is. Additionally, Xa is the same as above.

(In the formula, t1 is equal to t'.)

(In the formula, p1 and q1 are the same as p' and q', respectively.)

(In the formula, p1 and q1 are the same as p' and q', respectively.)

(In the formula, p1 and q1 are the same as p' and q', respectively.)

(In the formula, Rfa=-CF ₂ O-(C ₂ F ₄ O) _q1 (CF ₂ O) _p1 -CF ₂ -, and p1 and q1 are the same as p' and q', respectively. f1 is 1 to 10 It is an integer.)

(In the formula, p1 and q1 are the same as p' and q', respectively. f1 is an integer from 1 to 10.)

(In the formula, p1 and q1 are the same as p' and q', respectively.)

(In the formula, Rfb is -CF ₂ O-(C ₂ F ₄ O) _q1 (CF ₂ O) _p1 -CF ₂ -, and p1 and q1 are the same as p' and q', respectively. R ⁴ is -CH ₂ CH ₂ - and/or -CH(CH ₃ )-.)

(In the formula, Rfb is -CF ₂ O-(C ₂ F ₄ O) _q1 (CF ₂ O) _p1 -CF ₂ -, and p1 and q1 are the same as p' and q', respectively.)

(In the formula, p1, q1, and t1 are the same as p', q', and t', respectively.)

Polymer-modified hydrolyzable silanes containing fluoropolyether groups represented by the above formulas (5) and (6) include those having the following structures. Additionally, Xa is the same as above.

(In the formula, p1, q1, and t1 are the same as p', q', and t', respectively.)

(In the formula, p1, q1, and t1 are the same as p', q', and t', respectively.)

(In the formula, p1, q1, and t1 are the same as p', q', and t', respectively.)

(In the formula, p1, q1, and t1 are the same as p', q', and t', respectively.)

(In the formula, p1, q1, and t1 are the same as p', q', and t', respectively.)

In the fluorinated coating composition of the present invention, the terminal hydrolyzable group of silane having a hydrolyzable silyl group modified with the above fluoropolyether group-containing polymer as component (A) or component (B) is partially added by a previously known method. It may contain a partially hydrolyzed condensate obtained by hydrolyzing and condensing.

In addition, the molecular weights of component (A) and component (B) are the same (for example, the weight average molecular weight of component (B) is 0.6 to 1.3 times, especially 0.7 to 1.2 times the weight average molecular weight of component (A), In particular, it is preferably within the range of about 0.74 to 1.1 times), and these weight average molecular weights are preferably 1,000 to 20,000, respectively, and more preferably 2,000 to 10,000. If the weight average molecular weight is too small, the water/oil repellency or low friction friction properties of the fluoropolyether group may not be achieved, and if the weight average molecular weight is too large, the adhesion to the substrate may deteriorate. In addition, in the present invention, the weight average molecular weight can be measured as a standard polystyrene conversion value by gel permeation chromatography (GPC) using AK-225 (manufactured by Asahi Glass Co., Ltd.) as a developing solvent (the same applies hereinafter).

The fluorinated coating composition of the present invention also has the following general formula (11) as component (C):

(Wherein, A is the same as above, and Rf' is a polymer residue containing a divalent fluoroxyalkylene group.)

It may contain a fluoropolyether group-containing polymer (hereinafter also referred to as a non-functional polymer) represented by .

In the above equation (11), A may be the same as A exemplified above, and A may be

-F

-CF ₃

-CF ₂ CF ₃

-CF ₂ CF ₂ CF ₃

is desirable.

Rf' is a polymer residue containing a divalent fluoroxyalkylene group, and may be the same as or different from Rf exemplified above, and Rf' is preferably shown below.

(Wherein, p2 is an integer of 5 to 200, preferably 10 to 100, q2 is an integer of 5 to 200, preferably 10 to 100, r2 is an integer of 10 to 200, preferably 20 to 100, t2 is an integer of 5 to 200, preferably 10 to 100, t3 is an integer of 10 to 200, preferably 20 to 100, t2+p2 is an integer of 10 to 200, preferably 20 to 100, q2+p2 is an integer of 10 to 200, preferably 20 to 100.)

Examples of non-woven polymers represented by formula (11) include the following.

(In the formula, p2, q2, r2, t2, and t3 are the same as above.)

The weight average molecular weight of the fluoropolyether group-containing polymer of component (C) is preferably 1,000 to 50,000, more preferably 1,000 to 10,000, and further in the range of 0.5 to 1.5 times the weight average molecular weight of component (A). It is preferable that the weight average molecular weight is . If the weight average molecular weight is too small, component (A) may impair the good sliding properties, and if it is too large, the transparency of the coating film may decrease.

In addition, the non-woven polymer of component (C) can be used as a commercial product, for example, it is sold under the brand names of FOMBLIN, DEMNUM, and KRYTOX, so it can be easily obtained. Examples of such polymers include those having the following structures.

FOMBLIN Y (trade name manufactured by Solvay Solexis, FOMBLIN Y25 (weight average molecular weight: 3,200), FOMBLIN Y45 (weight average molecular weight: 4,100))

(In the formula, t2' and p2' are numbers that satisfy the above weight average molecular weight.)

FOMBLIN Z (trade name manufactured by Solvay Solexis, FOMBLIN Z03 (weight average molecular weight: 4,000), FOMBLIN Z15 (weight average molecular weight: 8,000), FOMBLIN Z25 (weight average molecular weight: 9,500))

(In the formula, q2' and p2' are numbers that satisfy the above weight average molecular weight.)

DEMNUM (product name manufactured by Daikin Kogyo, DEMNUM S20 (weight average molecular weight: 2,700), DEMNUM S65 (weight average molecular weight: 4,500), DEMNUM S100 (weight average molecular weight: 5,600))

(In the formula, r2' is a number that satisfies the above weight average molecular weight.)

KRYTOX (product name manufactured by DuPont, KRYTOX 143AB (weight average molecular weight: 3,500), KRYTOX 143AX (weight average molecular weight: 4,700), KRYTOX 143AC (weight average molecular weight: 5,500), KRYTOX 143AD (weight average molecular weight: 7,000))

(In the formula, t3' is a number that satisfies the above weight average molecular weight.)

The amount used when mixing component (C) is not particularly limited, but is preferably in the range of 0 to 50% by mass, and more preferably in the range of 5 to 50% by mass relative to the mass of component (A).

Additionally, other additives may be added to the fluorine-containing coating composition of the present invention, if necessary, within a range that does not impair the present invention. Specifically, hydrolysis condensation catalysts, such as organic tin compounds (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), organic titanium compounds (tetra n-butyl titanate, etc.), organic acids (fluorine-based carbon dioxide, etc.) Basic organic compounds such as boxylic acid, acetic acid, methanesulfonic acid, etc.), inorganic acids (hydrochloric acid, sulfuric acid, etc.), compounds having a primary amino group, compounds having a secondary amino group, compounds having a tertiary amino group, and compounds having a guanidyl group. , compounds containing alkali metals such as lithium, sodium, and potassium, and compounds containing alkaline earth metals such as magnesium and calcium. Among these, fluorine-based carboxylic acids, acetic acid, tetran-butyl titanate, and dibutyltin dilaurate are particularly preferable. The addition amount of the hydrolysis condensation catalyst is a catalytic amount, but is usually 0.01 to 5 parts by mass, especially 0.1 to 1 part by mass, per 100 parts by mass of component (A).

The fluorinated coating composition of the present invention can be prepared by uniformly mixing the above components according to a conventional method.

The surface treatment agent of the present invention includes the fluorine-containing coating composition.

The surface treatment agent of the present invention comprising a fluorinated coating composition containing component (A) and component (B) is generally dissolved and diluted in a solvent in which these polymers (component (A) and (B)) are soluble. It is used. The diluting solvent is not particularly limited as long as it can be dissolved uniformly. Such solvents include fluorine-modified aliphatic hydrocarbon-based solvents (perfluorohexane, perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon-based solvents (m-xylenehexafluoride, benzotrifluoride, 1,3- trifluoromethylbenzene, etc.), fluorine-modified ether-based solvents (methyl perfluoropropyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), etc.), fluorine-modified Alkylamine-based solvents (perfluorotributylamine, perfluorotripentylamine, etc.), partially fluorine-modified solvents (1,1,1,2,2,3,3,4,4-nonafluorohexane, 1,1 ,1,2,2,3,4,5,5,5-decafluoropentane, 1,1,1,2,2,3,3,4,4,5,5,6,6-trideca Fluorohexane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, 1,1,1,3,3-pentafluorobutane etc.), hydrocarbon solvents (petroleum benzine, mineral spirits, toluene, xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, fluorine-modified fluorine-containing solvents are preferred in terms of solubility, wettability, etc., especially ethyl perfluorobutyl ether, decafluoropentane, and 1,1,1,3,3-pentafluorobutane. This is more preferable. The above solvents may be used individually or in combination of two or more types.

The optimal concentration of component (A) and component (B) to be dissolved in the solvent varies depending on the coating treatment method, but the content of component (A) in the entire surface treatment agent including the fluorinated coating composition and the solvent is 0.01 to 50%. The amount is in the range of mass%, and is particularly preferably in the range of 0.03 to 25 mass%. If the concentration of component (A) is too low, sufficient anti-fouling properties or water and oil repellency cannot be obtained after coating treatment, and if the concentration is too high, the coating film becomes uneven, transparency decreases, or surface stickiness occurs.

The surface treatment agent comprising the fluorine-containing coating composition of the present invention can be applied to the substrate by known methods such as brush coating, dipping, spraying, and vapor deposition. In addition, the curing temperature varies depending on the curing method, but for example, when applied by spraying, inkjet, dipping, brush coating, or vacuum deposition, it is room temperature (20℃) to 200℃, especially 50 to 150℃. range is desirable. Curing humidity is preferably carried out under humidification to promote the reaction. In addition, the film thickness of the cured film is appropriately selected depending on the type of substrate, but is usually 0.1 to 100 nm, especially 3 to 30 nm.

Additionally, when adhesion is poor, adhesion can be improved by providing a SiO ₂ layer as a primer layer, or by vacuum plasma treatment, atmospheric pressure plasma treatment, or alkali treatment.

The substrate treated with the surface treatment agent comprising the fluorine-containing coating composition of the present invention is not particularly limited, and may be made of various materials such as paper, cloth, metal and its oxides, glass, plastic, ceramic, and quartz. The surface treatment agent comprising the fluorine-containing coating composition of the present invention can impart water and oil repellency, chemical resistance, release properties, low dynamic friction, and antifouling properties to these substrates. In particular, it can provide excellent antifouling performance without impairing the transparency or texture of various articles, protect the base material from penetration by chemicals, etc., and maintain antifouling performance over a long period of time. Articles treated with a surface treatment agent comprising the fluorine-containing coating composition of the present invention include optical articles, films, glass, quartz substrates, and anti-reflection films, and in particular, touch panels, anti-reflection treated articles, glass, Used for tempered glass, sapphire glass, quartz glass, and SiO ₂ processed substrates.

Example

Hereinafter, the present invention will be described in more detail by presenting examples and comparative examples, but the present invention is not limited to the following examples.

As a silane (A) containing a hydrolyzable alkoxysilyl group and/or aryloxysilyl group modified with a polymer containing a fluoropolyether group, the following compounds A1 to A4 are used as a hydrolyzable acyloxy group modified with a polymer containing a fluoropolyether group. The following compounds B1 and B2 were prepared as silane (B) containing a silyl group and/or aroyloxysilyl group.

Compound A1

(Weight average molecular weight: 4,600)

Compound A2

(Rfa: -CF ₂ O-(C ₂ F ₄ O) _q1 (CF ₂ O) _p1 -CF ₂ -, q1/p1=0.9, p1+q1≒45, f=3)

(Weight average molecular weight: 5,500)

Compound A3

(Rfb: -CF ₂ O-(C ₂ F ₄ O) _q1 (CF ₂ O) _p1 -CF ₂ -, q1/p1=1.1, p1+q1≒50, f=3)

(Weight average molecular weight: 4,800)

Compound A4

(Rfb: -CF ₂ O-(C ₂ F ₄ O) _q1 (CF ₂ O) _p1 -CF ₂ -, q1/p1=1.1, p1+q1≒40)

(Weight average molecular weight: 4,100)

Compound B1

(Rfb:- CF ₂ O-(C ₂ F ₄ O) _q1 (CF ₂ O) _p1 -CF ₂ -, q1/p1=1.1, p1+q1≒50, f=3)

(Weight average molecular weight: 4,800)

Compound B2

(Rfb: -CF ₂ O-(C ₂ F ₄ O) _q1 (CF ₂ O) _p1 -CF ₂ -, q1/p1=1.1, p1+q1≒40)

(Weight average molecular weight: 4,100)

The following C1 and C2 were prepared as curing catalysts for comparative examples.

C1: Trifluoroacetic acid

C2: Acetic acid

[Examples 1 to 6 and Comparative Examples 1 to 6]

Preparation of surface treatment agent

In Examples 1 to 6, one of the above-mentioned A1 to A4 components and one of the B1 and B2 components were mixed in the compositions shown in Table 1 below (mixtures 1 to 6), and this mixture (total of 100 parts by mass) ) was dissolved in 400 parts by mass of Novec 7200 (manufactured by 3M) so that the concentration was 20% by mass to prepare a surface treatment agent. In Comparative Examples 1 to 6, any one of the components A1 to A4 described above, or this and any one of the curing catalysts C1 and C2 for comparative examples, were mixed in the compositions shown in Table 2 below (mixtures 7 to 12), and A surface treatment agent was prepared by dissolving the mixture (total of 100 parts by mass) in 400 parts by mass of Novec 7200 (manufactured by 3M) so that the concentration was 20% by mass.

Formation of a cured film by vacuum deposition

Each of the surface treatment agents prepared above was vacuum deposited on glass (Gorilla3 manufactured by Corning Co., Ltd.) whose outermost surface was treated with 15 nm of SiO ₂ under the following conditions, and cured for 1 hour in an atmosphere of 25°C and 50% humidity to form a film (film thickness: Approximately 10 nm) was used as a test specimen for the following evaluation.

[Coating conditions and equipment by vacuum deposition]

Measuring device: Compact vacuum deposition device VPC-250F

Pressure: 2.0×10 ^-3 Pa∼3.0×10 ^-2 Pa

Deposition temperature (achieved temperature in boat): 500℃

Deposition distance: 20mm

Charge amount of treatment agent: 5mg

Deposition amount: 5mg

The cured film on the test specimen was evaluated by the following method.

[Water repellency]

The contact angle of the cured film with respect to water was measured using a contact angle meter DropMaster (manufactured by Kyowa Kaimen Chemical Co., Ltd.). The results are shown in Table 3 below.

[Abrasion resistance]

Abrasion resistance on steel wool (#0000):

Using Tribogia TYPE: 30S (manufactured by Shinto Kagaku Co., Ltd.), the cured film was reciprocally abraded 5,000 times and 10,000 times under the following conditions, and then the contact angle of the cured film with water was measured using a contact angle meter DropMaster (manufactured by Kyowakai Menu Chemical Co., Ltd.). ) was measured using . The results are shown in Table 3 below. Additionally, if the water contact angle is less than 100° after 5,000 wears, subsequent tests are not performed.

Contact area: 1cm ²

Load: 1kg

Travel distance (one way): 30 mm

Travel speed: 3,600 mm/min

Description of Table 3

Comparison of Examples 1 to 6 and Comparative Examples 1 to 4

Examples 1 to 6 are cases in which a polymer (B) having an acyloxysilyl group at a terminal having the same molecular weight distribution is added to a polymer (A) having an alkoxysilyl group at the terminal. On the other hand, Comparative Examples 1 to 4 contain only polymer (A) and do not contain polymer (B). In Examples 1 to 6, when polymer (A) and polymer (B) are deposited and coated on a substrate, curing is promoted by acid (acetic acid) generated by hydrolysis of polymer (B). On the other hand, since Comparative Examples 1 to 4 were only polymers of terminal alkoxysilane (methoxysilane), hydrolysis was slow, film curing on the substrate was slow, and wear durability was inferior to that of the Examples.

Comparison of Example 6 and Comparative Examples 5 and 6

Comparative Examples 5 and 6 are examples in which an organic acidic compound was added as a catalyst instead of component (B). In vacuum deposition, these additives have a low boiling point, so they are easily drawn into the vacuum exhaust line and can hardly settle on the surface of the substrate, so the effect of accelerating curing is not observed, and the same level as Comparative Example 4 in which nothing was added. It was.

Claims (16)

It contains the following components (A) and (B), and the mass ratio of component (A) and component (B) is (A)/(B) = 99.9/0.1 to 80/20 (component (A) and (B)) A fluorine-containing coating composition, characterized in that the sum of the masses of the components is 100.
(A) A compound that is a silane and/or a partially hydrolyzed condensate thereof having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer, wherein the hydrolyzable silyl group is an alkoxysilyl group and/or an aryloxysilyl group,
(B) A compound that is a silane and/or a partially hydrolyzed condensate thereof having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer, wherein the hydrolyzable silyl group is an acyloxysilyl group and/or an aroyloxysilyl group. According to paragraph 1,
The silane having a hydrolyzable silyl group modified with the fluoropolyether group-containing polymer of component (A) has the following general formula (1)
-C _g F _2g O- (1)
(In the formula, g is an integer of 1 to 6 independently for each unit.)
The molecule contains 10 to 200 repeating units, and at least one terminal of the fluoropolyether group-containing polymer has the following general formula (2a):

(Wherein, R ¹ is an alkyl group having 1 to 4 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R is a monovalent hydrocarbon group having 1 to 6 carbon atoms in which part of the hydrogen atoms may be replaced with halogen atoms, , a is 2 or 3.)
A fluorine-containing coating composition, characterized in that it has at least one hydrolyzable alkoxysilyl group and/or aryloxysilyl group represented by . The fluorine-containing coating composition according to claim 2, wherein in formula (2a), R ¹ is a methyl group or an ethyl group. According to any one of claims 1 to 3,
The silane having a hydrolyzable silyl group modified with the fluoropolyether group-containing polymer of component (B) has the following general formula (1)
-C _g F _2g O- (1)
(In the formula, g is an integer of 1 to 6 independently for each unit.)
A polymer containing 10 to 200 repeating units represented by , and also containing a fluoropolyether group, has the following general formula (2b) at at least one terminal:

(In the formula, R ² is an alkyl group with 1 to 4 carbon atoms, an alkoxy-substituted alkyl group with 2 to 4 carbon atoms, or a phenyl group, and R is a monovalent hydrocarbon group with 1 to 6 carbon atoms in which part of the hydrogen atoms may be substituted with a halogen atom. , a' is 1, 2 or 3.)
A fluorine-containing coating composition, characterized in that it has at least one hydrolyzable acyloxysilyl group and/or aroyloxysilyl group represented by . The fluorine-containing coating composition according to claim 4, wherein in the formula (2b), R ² is a methyl group or an ethyl group, and a' is 1 or 2. The silane according to any one of claims 1 to 5, wherein the silane having a hydrolyzable silyl group modified with the fluoropolyether group-containing polymer of component (A) and component (B) is of the following general formulas (3) and (4) ), (5), and (6).
A-Rf-QZ(W) _α (3)
Rf-(QZ(W) _α ) ₂ (4)
A-Rf-Q-(Y) _β B (5)
Rf - (Q - (Y) _β B) ₂ (6)
[In the formula, Rf is
-(CF ₂ ) _d -O-(CF ₂ O) _p (CF ₂ CF ₂ O) _q (CF ₂ CF ₂ CF ₂ O) _r (CF ₂ CF ₂ CF ₂ CF ₂ O) _s (CF(CF ₃ )CF ₂ O) _t -(CF ₂ ) _d -, and p, q, r, s, and t are each independently integers of 0 to 200, and p+q+r+s+t=10 to 200 is an integer, each unit displayed within these parentheses may be randomly combined, and d is independently an integer from 0 to 5. A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a -CF ₃ group, -CF ₂ H group, or -CFH ₂ group, and Q is a single bond or a divalent organic group that may be fluorine substituted, Z is a single bond, a diorganosilylene group, -JC=[J is an alkyl group, a hydroxyl group, or K ₃ SiO- (K is a silyl ether group independently represented by a hydrogen atom, an alkyl group, an aryl group, or an alkoxy group)] Selected from the trivalent group indicated, the trivalent group indicated by -LSi=(L is an alkyl group), the tetravalent group indicated by -C≡, the tetravalent group indicated by -Si≡, and the 2 to 8 valent siloxane residues. W is a group having the following general formulas (7a) to (7d):




[In the formula, X is the following general formula (2a) or general formula (2b)

(In the formula, R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R is an alkyl group having 1 to 6 carbon atoms in which some of the hydrogen atoms may be substituted with halogen atoms. is a monovalent hydrocarbon group, a is 2 or 3, and a' is 1, 2, or 3.)
is a group represented by , f is an integer of 1 to 10, D is a single bond or a divalent organic group having 1 to 20 carbon atoms that may be fluorine-substituted, m is an integer of 2 to 6, and Me is a methyl group. ]
It is a group selected from groups having a hydrolyzable silyl group represented by , and α is an integer of 1 to 7. Y is a divalent group having an alkoxysilyl group, an aryloxysilyl group, an acyloxysilyl group, or an aroyloxysilyl group, β is an integer of 1 to 10, and B is a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or a halogen. It is an atom.] The fluorine-containing coating composition according to claim 6, wherein Y is at least one selected from groups represented by the following general formulas (8) to (10).

(Wherein, It is a divalent organic group that may be substituted with ~10 fluorine atoms, R ³ is a monovalent hydrocarbon group with 1 to 20 carbon atoms, and e is 1 or 2.) The fluorine-containing coating composition according to claim 6 or 7, wherein Q is selected from a single bond or a divalent group represented by the following formula.



(In the formula, b is an integer of 2 to 4, c is an integer of 2 to 4, and Me is a methyl group.) The fluorine-containing coating composition according to any one of claims 6 to 8, wherein Z is selected from a single bond or a group represented by the following formula.





(In the formula, h is an integer of 2 to 4, and Me is a methyl group.) The fluorine-containing coating composition according to any one of claims 1 to 9, further comprising a fluoropolyether group-containing polymer (C) represented by the following general formula (11).

(In the formula, Rf' is a polymer residue containing a divalent fluoroxyalkylene group. A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a -CF ₃ group, -CF ₂ H group, or -CFH ₂ group. am.) A surface treatment agent comprising the fluorine-containing coating composition according to any one of claims 1 to 10. The surface treatment agent according to claim 11, which is further diluted with a solvent containing a fluorine atom. An article treated with the surface treatment agent according to claim 11 or 12. A touch panel treated with the surface treatment agent according to claim 11 or 12. An anti-reflection treated article treated with the surface treatment agent according to claim 11 or 12. A glass, tempered glass, sapphire glass, quartz glass or SiO ₂ treated substrate treated with the surface treatment agent according to claim 11 or 12.