KR20200072515A - Fluorine-containing coating composition, surface treatment agent and article - Google Patents

Abstract

(A) a silane having an alkoxysilyl group and/or an aryloxysilyl group modified with a fluoropolyether group-containing polymer, and/or a partially hydrolyzed condensate thereof, and (B) an acyl modified with a fluoropolyether group-containing polymer. A silane having an oxysilyl group and/or an aroyloxysilyl group and/or a partially hydrolyzed condensate thereof, the mass ratio of (A)/(B)=99.9/0.1 to 80/20 (total of 100) By setting it as a range, in particular in a vacuum deposition coating, the curing rate after coating is improved, and a fluorine-containing coating composition capable of forming a stable uniform film in a short time is obtained.

Description

Fluorine-containing coating 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 particularly in a vacuum deposition coating, the curing rate after coating It is possible to improve the fluorine-containing coating composition that can form a stable film in a short time, and provides a surface treatment agent comprising the coating composition, and an article treated with the surface treatment agent.

2. Description of the Related Art In recent years, touch panelization of screens, including the display of mobile phones, has accelerated. However, it is a problem that the touch panel has a lot of screens, and there are many opportunities for a finger, a ball, etc. to directly contact, and it is easy to get rid of sebum. Therefore, in order to improve the appearance and visibility, there is an increasing demand for a technique that makes it difficult to get fingerprints on the surface of the display or a technique that makes it easy to remove dirt.

In general, since the fluoropolyether group-containing compound has a very small surface free energy, it has water and oil repellency, chemical resistance, lubricity, releasability, and antifouling properties. Using its properties, industrially, water and oil-repellent and anti-fouling agents such as paper and fibers, lubricants for magnetic recording media, oil-repellents for precision equipment, mold release agents, cosmetics, and protective films are widely used. However, the properties mean that they are non-adhesive and non-adhesive to other substrates at the same time, and although it can be applied to the substrate surface, it is difficult to adhere the coating to the substrate.

On the other hand, silane coupling agents are well known as bonding organic surfaces with substrate surfaces such as glass or cloth, and are widely used as coating agents for various substrate surfaces. The silane coupling agent has an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule. The hydrolyzable silyl group undergoes a self-condensation reaction due to moisture in the air or the like to form a film. This film becomes a durable, durable film by chemically and physically bonding a hydrolyzable silyl group to a surface such as glass or metal.

Thus, by introducing a hydrolyzable silyl group into the fluoropolyether group-containing compound, it is easy to adhere to the surface of the substrate and can form a film having water and oil repellency, chemical resistance, lubricity, releasability and antifouling properties on the surface of the substrate. The composition has been disclosed (Patent Documents 1 to 8: Japanese Patent Publication 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 Publication 2012-157856, Japanese Patent Publication 2013-136833).

These compositions are generally used by diluting a fluoropolyether group-containing silane compound with a solvent capable of dissolving. The dilution concentration varies depending on the application method, but in the case of evaporation 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 a compound containing an alkoxysilyl group such as a methoxy group or an ethoxy group is used. When coated on the surface of a substrate such as glass, it is hydrolyzed by moisture in the air or adsorbed water on the substrate, and crosslinks with the active groups on the polymer or on the substrate surface to form a chemical bond. When this crosslinking reaction is rapid, the formation of a coating film proceeds rapidly, and a durable film can be formed. However, from the viewpoint of hydrolysis property, the alkoxysilyl group does not have a sufficient reaction rate, and faster curing is required.

Thus, in the prior art document, a method of adding basic compounds such as various inorganic acids, organic acids and amines as a catalyst is described for the purpose of increasing the curing rate. However, if these catalyst components remain after coating, recombination of the cross-linked portion may occur, or surface properties such as contact angle and friction coefficient may be adversely affected. In addition, in the case of the use of the surface of a touch panel such as a smartphone, since it directly contacts with a finger, from these viewpoints, a compound that volatilizes slowly with time and does not remain on the surface is preferable.

On the other hand, the evaporation coating takes the process of heating and evaporating the polymer component in the vacuum, and attaching it to the substrate. When the additive is easy to volatilize, it evaporates before the polymer, and is easily attracted to the vacuum line side, and settles on the substrate. There was a problem that a sufficient effect was not obtained because it was difficult to do.

Japanese Patent Publication 2003-238577 Japanese Patent No. 2860979 Japanese Patent No. 4672095 Japanese Special Issue 2008-534696 Japanese special number 2008-537557 Japanese Patent Publication 2012-072272 Japan Special 2012-157856 Japanese special edition 2013-136833

The present invention has been made in view of the above circumstances, and in particular, in a vacuum deposition coating, by improving the curing rate after coating, performance expression such as wear durability is fast, and a fluorine-containing coating composition capable of forming a stable film in a short time, and An object of the present invention is to provide a surface treatment agent comprising the coating composition and an article treated with the surface treatment agent.

As a result of repeated studies of the present inventors to achieve the above object, (A) a silane having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer and/or a partial hydrolysis condensate thereof, the hydrolyzable silyl group A compound which is an alkoxysilyl group and/or an aryloxysilyl group, and (B) a silane having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer and/or a partial hydrolysis condensate thereof, wherein the hydrolyzable silyl group is acyloxysilyl In the coating composition containing a compound which is a group and/or an aroyloxysilyl group, the mass ratio of the component (A) and the 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 a hydrolyzable silyl group which has a molecular weight distribution equal to that of the main subject and which has a catalytic activity by hydrolysis is released. By adding, it has been found that it is possible to improve the curing rate after coating, especially in vacuum deposition coating, and to be a fluorine-containing coating composition capable of forming a stable film in a short time, and to achieve 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]

The following (A) component and (B) component are contained, and the mass ratio of (A) component and (B) component is (A)/(B)=99.9/0.1 to 80/20 ((A) component and (B) Fluorine-containing coating composition, characterized in that the sum of the mass of the component is 100).

(A) 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 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 and/or an aroyloxysilyl group.

[2]

Silane having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer of component (A) is represented by 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.)

10 to 200 repeat units represented by a molecule, and at least one terminal of a fluoropolyether group-containing polymer is represented by the following general formula (2a)

(In the formula, 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 a part of the hydrogen atoms may be substituted with a halogen atom. , a is 2 or 3.)

A 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), the fluorine-containing coating composition according to [2], wherein R ¹ is a methyl group or an ethyl group.

[4]

Silane having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer of the component (B) is represented by 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.)

10 to 200 repeat units represented by a molecule, and at least one terminal of a fluoropolyether group-containing polymer is represented by the following general formula (2b)

(In the formula, 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 a part of the hydrogen atom may be substituted with a halogen atom. , a'is 1, 2 or 3.)

The fluorine-containing 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]

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

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)

[Wherein, Rf

-(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 -, 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, and each unit indicated in these parentheses may be randomly combined, and d is an integer from 0 to 5 independently. A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a -CF ₃ group, -CF ₂ H group or -CFH ₂ group at the terminal, and Q is a single bond or a divalent organic group which 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 independently a hydrogen atom, an alkyl group, an aryl group, or an alkoxy group)] Choose from a trivalent group represented by -LSi=(L is an alkyl group), a trivalent group represented by -C≡, a tetravalent group represented by -Si≡, and a 2-8 siloxane residue Group, and W is the following general formula (7a) to (7d)

[Wherein, 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 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 optionally substituted with 1 to 20 carbon atoms, m is an integer of 2 to 6, and Me is a methyl group. ]

It is a group selected from the group which has a hydrolyzable silyl group represented by, and (alpha) is an integer of 1-7. Y is an alkoxysilyl group, an aryloxysilyl group, an acyloxysilyl group or a divalent group having an aroyloxysilyl group, β is an integer of 1 to 10, B is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or halogen It is an atom.]

[7]

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

(Wherein, X is a group represented by the above general formula (2a) or general formula (2b), D is a single bond or a divalent organic group which may be fluorine substituted with 1 to 20 carbon atoms, D'is carbon number 1 ∼10 is a divalent organic group which may be substituted with fluorine, R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and e is 1 or 2.)

[8]

The 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 from 2 to 4, c is an integer from 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 selected from a single bond or a group represented by the following formula.

(Wherein, h is an integer of 2 to 4, Me is a methyl group.)

[10]

Further, 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).

(Wherein, Rf' is a divalent fluorooxyalkylene group-containing polymer residue. A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a -CF ₃ group, -CF ₂ H group, or -CFH ₂ group. to be.)

[11]

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

[12]

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

[13]

An article treated with the surface treatment agent of [11] or [12].

[14]

A touch panel treated with the surface treatment agent of [11] or [12].

[15]

[11] An antireflection article treated with the surface treatment agent of [12].

[16]

[11] A glass treated with the surface treatment agent described in [12], a tempered glass, a sapphire glass, a quartz glass, or an SiO ₂ treated substrate.

The fluorine-containing 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 hydrolyzable acyloxysilyl group and/or an aroyloxysilyl group having a molecular weight distribution similar to that of the polymer and having a catalytic activity leaving the catalytic activity by hydrolysis, vacuum deposition coating is performed. At the same time, the two types of polymers evaporate at the same time, uniformly dispersed on the substrate, and then hydrolyzed to uniformly generate the catalyst compound, thereby improving the curing rate after coating and forming a stable uniform coating in a short time. . In addition, it exhibits an effect of promoting curing in wet coating (spray coating, dipping coating) as well as vacuum deposition coating.

(Form for carrying out the invention)

The fluorine-containing coating composition of the present invention is (A) a silane having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer and/or a partially hydrolyzed condensate thereof, the hydrolyzable silyl group being an alkoxysilyl group and/or aryl A compound which is an oxysilyl group and (B) a silane having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer and/or a partial hydrolysis condensate thereof, the hydrolyzable silyl group being an acyloxysilyl group and/or aroyl In the coating composition containing a compound which is an oxysilyl group, the mass ratio of (A) component to (B) component is (A)/(B)=99.9/0.1 to 80/20 ((A) component and (B) component) The sum of 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, more preferably 99.5/0.5 to 90 It is /10 (the sum of the mass of (A) component and (B) component is 100). When the component (B) is less than the above ratio, the effect of promoting hardening may be difficult to be exhibited, and if it is more than the above ratio, the storage stability of the polymer during uncuring may decrease.

In addition, components (A) and (B) have different hydrolyzable silyl groups bonded to silicon atoms ((A) components are alkoxysilyl groups and/or aryloxysilyl groups, and (B) components are acyloxysilyl groups and And/or an aroyloxysilyl group.), the structure of the silane modified with a fluoropolyether group-containing polymer other than that may have the same molecular weight distribution. You may use

As the silane having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer of the component (A), the fluoropolyether group of the component (A) is represented by 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.)

10 to 200 repeat units, preferably 20 to 100 repeat units, represented by a fluoropolyether group-containing polymer, at least one terminal, preferably one or two terminals, more preferably Is the following general formula (2a) at one end

(In the formula, 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 a part of the hydrogen atoms may be substituted with a halogen atom. , a is 2 or 3.)

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

Further, the component (A) has at least one, preferably 1 to 12, hydrolyzable alkoxysilyl groups and/or aryloxysilyl groups represented by the formula (2a) in the molecule, more preferably 1 to 6 It is desirable to have a dog.

As a silane having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer of the component (B), the fluoropolyether group of the component (B) is represented by 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.)

10 to 200 repeat units, preferably 20 to 100 repeat units, represented by a fluoropolyether group-containing polymer, at least one terminal, preferably one or two terminals, more preferably Is the following general formula (2b) at one end

(In the formula, 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 a part of the hydrogen atom may be substituted with a halogen atom. , a'is 1, 2 or 3.)

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

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

As a repeating unit represented by the said general formula (1) which is a fluoropolyether group, the following unit etc. are mentioned, for example. Further, the fluoropolyether group may be composed of one kind of these repeating units alone, or may be a combination of two or more kinds, and each repeating unit may be bonded at random.

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

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

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

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

Hydrolyzable alkoxysilyl groups modified with a fluoropolyether group-containing polymer of component (A) and/or aryloxysilyl groups containing silane and hydrolyzable acyloxysilyl modified with a polymer containing fluoropolyether group of component (B). As the group and/or aroyloxysilyl group-containing silane, at least 1 selected from fluoropolyether group-containing polymer-modified hydrolyzable silanes 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)

[Wherein, Rf

-(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 -, 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, and each unit indicated in these parentheses may be randomly combined, and d is an integer from 0 to 5 independently. A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a -CF ₃ group, -CF ₂ H group or -CFH ₂ group at the terminal, and Q is a single bond or a divalent organic group which 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 independently a hydrogen atom, an alkyl group, an aryl group, or an alkoxy group)] Choose from a trivalent group represented by -LSi=(L is an alkyl group), a trivalent group represented by -C≡, a tetravalent group represented by -Si≡, and a 2-8 siloxane residue Group, and W is the following general formula (7a) to (7d)

(Wherein, X is a group represented by the general formula (2a) or (2b), f is an integer of 1 to 10, D is a single bond or a divalent organic group which may be substituted with fluorine having 1 to 20 carbons , M is an integer from 2 to 6, and Me is a methyl group.)

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

In the formulas (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 from 0 to 200, preferably p is an integer from 5 to 100, q is an integer from 5 to 100, R is an integer from 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 of these is indicated in parentheses. The units may be randomly combined. d is an integer of 0-5 independently, Preferably it is an integer of 0-2, More preferably, it is 1 or 2.

What is specifically shown below can be illustrated as Rf.

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

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

-CF ₃

-CF ₂ CF ₃

-CF ₂ CF ₂ CF ₃

-CF ₂ H

-CFH ₂

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

Here, as an unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), hexamethylene group, octa 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. In addition, some or all of the hydrogen atoms of these groups are halogens such as fluorine and iodine. The thing substituted with an atom etc. are mentioned, Especially, an unsubstituted or substituted C2-C4 alkyl group and a phenyl group are preferable.

As such Q, the following group is mentioned, for example.

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

In the formulas (3) and (4) above, Z is a single bond, preferably a diorganosilylene group such as a dialkylsilylene group having 1 to 3 carbon atoms, -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 having 1 to 3 carbon atoms, an aryl group such as a phenyl group, or preferably an alkoxy group having 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 trivalent group represented by -C≡, a tetravalent group represented by -Si≡ A valent group and a group selected from 2 to 8-valent, preferably 2- to 4-valent siloxane residues, and when containing a siloxane bond, 2 to 13 silicon atoms, preferably 2 to 5 silicon atoms It is preferably a chain, branched or cyclic organopolysiloxane residue. Further, a silalkylene structure in which two silicon atoms are bonded to an alkylene group, that is, Si-(CH ₂ ) _n -Si may be included (where n is an integer from 2 to 6).

It is preferable that the organopolysiloxane residue has an alkyl group or a phenyl group having 1 to 8 carbon atoms, more preferably 1 to 4 methyl groups, ethyl groups, propyl groups, and butyl groups. Moreover, the alkylene group in the real alkylene bond has 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.

As such Z, what is shown below is mentioned.

(Wherein, h is an integer of 2 to 4, Me is a methyl group.)

In the 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, X is as described above, f is an integer of 1 to 10, preferably 2 to 8, D is a single bond or a divalent organic group which may be substituted with 1 to 20 carbon atoms, m is 2 ∼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 which may be substituted with fluorine having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms, preferably a divalent hydrocarbon group, and as the divalent hydrocarbon group, a methylene group, ethylene group, and propylene Group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), alkylene group such as hexamethylene group and octamethylene group, arylene group such as phenylene group, or a combination of two or more of these groups (Alkylene-arylene groups, etc.), etc., and those in which some or all of the hydrogen atoms of these groups are substituted with fluorine atoms may be mentioned. As D, an ethylene group, a propylene group, and a phenylene group are preferable.

As W, specifically, what is shown below can be illustrated.

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

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

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

(Wherein, X and D are as described above, D'is a divalent organic group which may be fluorine substituted with 1 to 10 carbon atoms, R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, e is 1 or 2 to be.)

Here, X and D are as above.

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

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

The following groups are specifically mentioned as Y.

(Wherein, X is as described above, Me is a methyl group.)

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

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

As the fluoropolyether group-containing polymer-modified hydrolyzable silane represented by the formulas (3) and (4), the linking group Q is

Let Z be

W group containing a hydrolyzable silyl group

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

to be.)

What is indicated as is illustrated below. The combination of these Q, Z and W is not limited to these, and several fluoropolyether group-containing polymer-modified hydrolysable silanes are obtained by simply changing Q, Z and W. The effect of the present invention can be exhibited in 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, v1 are integers of 1 or more, u1+v1=t1, and t1 is the same as t'.)

In addition, as the fluoropolyether group-containing polymer-modified hydrolyzable silanes represented by the formulas (3) and (4) in which those other than Q, Z, and W are used, and combinations thereof, those of the following structures are further mentioned. have. In addition, Xa is as above.

(In the formula, t1 is the same as 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.)

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

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

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

(Wherein, Rfb is -CF ₂ O-(C ₂ F ₄ O) _q1 (CF ₂ O) _p1 -CF ₂ -, p1, q1 are the same as p', 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.)

Examples of the polymer-modified hydrolyzable silane containing the fluoropolyether group represented by the formulas (5) and (6) include the following structures. In addition, Xa is 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 fluorine-containing coating composition of the present invention, the terminal hydrolysable group of the silane having a hydrolysable silyl group modified with the fluoropolyether group-containing polymer as the component (A) or (B) is partially obtained by a known method in advance. It may contain a partial hydrolysis-condensation product obtained by hydrolysis and condensation.

In addition, the molecular weight of the component (A) and the component (B) is the same degree (for example, the weight average molecular weight of the component (B) is 0.6 to 1.3 times the weight average molecular weight of the component (A), particularly 0.7 to 1.2 times, In particular, it is preferably in the range of about 0.74 to 1.1 times), and the weight average molecular weight of these is 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-repellent and oil-repellent properties of the fluoropolyether group may not be exhibited, and if it is too large, the adhesion to the substrate may be deteriorated. In the present invention, the weight average molecular weight can be measured as a standard polystyrene conversion value of gel permeation chromatography (GPC) using AK-225 (manufactured by Asahi Glass Co., Ltd.) as a developing solvent (hereinafter, the same).

The fluorine-containing coating composition of the present invention is also the following general formula (11) as component (C)

(Wherein, A is as described above, Rf' is a divalent fluorooxyalkylene group-containing polymer residue.)

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

In the formula (11), A can exemplify the same as A exemplified above, and as A

-F

-CF ₃

-CF ₂ CF ₃

-CF ₂ CF ₂ CF ₃

Is preferred.

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

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

The following are mentioned as a non-woven polymer represented by Formula (11).

(Wherein, p2, q2, r2, t2, t3 are as above.)

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

In addition, commercially available products can be used as the non-woven polymer of the component (C), and are available, for example, under the trade names FOMBLIN, DEMNUM, and KRYTOX, and thus can be easily obtained. As such a polymer, the thing of the following structure is mentioned, for example.

FOMBLIN Y (trade name 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 weight average molecular weight.)

FOMBLIN Z (trade name 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 weight average molecular weight.)

DEMNUM (trade name of Daikin High School, 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 weight average molecular weight.)

KRYTOX (trade name 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 weight average molecular weight.)

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

In addition, other additives may be added to the fluorine-containing coating composition of the present invention, as necessary, within a range not impairing the present invention. Specifically, a hydrolysis condensation catalyst, for example, an organotin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organic titanium compound (tetran-butyltitanate, etc.), an organic acid (fluorine-based carbohydrate Basic organic compounds such as carboxylic 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, compounds having a guanidil 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 acid, acetic acid, tetran-butyl titanate and dibutyltin dilauric acid are particularly preferable. The addition amount of the hydrolysis-condensation catalyst is a catalyst amount, but is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, relative to 100 parts by mass of the component (A).

The fluorine-containing coating composition of the present invention can be prepared by uniformly mixing the above components according to the 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 the fluorine-containing coating composition containing the components (A) and (B) is generally dissolved and diluted in a solvent in which these polymers ((A) and (B) components) are soluble. Is used. The diluting solvent is not particularly limited as long as it can be dissolved uniformly. Examples of such solvents include fluorine-modified aliphatic hydrocarbon-based solvents (perfluorohexane, perfluoroheptane, and perfluorooctane), and fluorine-modified aromatic hydrocarbon-based solvents (m-xylenehexafluoride, benzotrifluoride, 1,3- Trifluoromethylbenzene, etc.), fluorine-modified ether-based solvents (methylperfluoropropyl ether, methylperfluorobutyl ether, ethylperfluorobutyl ether, perfluor (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.), and solvents such as 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 from the viewpoint of solubility, wettability, and the like, particularly ethyl perfluorobutyl ether, decafluoropentane and 1,1,1,3,3-pentafluorobutane It is more preferable. The solvent may be used alone or in combination of two or more.

Although the optimum concentrations of the components (A) and (B) to be dissolved in the solvent differ depending on the method of the coating treatment, the content of the component (A) is 0.01 to 50 in the entire surface treatment agent comprising the fluorine-containing coating composition and the solvent. It is an amount in the range of mass%, and particularly preferably an amount in the range of 0.03 to 25 mass%. When the concentration of the component (A) is too low, sufficient antifouling property or water and oil repellency is not obtained after the coating treatment, and when it is too high, the coating film becomes non-uniform, resulting in deterioration in transparency or stickiness on the surface.

The surface treatment agent comprising the fluorine-containing coating composition of the present invention can be applied to a substrate by a known method such as brush coating, dipping, spraying, and deposition treatment. Further, the curing temperature varies depending on the curing method, but, for example, when applied by a spray method, an inkjet method, a dipping method, a brush coating, or a vacuum deposition method, room temperature (20°C) to 200°C, particularly 50 to 150°C The range is preferred. Curing humidity is preferably performed under humidification to accelerate the reaction. Further, the film thickness of the cured film is appropriately selected depending on the type of the substrate, but is usually 0.1 to 100 nm, particularly 3 to 30 nm.

In addition, when the adhesion is poor, the adhesion can be improved by providing an SiO ₂ layer as a primer layer, or by vacuum plasma treatment, atmospheric plasma treatment, or alkali treatment.

The base material 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 oxide, glass, plastic, ceramic, quartz. The surface treatment agent comprising the fluorine-containing coating composition of the present invention can impart water and oil repellency, chemical resistance, mold release, low friction and antifouling properties to these substrates. In particular, it is possible to impart excellent antifouling performance without impairing the transparency and texture of various articles, and to protect the substrate from intrusion of chemicals and the like, and to maintain antifouling performance in the long term. Examples of the article treated with the surface treatment agent comprising the fluorine-containing coating composition of the present invention include an optical article, a film, a glass, a quartz substrate, an antireflection film, and particularly, a touch panel, an antireflective treatment article, glass, Used for tempered glass, sapphire glass, quartz glass, and SiO ₂ treated 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 by the following examples.

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

Compound A One

(Weight average molecular weight: 4,600)

Compound A 2

(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 A 3

(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 A 4

(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 B One

(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 B 2

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

Formation of cured film by vacuum deposition

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

[Coating conditions and devices by vacuum deposition]

Measuring device: Small vacuum deposition device VPC-250F

Pressure: 2.0×10 ^-3 Pa to 3.0×10 ^-2 Pa

Deposition temperature (boat reaching temperature): 500℃

Deposition distance: 20mm

Charge amount of treatment agent: 5mg

Deposition amount: 5mg

The cured film in the said test body 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 Chemicals Co., Ltd.). Table 3 shows the results.

[Abrasion resistance]

Wear resistance to steel wool (#0000):

Triboa TYPE: Using 30S (manufactured by Shinto Chemical Co., Ltd.), the cured film is recursively worn 5,000 times and 10,000 times under the following conditions, and then the contact angle of the cured film with water is measured using a contact angle gauge DropMaster (manufactured by Kyowa Chemicals, Inc.) ). Table 3 shows the results. In the case where the water contact angle is less than 100° at the time of 5,000 wear, subsequent tests are not carried out.

Contact area: 1cm ²

Load: 1kg

Travel distance (one way): 30mm

Travel speed: 3,600mm/min

Description in Table 3

Example Lessons 1-6 Comparative example Contrast of 1-4

Examples 1-6 are the cases where the polymer (B) having an acyloxysilyl group at the terminal with the same molecular weight distribution is added to the polymer (A) having an alkoxysilyl group at the terminal. On the other hand, in Comparative Examples 1 to 4, only polymer (A) was used, and polymer (B) was not blended. In Examples 1 to 6, when the polymer (A) and the polymer (B) were deposited and deposited on the substrate, curing was accelerated by acid (acetic acid) generated by hydrolysis of the polymer (B). On the other hand, since Comparative Examples 1 to 4 are only polymers of terminal alkoxysilanes (methoxysilanes), the hydrolysis was slow, the film hardening on the substrate was slow, and the wear durability was inferior to the Examples.

Example Lesson 6 Comparative example 5, 6 contrast

Comparative Examples 5 and 6 are examples in which an organic acid compound was added as a catalyst instead of the component (B). In vacuum evaporation, these additives have a low boiling point, so they are easily attracted to the vacuum exhaust line side and hardly settle to the surface of the substrate, so that the effect of promoting curing is not exhibited, and the level is the same as in Comparative Example 4 in which nothing was added. Was.

Claims (16)

The following (A) component and (B) component are contained, and the mass ratio of (A) component and (B) component is (A)/(B)=99.9/0.1 to 80/20 ((A) component and (B) Fluorine-containing coating composition, characterized in that the sum of the mass of the component is 100).
(A) 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 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 and/or an aroyloxysilyl group. According to claim 1,
Silane having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer of component (A) is represented by 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.)
10 to 200 repeat units represented by a molecule, and at least one terminal of a fluoropolyether group-containing polymer is represented by the following general formula (2a)

(In the formula, 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 a part of the hydrogen atoms may be substituted with a halogen atom. , a is 2 or 3.)
A fluorine-containing coating composition comprising 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. The method according to any one of claims 1 to 3,
Silane having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer of the component (B) is represented by 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.)
10 to 200 repeat units represented by a molecule, and at least one terminal of a fluoropolyether group-containing polymer is represented by the following general formula (2b)

(In the formula, 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 a part of the hydrogen atom may be substituted with a halogen atom. , a'is 1, 2 or 3.)
A fluorine-containing coating composition comprising at least one hydrolyzable acyloxysilyl group and/or aroyloxysilyl group represented by. The fluorine-containing coating composition according to claim 4, wherein in Formula (2b), R ² is a methyl group or an ethyl group, and a′ is 1 or 2. The silane having a hydrolyzable silyl group modified with a fluoropolyether group-containing polymer of the components (A) and (B) according to any one of claims 1 to 5, ), (5) and (6) is a fluoropolyether group-containing polymer-modified hydrolyzable silane-containing fluorine-containing coating composition, characterized in that at least one selected from.
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)
[Wherein, Rf
-(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 -, 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, and each unit indicated in these parentheses may be randomly combined, and d is an integer from 0 to 5 independently. A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a -CF ₃ group, -CF ₂ H group or -CFH ₂ group at the terminal, and Q is a single bond or a divalent organic group which 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 independently a hydrogen atom, an alkyl group, an aryl group, or an alkoxy group)] Choose from a trivalent group represented by -LSi=(L is an alkyl group), a trivalent group represented by -C≡, a tetravalent group represented by -Si≡, and a 2-8 siloxane residue Group, and W is the following general formula (7a) to (7d)

[Wherein, 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 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 optionally substituted with 1 to 20 carbon atoms, m is an integer of 2 to 6, and Me is a methyl group. ]
It is a group selected from the group which has a hydrolyzable silyl group represented by, and (alpha) is an integer of 1-7. Y is an alkoxysilyl group, an aryloxysilyl group, an acyloxysilyl group or a divalent group having an aroyloxysilyl group, β is an integer of 1 to 10, B is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or halogen It is an atom.] The fluorine-containing coating composition according to claim 6, wherein Y is at least one selected from the groups represented by the following general formulas (8) to (10).

(Wherein, X is a group represented by the above general formula (2a) or general formula (2b), D is a single bond or a divalent organic group which may be fluorine substituted with 1 to 20 carbon atoms, D'is carbon number 1 ∼10 is a divalent organic group which may be substituted with fluorine, R ³ is a monovalent hydrocarbon group having 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 from 2 to 4, c is an integer from 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.

(Wherein, h is an integer of 2 to 4, 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).

(Wherein, Rf' is a divalent fluorooxyalkylene group-containing polymer residue. A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a -CF ₃ group, -CF ₂ H group, or -CFH ₂ group. to be.) 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, 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 treatment 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.