TW201605996A - Fluorine-containing coating agent and article treated with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorine-containing coating agent and an article surface-treated with the coating agent. The coating agent improves the storage stability in a solution state before use and can stably form a uniform coating film on a substrate. SOLUTION: A fluorine-containing coating agent comprises the following components: (A) a hydrolyzable group-containing silane and/or its partially hydrolyzed condensate, wherein the silane is modified by polymer containing a fluoro-polyether group (B) a solvent capable of uniformly dissolving the aforesaid component (A), (C) a coating agent of alcohol compound having 1 to 6 carbon atoms. This invention is characterized in that the content of component (A) is 0.01 to 50% by mass with respect to the whole coating agent, and the content of component (C) is 0.01 to 5% by mass with respect to the whole coating agent.

Description

Fluorine-containing coating agent and articles treated by the coating agent

The present invention relates to a coating agent containing a hydrolyzable group-containing decane and/or a partially hydrolyzed condensate thereof modified by a fluoropolyether group-containing polymer, and more specifically, in the state of a solution before use. The storage stability is improved, and a uniform coating film can be stably formed on the substrate, and the film having excellent water repellency and low dynamic friction property contains a hydrolyzable group modified by a polymer containing a fluoropolyether group. A fluorine-containing coating agent of decane and/or a partially hydrolyzed condensate thereof, and an article treated by the coating agent.

In recent years, starting with the display of mobile phones, the touch panel of the screen is accelerating. However, many touch panels are exposed to the outside, and there are many opportunities for direct contact with fingers or cheeks, and sebum and the like are easily attached. Therefore, in order to improve the appearance or visibility, the technology for attaching a fingerprint to the surface of the display or the technique for easily removing the stain is increasing year by year.

In general, a compound containing a fluoropolyether group has a very small surface free energy, and thus has water repellency, chemical resistance, lubricity, mold release property, antifouling property and the like. Utilizing this property, it is widely used in industry. It is used for water and oil antifouling agents for paper, fiber, etc., lubricants for magnetic recording media, oil repellents for precision machines, mold release agents, cosmetics, protective films, etc. However, this property also means non-adhesiveness and non-adhesiveness to other substrates, and it is difficult to adhere the film to the substrate even if it can be applied to the surface of the substrate.

On the other hand, as a surface of a substrate or an organic compound such as glass or cloth, a decane coupling agent is widely known, and it is widely used as a coating agent for various substrate surfaces. The decane coupling agent is an organic functional group and a reactive decyl group (generally a hydrolyzable decyl group such as an alkoxyalkyl group) in one molecule. The hydrolyzable decyl group forms a film by causing a self-condensation reaction by moisture or the like in the air. The film is chemically/physically bonded to the surface of glass or metal by a hydrolyzable alkylene group to form a strong film having durability.

Therefore, it has been revealed that a hydrolyzable alkylene group is introduced into a compound containing a fluoropolyether group, and it is easy to adhere to the surface of the substrate, and it can be formed on the surface of the substrate to have water repellency, chemical resistance, lubricity, and release. A composition of a film such as a mold and an antifouling property (Patent Documents 1 to 8: Japanese Laid-Open Patent Publication No. 2003-238577, Japanese Patent No. 2860979, Japanese Patent No. 4672095, and Japanese Patent Publication No. 2008-534696 Japanese Laid-Open Patent Publication No. 2008-537557, Japanese Laid-Open Patent Publication No. 2012-072272, No. 2012-157856, and Japanese Patent Application Laid-Open No. 2013-136833.

These compositions are generally used by being diluted with a solvent capable of dissolving a fluorinated polyether group-containing decane compound. Dilution concentration The coating method differs, but in the case of spray coating, dip coating, or the like, it is usually used in a range of 0.03 to 5% by mass. These solvents are generally used by solvent manufacturers, but usually contain a small amount of water. These waters are considered to be derived from the incorporation of the solvent, or the absorption of moisture in the atmosphere or moisture adhering to the wall surface of the container after the production. The water in the solvent reacts with the hydrolyzable decyl group to cause 2-polymerization-polymerization between the polymers, which may cause gelation or polymer sedimentation depending on the case, causing problems in storage stability.

Further, even if gelation or gelation of the polymer does not occur, when the molecular weight of the polymer is increased, in the case of spray coating, inkjet coating or dip coating, there is a case where the nozzle is clogged, or the substrate is defective. The film thickness of the surface tends to be faint, and a uniform film cannot be formed, and sufficient performance cannot be obtained, and transparency or optical characteristics are impaired.

[Previous Technical Literature] [Patent Literature]

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

[Patent Document 2] Japanese Patent No. 2860979

[Patent Document 3] Japanese Patent No. 4672095

[Patent Document 4] Japanese Patent Publication No. 2008-534696

[Patent Document 5] Japanese Patent Publication No. 2008-537557

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2012-072272

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2012-157856

[Patent Document 8] Japanese Laid-Open Patent Publication No. 2013-136833

The present invention has been made in view of the above circumstances, and an object thereof is to provide a fluorine-containing coating agent which can improve a storage stability in a solution state before use and which can stably form a uniform coating film on a substrate and which is coated. A surface treated article.

In order to achieve the above object, the inventors of the present invention have found that (A) a hydrolyzable group-containing decane and/or a partially hydrolyzed condensate thereof, which is modified with a polymer containing a fluoropolyether group, and (B) The coating agent of the solvent in which the component (A) is uniformly dissolved is made to have a content of the component (A) of 0.01 to 50% by mass based on the entire coating agent, and is contained in the coating agent. The entire amount of the agent is 0.01 to 5% by mass of (C) an alcohol compound having 1 to 6 carbon atoms, which can improve storage stability in a solution state before use, and can stably form a uniform coating on a substrate. The present invention has been completed by a fluorine-containing coating agent for a film.

Accordingly, the present invention provides a fluorine-containing coating agent described below and an article treated therewith.

〔1〕

A fluorine-containing coating agent comprising the following components (A) to (C): (A) a hydrolyzable group-containing decane and/or a partially hydrolyzed condensate thereof modified by a fluoropolyether group-containing polymer And (B) a solvent capable of uniformly dissolving the above component (A), (C) A coating agent for an alcohol compound having 1 to 6 carbon atoms, characterized in that the content of the component (A) is 0.01 to 50% by mass based on the total amount of the coating agent, and the content of the component (C) It is 0.01 to 5% by mass based on the entire coating agent.

〔2〕

A fluorine-containing coating agent according to [1], wherein the component (C) is methanol or ethanol.

[3]

The fluorine-containing coating agent according to [1] or [2], wherein the hydrolyzable group-containing decane modified by the fluoropolyether group-containing polymer of the component (A) contains 10 to 200 of the following general contents. Formula (1)-C _g F _2g O- (1)

(wherein, g is an integer of 1 to 6 per unit independently), and has at least one of the following general formulas (2)

(In the formula, R is a hydrolyzable alkylene group represented by an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolyzable group, and a is 2 or 3).

[4]

A fluorine-containing coating agent according to [3], wherein the hydrolyzable group X of the formula (2) is a methoxy group or an ethoxy group.

[5]

The fluorine-containing coating agent according to any one of [1] to [4] wherein the hydrolyzable group-containing decane modified by the fluoropolyether group-containing polymer of the component (A) is a general formula (3), (4), (5), and (6) at least one selected from the group consisting of fluoropolyether-containing polymer modified decane, 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 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 -, d is independently an integer from 0 to 5, and p, q, r, s, and t are each independently an integer from 0 to 200. And is an integer of p+q+r+s+t=10~200, and each unit shown in parentheses can be randomly bonded. A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a terminal -CF ₃ group, a -CF ₂ H group or a -CFH ₂ group, and Q is a single bond or a divalent organic group which may be substituted by fluorine. Z is a decane represented by a single bond, a diorganosilylene group, -JC=[J is an alkyl group, a hydroxyl group or a K ₃ SiO- (K is independently a hydrogen atom, an alkyl group, an aryl group or an alkoxy group). a trivalent group represented by a group of an ether group, a trivalent group represented by -LSi = (L is an alkyl group), a tetravalent group represented by -C≡, a tetravalent group represented by -Si≡, and 2~ a group selected from the valence of a valence of 8 valence, W having the following general formula (7a) to (7d)

(wherein R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolyzable group, a is 2 or 3, f is an integer of 1 to 10, and D is a single bond or a carbon number of 1 to 20 a divalent organic group which may be substituted by fluorine, m is an integer of 2 to 6, and Me is a methyl group)

The base of the hydrolyzable group, α is an integer of 1 to 7; Y is a divalent group having a hydrolyzable alkyl group in the side chain, β is an integer of 1 to 10, and B is a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. Base, or halogen atom].

[6]

A fluorine-containing coating agent according to [5], wherein Y is represented by the following formulas (8) to (10),

(wherein R is an alkyl group having 1 to 4 carbon atoms, or a phenyl group, X is a hydrolyzable group, a is 2 or 3, and D is a single bond or a divalent organic compound having a carbon number of 1 to 20 which may be substituted by fluorine. The group D' is a divalent organic group which may be substituted by fluorine with a carbon number of 1 to 10, and R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and e is 1 or 2).

[7]

A fluorine-containing coating agent according to [5] or [6], wherein Q is a single bond or is selected from a divalent group represented by the following formula,

(wherein b is an integer from 2 to 4, c is an integer from 1 to 4, j is an integer from 1 to 50, and Me is a methyl group).

〔8〕

The fluorine-containing coating agent according to any one of [5] to [7] wherein Z is a single bond or is selected from 2 to 8 valent groups represented by the following formula,

(wherein h is an integer from 2 to 4, and Me is a methyl group).

〔9〕

The fluorine-containing coating agent according to any one of [1] to [8] further comprising a fluoropolyether group-containing polymer (D) represented by the following general formula (11), [Chem. 13] A-Rf -A (11)

(wherein 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 -, d is independently an integer from 0 to 5, and p, q, r, s, and t are each independently an integer from 0 to 200. And is an integer of p+q+r+s+t=10~200, and each unit shown in parentheses can be randomly bonded. A is a fluorine atom, a hydrogen atom, or a terminal is -CF ₃ group, - a monovalent fluorine-containing group of a CF ₂ H group or a -CFH ₂ group.

[10]

The fluorine-containing coating agent according to any one of [1] to [9] wherein the solvent of the component (B) is a fluorine-containing solvent.

[11]

An article treated with a fluorine-containing coating agent according to any one of [1] to [10].

[12]

A touch panel which is treated with a fluorine-containing coating agent according to any one of [1] to [10].

[13]

An antireflection-treated article which is treated with a fluorine-containing coating agent according to any one of [1] to [10].

[14]

A glass, tempered glass, sapphire glass, quartz glass or SiO ₂ treated substrate, which is treated with a fluorine-containing coating agent according to any one of [1] to [10].

The fluorine-containing coating agent of the present invention is added with a carbon number of 1 to 6 by a solution containing a hydrolyzable group-containing decane and/or a partially hydrolyzed condensate thereof modified by a polymer containing a fluoropolyether group. When the alcohol compound is mixed with water in the solution, hydrolysis of the polymer terminal during storage until use or inhibition of crosslinking reaction between the hydrolyzable groups is suppressed. Thereby, the storage stability is improved, and the barrier at the time of coating can be prevented, and a uniform coating film can be stably formed on the substrate. Therefore, excellent antifouling performance can be imparted without impairing the transparency or texture of various articles, and the substrate can be prevented from being invaded by medicines and the like, and the antifouling performance can be maintained for a long period of time.

The fluorine-containing coating agent of the present invention contains (A) a hydrolyzable group-containing decane and/or a partially hydrolyzed condensate thereof modified by a fluoropolyether group-containing polymer, and (B) the above (A) a solvent for uniformly dissolving a component, and a coating agent for (C) an alcohol compound having 1 to 6 carbon atoms, characterized in that the content of the component (A) is 0.01 to 50% by mass based on the entire coating agent, and The content of the component C) is 0.01 to 5% by mass based on the entire coating agent.

The fluoropolyether group of the component (A) having a fluoropolyether group-containing polymer modified with a fluoropolyether group-containing polymer (A) may suitably be used in an amount of 10 to 200, preferably 20~100 of the following general formula (1)-C _g F _2g O- (1)

(where g is an integer of 1 to 6 per unit independently)

The repeating unit is represented, and has at least one of the following general formulas (2) at least one end, preferably at one end.

(In the formula, R is a hydrolyzable alkylene group represented by an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolyzable group, and a is 2 or 3).

Further, the component (A) is a hydrolyzable alkylene group represented by the above formula (2) having at least one, preferably 1 to 12, and further preferably has a plurality of, preferably 2 to 36, More preferably, it is a hydrolyzable base represented by 2 to 18 X.

Examples of the repeating unit represented by the above general formula (1) as the fluoropolyether group include the following units. Further, the fluoropolyether group may be composed of one type of these repeating units or a combination of two or more types, and the respective repeating units may be randomly bonded.

-CF ₂ O-

-CF ₂ CF ₂ O-

-CF ₂ CF ₂ CF ₂ O-

-CF(CF ₃ )CF ₂ O-

-CF ₂ CF ₂ CF ₂ CF ₂ O-

-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O-

-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O-

-C(CF ₃ ) ₂ O-

In the above formula (2), R is a methyl group having 1 to 4 carbon atoms, and An alkyl group such as a propyl group, a butyl group or the like, or a phenyl group.

X is a hydrolyzable group, and the hydrolyzable group may be an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group; a trifluoromethoxy group; a trifluoroethoxy group; a halogenated alkoxy group having 1 to 6 carbon atoms such as trichloroethoxy group; an alkoxy alkoxy group having 2 to 10 carbon atoms such as a methoxymethoxy group or a methoxyethoxy group; And the like: an oxy group having 1 to 10 carbon atoms; an alkenyl group having 2 to 10 carbon atoms such as an isopropenyloxy group; a halogen group having a chlorine group, a bromine group or an iodine group; and the like. Among them, a methoxy group, an ethoxy group, an isopropenyloxy group or a chlorine group is particularly preferable.

The hydrolyzable group-containing decane modified with the fluoropolyether group-containing polymer of the component (A) is more preferably contained in the following general formulas (3), (4), (5) and (6). The fluoropolyether-based polymer is at least one selected from the group consisting of decane.

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 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 -, d is independently an integer from 0 to 5, and p, q, r, s, and t are each independently an integer from 0 to 200. And is an integer of p+q+r+s+t=10~200, and each unit shown in parentheses can be randomly bonded. A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a terminal -CF ₃ group, a -CF ₂ H group or a -CFH ₂ group, and Q is a single bond or a divalent organic group which may be substituted by fluorine. Z is a decane represented by a single bond, a diorganosilylene group, -JC=[J is an alkyl group, a hydroxyl group or a K ₃ SiO- (K is independently a hydrogen atom, an alkyl group, an aryl group or an alkoxy group). a trivalent group represented by a group of an ether group, a trivalent group represented by -LSi = (L is an alkyl group), a tetravalent group represented by -C≡, a tetravalent group represented by -Si≡, and 2~ a group selected from the valence of a valence of 8 valence, W having the following general formula (7a) to (7d)

(wherein R, X, and a are as defined above, and f is an integer of 1 to 10, and D is a single bond or a divalent organic group having a carbon number of 1 to 20 which may be substituted by fluorine, and m is 2 to 6 Integer, Me is methyl)

The base of the hydrolyzable group represented by α , and α is an integer of 1 to 7. Y is a divalent group having a hydrolyzable alkyl group in the side chain, β is an integer of 1 to 10, and B is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom.

In the above 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, d is independently an integer of 0 to 5, preferably an integer of 0 to 2, more preferably 1 or 2, and p, q, r, s, and t are each independently an integer of 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 unit shown in parentheses can be randomly bonded.

Specific examples of Rf include the following.

(wherein d' is the same as the above d, and p', q', r', s', and t' are each an integer of 1 or more, and the upper limit is the same as the upper limit of the above p, q, r, s, and t ).

In the above formulas (3) and (5), A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a terminal -CF ₃ group, a -CF ₂ H group or a -CFH ₂ group, and is contained as a monovalent group. Specific examples of the fluorine group include the following.

-CF ₃

-CF ₂ CF ₃

-CF ₂ CF ₂ CF ₃

-CF ₂ H

-CFH ₂

In the above formulae (3) to (6), Q is a single bond or a divalent organic group which may be substituted by fluorine, and is a linking group between the Rf group and the terminal group. As Q, it is preferable to contain an unsubstituted or one or more structures selected from the group consisting of a guanamine bond, an ether bond, an ester bond, or a diorganosilylene group such as a dimethylarylene group. The substituted bis-valent organic group having 2 to 12 carbon atoms is preferably an unsubstituted or substituted C 2-12 divalent hydrocarbon group having the above-mentioned structure.

Here, the unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms may be an exoethyl group, a propyl group (trimethylene group, a methyl group ethyl group), a butyl group (tetramethylene group, a methyl group). An alkyl group such as a propyl group, a hexamethylene group or an octamethyl group; an extended aryl group such as a phenyl group; or a combination of two or more kinds of these groups (alkyl group, aryl group, etc.), Further, a part or all of the hydrogen atoms of these groups may be substituted by a halogen atom such as fluorine, and among them, an unsubstituted or substituted alkyl group having 2 to 4 carbon atoms or a phenyl group is preferred.

As such Q, for example, the following groups can be mentioned.

(wherein b is an integer from 2 to 4, c is an integer from 1 to 4, j is an integer from 1 to 50, and Me is a methyl group).

In the above formulas (3) and (4), Z is a single bond, preferably a diorganosilylene group such as a dialkylarylene group having 1 to 3 carbon atoms; -JC=[J is preferably carbon An alkyl group having 1 to 3, a hydroxyl group or a 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 the like, or preferably a carbon number of 1 to 3 The trivalent group represented by the alkylene ether group shown by the alkoxy group), the trivalent group represented by -LSi=(L is preferably an alkyl group having 1 to 3 carbon atoms), and -C≡ a 4-valent group, a tetravalent group represented by -Si≡; and a selected one of a 2 to 8 valence, preferably a 2 to 4 valence alkoxysilane residue, and a ruthenium atomic bond number 2 Preferably, the chain of the chain or the cyclic organopolyoxane residue of ~13, preferably having 2 to 5 atoms. Further, it may contain two silylene atoms to form an alkyl-bonded silalkylene structure, that is, Si-(CH ₂ ) _n -Si (where n is an integer of 2 to 6).

The organopolyoxyalkylene residue is preferably an alkyl group or a phenyl group having a carbon number of 1 to 8, more preferably 1 to 4, a methyl group, an ethyl group, a propyl group or a butyl group. Further, the alkylene group in the alkylene structure is preferably a carbon number of 2 to 6, preferably 2 to 4.

Such Z can be exemplified below.

(wherein h is an integer from 2 to 4, and Me is a methyl group).

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

(wherein R, X, and a are the same as above, f is an integer of 1 to 10, preferably 2 to 8, and D is a single bond or a divalent organic group having a carbon number of 1 to 20 which may be substituted by fluorine. m is an integer of 2 to 6, preferably 2 to 4, and Me is a methyl group).

Here, R, X, and a are the same as described above, and the same as described above can be exemplified.

D is a single bond, or a divalent organic group having a carbon number of 1 to 20, preferably a carbon number of 2 to 8, which may be substituted by fluorine, preferably a divalent hydrocarbon group, and a divalent hydrocarbon group may be a methylene group or an exoethyl group. , propyl (trimethylene, methyl ethyl), butyl (tetramethylene, methyl propyl), hexamethylene, octamethyl, etc. Or such an aryl group; or a combination of two or more kinds of these groups (such as an alkyl group, an aryl group, etc.), or a part or all of the hydrogen atoms of the group is replaced by a fluorine atom. D is preferably an ethyl group, a propyl group, or a phenyl group.

W specifically shows the following.

[32]-(CH ₂ ) _f -Si-(OCH ₃ ) ₃

(wherein f is the same as above).

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

In the above formulae (5) and (6), Y is a divalent group having a hydrolyzable alkylene group in the side chain, and is preferably a group represented by the following general formula (8), (9) or (10).

(wherein R, X, a, and D are the same as defined above, D' is a divalent organic group substituted by fluorine having 1 to 10 carbon atoms, and R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and e is 1 or 2).

Here, R, X, a, and D are the same as described above, and the same as described above can be exemplified.

D' is a divalent organic group which may be substituted by fluorine with a carbon number of 1 to 10, preferably a carbon number of 2 to 8, preferably a divalent hydrocarbon group, and a divalent hydrocarbon group may, for example, a methylene group, an exoethyl group, or a propenyl group. Base (trimethylene, methyl extended ethyl), butyl (four sub a methyl group, a methyl propyl group, a hexamethylene group, an octamethyl group or the like; an extended aryl group such as a phenyl group; or a combination of two or more kinds of these groups (alkyl group. An aryl group or the like, or a part or all of the hydrogen atoms of these groups are substituted by a fluorine atom or the like. D' is preferably an ethyl group or a propyl group.

Further, R ¹ 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 a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. An alkyl group such as tert-butyl, pentyl, neopentyl, hexyl or octyl; a cycloalkyl group such as a cyclohexyl group; an alkenyl group such as a vinyl group, an allyl group or a propenyl group; a phenyl group, a tolyl group or the like; An aryl group; an aralkyl group such as a benzyl group, a phenylethyl group or a phenylpropyl group. Among these, a methyl group is preferred.

Specific examples of Y include the following groups.

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

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

Further, in the above formulae (5) and (6), B is an alkyl group such as a hydrogen atom, a methyl group having 1 to 4 carbon atoms, an ethyl group, a propyl group or a butyl group; or a fluorine atom, a chlorine atom or a bromine atom; A halogen atom such as an iodine atom.

The fluoropolyether group-containing polymer modified decane represented by the above formulas (3) and (4) is exemplified by the linking group Q. With Z base , the W group containing a hydrolyzable group is

Represented. The combination of these Q, Z, and W is not limited thereto, and a plurality of polymer-modified decane containing a fluoropolyether group can be obtained by simply changing Q, Z, and W. All of the polymer modified decane containing a fluoropolyether group can exert the effects of the present invention.

In addition, in addition to the above-mentioned Q, Z, and W, and the fluoropolyether group-containing polymer-modified decane represented by the above formulas (3) and (4), the following structures can be further exemplified.

HF ₂ CO(C ₂ F ₄ O) _q1 (CF ₂ O) _p1 CF ₂ -CH ₂ OC ₃ H ₆ Si(OCH ₃ ) ₃ (q1/p1=0.9, p1+q1≒45)

[Chemical Formula 45] _{F 3 CO (C 2 F 4} O) q1 (CF 2 O) p1 CF 2 -CH 2 OC 3 H 6 Si (OCH 3) 3 (q1 / p1 = 0.9, p1 + q1 ≒ 45)

(CH ₃ O) ₃ SiC ₃ H ₆ OCH ₂ -CF ₂ O(C ₂ F ₄ O) _q1 (CF ₂ O) _p1 CF ₂ -CH ₂ OC ₃ H ₆ Si(OCH ₃ ) ₃ ( Q1/p1=0.9, p1+q1≒45)

(CH ₃ O) ₃ SiC ₃ H ₆ OCH ₂ -CF ₂ O(C ₂ F ₄ O) _q1 (CF ₂ O) _p1 CF ₂ -CH ₂ OC ₃ H ₆ Si(OCH ₃ ) ₃ ( Q1/p1=0.9, p1+q1≒23)

(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)

(q1/p1=1.1, p1+q1≒45)

(q1/p1=0.9, p1+q1≒45)

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

(q1/p1=0.9, p1+q1≒45)

The polymer modified decane containing a fluoropolyether group represented by the above formulas (5) and (6) may be exemplified by the following structures.

(q1/p1=0.9, p1+q1≒45)

(q1/p1=0.9, p1+q1≒45)

(q1/p1=0.9, p1+q1≒45)

(q1/p1=0.9, p1+q1≒45)

(q1/p1=1.0, p1+q1≒40)

In the fluorine-containing coating agent of the present invention, the terminal hydrolyzable group of the hydrolyzable group-containing decane which is modified by the fluoropolyether group-containing polymer may be contained as the component (A), and is known in advance. The method is partially hydrolyzed and subjected to condensation to obtain a partially hydrolyzed condensate.

Further, the weight average molecular weight of the component (A) is preferably 1,000 to 20,000, more preferably 2,000 to 10,000. When the weight average molecular weight is too small, the water repellency or low dynamic friction property of the fluoropolyether group may not be exhibited, and when 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 equivalent value of gel permeation chromatography (GPC) using AK-225 (manufactured by Asahi Glass Co., Ltd.) as a developing solvent.

The solvent of the component (B) is not particularly limited as long as it dissolves the component (A) uniformly. Examples of the solvent include a fluorine-modified aliphatic hydrocarbon solvent (perfluorohexane, perfluoroheptane, perfluorooctane, etc.), a fluorine-modified aromatic hydrocarbon solvent (hexafluoromethane, xylene, trifluoromethane). Methylbenzene, 1,3-trifluoromethylbenzene, etc., fluorine modified ether solvent (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), etc.) Fluorine modified alkyl amine solvent (perfluorotributylamine, perfluorotributylamine, etc.), partially fluorine modified solvent (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-tridecafluorohexane, 1,1,1,2,2,3,3,4,4,5,5,6,6-trifluorooctane, 1,1,1, 3,3-pentafluorobutane, etc., hydrocarbon solvent (petroleum ether, mineral spirits, toluene, xylene, etc.), ketone solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), etc. Solvent. Among these, from the viewpoints of solubility, wettability, etc., it is desirable to use a fluorine-modified fluorine-containing solvent, particularly ethyl perfluorobutyl ether or decafluoropentane. These solvents may be used alone or in combination of two or more.

The optimum concentration of the component (A) dissolved in the solvent is different depending on the method of the coating treatment, and the content of the component (A) in the fluorine-containing coating agent is preferably in the range of 0.01 to 50% by mass. Becomes 0.03~25 The amount in the range of mass %. When the concentration of the component (A) is too low, sufficient antifouling property or water repellency cannot be obtained after the coating treatment, and when it is too high, the coating film becomes uneven, transparency is lowered, or surface tackiness is generated.

Since the alcohol compound of the component (C) is a polar compound, it is coordinated by hydrogen bonding or the like in the coating agent so as to surround the hydrolyzable group of the component (A). Therefore, the role of protecting the hydrolyzable group from the water molecules mixed in from the outside can be achieved. Further, even if the hydrolyzable group of the component (A) is hydrolyzed to form a sterol group by the water molecule to be mixed, the alcohol compound is coordinated to the sterol group to inhibit the reaction of the sterol group with other hydrolyzable groups. The role.

Further, since the component (C) does not uniformly dissolve the component (A), it is not included in the component (B).

The component (C) is an alcohol compound having 1 to 6 carbon atoms. As such examples, methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-propanol, 2-butanol, 2-methyl-2-propene may be mentioned. Alcohol, 1,2-ethanediol, 1,3-propanediol, 1,2,3-propanetriol, and the like. After coating the fluorine-containing coating agent on the substrate, it is desirable that the hydrolyzable group-containing decane modified by the fluoropolyether group-containing polymer reacts rapidly with the substrate. From this point of view, it is desirable that the component (C) is rapidly volatilized from the surface of the substrate after coating, and it is preferably methanol or ethanol having a low boiling point.

The content of the component (C) is 0.01 to 5% by mass, preferably 0.05 to 3% by mass, and more preferably 0.05 to 1% by mass based on the total amount of the coating agent. When the content of the component (C) is too small, sufficient storage stability effect in a solution state cannot be obtained, and when it is too large, the appearance of coating unevenness is not Good is easy to produce.

The fluorine-containing coating agent of the present invention may further contain the following general formula (11) as a component (D): A-Rf-A (11)

(wherein Rf and A are the same as described above).

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

In the above formula (11), Rf and A may be the same as those exemplified above for Rf and A, and Rf may be the same as Rf in the above component (A), and is preferably Rf.

(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, and r2 is an integer of 10 to 200, preferably 20 to 100, t2 It is an integer of 5 to 200, preferably 10 to 100, t3 is an integer of 10 to 200, preferably 20 to 100, and t2+p2 is 10 to 200. Preferably, the integer is from 20 to 100, q2+p2 is from 10 to 200, preferably from 20 to 100, and further, as A, preferably

-F

-CF ₃

-CF ₂ CF ₃

-CF ₂ CF ₂ CF ₃ .

The non-functional polymer represented by the formula (11) includes the following ones.

(wherein, p2, q2, r2, t2, and t3 are the same as described above).

The weight average molecular weight of the fluoropolyether group-containing polymer of the component (D) is preferably from 1,000 to 50,000, more preferably from 1,000 to 10,000, still more preferably from 0.5 to 1.5 times the weight average molecular weight of the component (A). The weight average molecular weight of the range. When the weight average molecular weight is too small, the excellent lubricity of the component (A) may be impaired, and when it is too large, there may be a coating film. The case where the transparency is lowered.

Further, as the non-functional polymer of the component (D), a commercially available product can be used, and for example, it is commercially available under the trade names of FOMBLIN, DEMNUM, and KRYTOX, and thus it can be easily obtained. Examples of such a polymer include 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))

(wherein t2 and p2 satisfy the above-mentioned 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))

(wherein, q2 and p2 satisfy the above weight average molecular weight).

DEMNUM (trade name of Daikin Industries, DEMNUM S20 (weight average molecular weight: 2,700), DEMNUM S65 (weight average molecular weight: 4,500), DEMNUM S100 (weight average molecular weight: 5,600))

(wherein r2 is a number satisfying the above weight average molecular weight).

KRYTOX (trade 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))

(wherein t3 is a number satisfying the above weight average molecular weight).

The amount of the component (D) to be blended is not particularly limited, and is preferably in the range of 0 to 50% by mass based on the mass of the component (A). When the amount is too large, there is a problem that adhesion may occur. . In addition, the lower limit of the blending is preferably 5% by mass or more from the viewpoint of effectively exerting the effect of the component (D).

Further, in the fluorine-containing coating agent of the present invention, other additives may be blended as needed without damaging the scope of the present invention. Specific examples include a hydrolysis condensation catalyst such as an organotin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organic titanium compound (such as tetra-n-butyl titanate), and an organic acid (fluorine-based). A carboxylic acid, acetic acid, methanesulfonic acid, etc.), an inorganic acid (hydrochloric acid, sulfuric acid, etc.), etc. Among these, fluorine-based carboxylic acid, acetic acid, tetra-n-butyl titanate, and dibutyltin dilaurate are particularly preferred. Hydrolyzed condensation catalyst The amount of the catalyst is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, per 100 parts by mass of the component (A).

The fluorine-containing coating agent of the present invention can inhibit hydrolysis of the polymer terminal in the solution state preservation before use, thereby improving storage stability and preventing barriers during coating, and stably forming a uniform coating on the substrate. Laminating.

The fluorine-containing coating agent of the present invention can be applied to a substrate by a known method such as brush coating, dipping, spraying, or vapor deposition. Further, although the curing temperature varies depending on the curing method, for example, when applied by a spray method, an inkjet method, a dipping method, a brush coating method, or a vacuum vapor deposition method, it is room temperature (20 ° C) to 200 ° C, particularly 50 A range of ~150 ° C is desirable. The hardening humidity is desirably carried out under humidification in terms of promoting 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.

Further, when the adhesion is not good, the SiO ₂ layer may be provided as the undercoat layer, or the adhesion may be improved by vacuum plasma treatment, atmospheric piezoelectric slurry treatment, or alkali treatment.

The substrate to be treated by the fluorine-containing coating agent of the present invention is not particularly limited, and may be various materials such as paper, cloth, metal and its oxide, glass, plastic, ceramic, quartz, and the like. The fluorine-containing coating agent of the present invention can impart water repellency, chemical resistance, mold release property, low dynamic friction property, and antifouling property to the base material. In particular, it can impart excellent antifouling properties without impairing the transparency or texture of various articles, and can protect the substrate from intrusion of drugs and the like, and maintain antifouling properties for a long period of time. Treated by the fluorine-containing coating agent of the present invention Examples of the article include an optical article, a film, a glass, a quartz substrate, and an antireflection film, and can be particularly used for a touch panel, an antireflection article, and a tempered glass.

[Examples]

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

The following compounds 1 to 4 were prepared as a hydrolyzable group-containing decane modified by a fluoropolyether group-containing polymer.

Compound 1

(weight average molecular weight: 4,600)

Compound 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 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 4

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

R:_CH ₂ CH ₂ - or -CH(CH ₃ )-, -CH ₂ CH ₂ -/-CH(CH ₃ )-≒0.65/0.35

The following is prepared as a solvent for dissolving a hydrolyzable group-containing decane which is modified with a fluoropolyether group-containing polymer.

Solvent A: Novec 7200 (ethyl perfluorobutyl ether, 3M company)

Solvent B: Vertrel XF (1,1,1,2,2,3,4,5,5,5-decafluoropentane, manufactured by DuPont)

Solvent C: ASAHIKLIN AC-2000 (1,1,1,2,2,3,3,4,4,5,5,6,6-trifluorohexane, manufactured by Asahi Glass Co., Ltd.)

The amount of water in the above solvent was measured by AQUACOUNTER AQ-2100 (Karl Fischer type moisture analyzer; manufactured by Hiranuma Sangyo Co., Ltd.), and the results are shown in Table 1.

Preparation of coating agent

Treatment agent A~G:

100 parts by mass of the coating agent was prepared in the combination shown in Table 2, and the hydrolyzable group-containing decane modified by the fluoropolyether group-containing polymer was 0.10 part by mass, the alcohol compound was 0.20 part by mass, and the solvent was 99.70. For mass parts, place a 100 mL brown bottle and tighten.

Treatment agent H, I:

100 parts by mass of the coating agent was prepared in the combination shown in Table 2, and the hydrolyzable group-containing decane modified by the fluoropolyether group-containing polymer was 0.10. The mass fraction and the solvent were 99.90 parts by mass, placed in a 100 mL brown bottle and tied tightly.

After the treatment agents A to I were placed in an oven at 50 ° C for 72 hours, various tests were carried out.

[Examples 1 to 7, Comparative Examples 1, 2] Confirmation of Preservability

The treatment agent A to I, which is the above-mentioned coating agent, was measured by gel permeation chromatography (GPC), and the ratio of formation of the high molecular weight body of 2 or more was calculated. The measurement conditions are as follows. The results are shown in Table 3.

[Measurement conditions]

Developing solvent: Hydrochlorofluorocarbon (HCFC)-225

Flow rate: 1mL/min.

Detector: Evaporative light scattering detector

Pipe column: TSKgel Multipore HXL-M 7.8mm manufactured by Tosoh Corporation ×30cm using 2

Column temperature: 35 ° C

Sample injection amount: 100 μL (concentration 0.1% by mass solution)

[Examples 8 to 14, Comparative Examples 3 and 4] Evaluation of the formation of hardened film and transparency and abrasion resistance

On the glass (Gorilla II manufactured by Corning Co., Ltd.), a spray coating device (NST-51; manufactured by T&K Co., Ltd.) was used to coat the above-mentioned formulated coating agent, that is, the treatment agent A to I, at 80 ° C and a humidity of 80%. After hardening for 1 hour, a hardened film (film thickness: about 15 nm) was formed, and a test object was produced.

The haze (transparency) measurement and the abrasion resistance test of the test article were carried out under the conditions shown below. The results are shown in Table 4.

[Haze measurement conditions]

The haze of the test article prepared above was measured in accordance with JIS K 7136 by the following apparatus.

Device name: NDH-5000 (made by Nippon Denshoku Co., Ltd.)

[Abrasion resistance test conditions]

The 10,000-time abrasion test was carried out under the following conditions, and the surface after the abrasion test was evaluated as a pass for a water contact angle of 100 or more.

Device name: back and forth friction test machine TRIBOGEAR 30S (manufactured by Shinto Scientific Co., Ltd.)

Wear material: BEMCOT (made by Asahi Kasei Corporation)

Moving distance (one way): 30mm

Movement speed: 1,600mm / min

Load: 1kg/cm ²

Contact angle meter device name: Drop Master (Kyowa Interface Science Co., Ltd.)

As a result of the above, it was found that the treatment agents H and I in which the alcohol compound was not added were increased in the proportion of the polymer which was polymerized by the above polymerization due to hydrolysis during storage (Comparative Examples 1 and 2). Moreover, when such a treatment agent was used to form a film on the surface of the glass, the uniformity of the surface was poor, and the haze value was observed to increase, and the abrasion durability was also lowered (Comparative Examples 3 and 4). On the other hand, when the treatment agents A to G to which the alcohol compound was added, it was found that the polymer was less likely to be polymerized during storage (Examples 1 to 7), and the uniformity of the coating film after coating was good, and transparency and abrasion durability were obtained. Excellent (Examples 8 to 14).

Claims (14)

A fluorine-containing coating agent comprising the following components (A) to (C): (A) a hydrolyzable group-containing decane and/or a partially hydrolyzed condensate thereof modified by a fluoropolyether group-containing polymer And (B) a solvent which can uniformly dissolve the component (A), and (C) a coating agent of an alcohol compound having 1 to 6 carbon atoms, wherein the content of the component (A) is relative to the entire coating agent. In the case of 0.01 to 50% by mass, the content of the component (C) is 0.01 to 5% by mass based on the entire coating agent. A fluorine-containing coating agent according to claim 1, wherein the component (C) is methanol or ethanol. The fluorine-containing coating agent of claim 1, wherein the hydrolyzable group-containing decane modified by the fluoropolyether group-containing polymer of the component (A) contains 10 to 200 of the following general formula (1) -C _g F _2g O- (1) (wherein g is an integer of from 1 to 6 independently per unit), and has at least one of the following general formulas (2) (In the formula, R is a hydrolyzable alkylene group represented by an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolyzable group, and a is 2 or 3). The fluorine-containing coating agent of claim 3, wherein the hydrolyzable group X of the formula (2) is a methoxy group or an ethoxy group. The fluorine-containing coating agent according to any one of claims 1 to 4, wherein the hydrolyzable group-containing decane modified by the fluoropolyether group-containing polymer of the component (A) is the following general formula (3) And (4), (5) and (6) at least one selected from the group consisting of fluoropolyether-containing polymer modified decane, 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 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 -, d is independently an integer from 0 to 5, and p, q, r, s, and t are each independently an integer from 0 to 200, and are p+q+r+s+t= An integer of 10 to 200, each unit shown in parentheses may be randomly bonded; A is a fluorine atom, a hydrogen atom, or a terminal of -CF ₃ group, -CF ₂ H group or -CFH ₂ group. a fluorine-containing group, Q is a single bond, or a divalent organic group which may be substituted by fluorine, Z is a single bond, a diorganosilylene group, -JC=[J is an alkyl group, a hydroxyl group or a K ₃ SiO- (K system) a trivalent group represented by a halogenated alkyl ether group represented by a hydrogen atom, an alkyl group, an aryl group or an alkoxy group, and a trivalent group represented by -LSi=(L is an alkyl group) a group selected from the group consisting of a tetravalent group represented by -C≡, a tetravalent group represented by -Si≡, and a nonoxyalkylene residue of 2-8 valence, and W having the following general formula (7a) to (7d) ) (wherein R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolyzable group, a is 2 or 3, f is an integer of 1 to 10, and D is a single bond or a carbon number of 1 to 20 a divalent organic group which may be substituted by fluorine, m is an integer of 2 to 6, and Me is a methyl group), and α is an integer of 1 to 7; Y is a side chain having a hydrolyzable alkyl group; The valence group, β is an integer of 1 to 10, and B is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom. The fluorine-containing coating agent of claim 5, wherein Y is represented by the following formulas (8) to (10), (wherein R is an alkyl group having 1 to 4 carbon atoms, or a phenyl group, X is a hydrolyzable group, a is 2 or 3, and D is a single bond or a divalent organic compound having a carbon number of 1 to 20 which may be substituted by fluorine. The group D' is a divalent organic group which may be substituted by fluorine with a carbon number of 1 to 10, and R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and e is 1 or 2). The fluorine-containing coating agent of claim 5, wherein Q is a single bond or is selected from a divalent group represented by the following formula, (wherein b is an integer from 2 to 4, c is an integer from 1 to 4, j is an integer from 1 to 50, and Me is a methyl group). A fluorine-containing coating agent according to claim 5, wherein Z is a single bond or is selected from 2 to 8 valent groups represented by the following formula, (wherein h is an integer from 2 to 4, and Me is a methyl group). The fluorine-containing coating agent according to any one of claims 1 to 4, further comprising a fluoropolyether group-containing polymer (D) represented by the following general formula (11), [Chem. 13] A-Rf-A (11) (wherein 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 -, d is independently an integer from 0 to 5, and p, q, r, s, and t are independently 0~ An integer of 200, and an integer of p+q+r+s+t=10~200, each unit shown in parentheses can be randomly bonded; A is a fluorine atom, a hydrogen atom, or a terminal is -CF ₃ a monovalent fluorine-containing group of a -CF ₂ H group or a -CFH ₂ group). The fluorine-containing coating agent according to any one of claims 1 to 4, wherein the solvent of the component (B) is a fluorine-containing solvent. An article treated with a fluorine-containing coating agent according to any one of claims 1 to 4. A touch panel which is treated with a fluorine-containing coating agent according to any one of claims 1 to 4. An antireflection treatment article which is treated with a fluorine-containing coating agent according to any one of claims 1 to 4. A glass, tempered glass, sapphire glass, quartz glass or SiO ₂ treated substrate treated with a fluorine-containing coating agent according to any one of claims 1 to 4.