JP2008144144A - Coating agent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating composition rapidly forming a cured film exhibiting water- and oil-repellency with a simple process. <P>SOLUTION: The coating agent composition contains (A) at least one kind of fluorine-containing organic silicon compounds expressed by the following formulae (1) or (2): Rf<SP>1</SP>-QZ<SP>1</SP>A<SB>α</SB>(1); A<SB>α</SB>Z<SP>1</SP>Q-Rf<SP>2</SP>-(Q-Z<SP>2</SP>-Q-Rf<SP>2</SP>)<SB>x</SB>-QZ<SP>1</SP>A<SB>α</SB>(2) [wherein, Rf<SP>1</SP>is a perfluoroalkyl group or a perfluorooxyalkyl group; Rf<SP>2</SP>is a perfluorooxyalkylene group; Z<SP>1</SP>is a single bond or a 2-9 valent organic group containing 1-15 Si atoms; Z<SP>2</SP>is a 2-100Si, divalent polyorganosiloxylene group containing 2-100 Si atoms; Q is a 2-12C, 2-9 valent group, which may contain an oxygen atom and/or a nitrogen atom, but in formula (2) may be each different; α is an integer of 1-8; x is an integer of 0-5; and A is a group expressed by the following general formula: -C<SB>b</SB>H<SB>2b</SB>SiR<SB>3-a</SB>X<SB>a</SB>(wherein, R is a 1-4C alkyl group or a phenyl group; X is a hydrolyzable group; a is 2 or 3; and b is an integer of 0-6)], and (B) a fluorine-containing carboxylic acid having a number-average molecular weight of 100-10,000 and containing 25% by weight, based on the molecular weight, of fluorine atoms, in a ratio of 0.001-10 parts by mass relative to 100 parts by mass of the above (A) component. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention provides a coating composition that can be cured in a short time, obtain a cured film excellent in water repellency, oil repellency, and antifouling property and impart antifouling properties to various substrate surfaces.

  Surfaces of various electronic devices such as eyeglass lenses, sunglasses, mobile phones, electronic notebooks, music players, and various display elements such as liquid crystal displays, CRT displays, plasma displays, EL displays, CDs (Compact Disks), DVDs (Digital) Optical recording media such as Versatile Disk), window glass, and the like are often provided with an antifouling coating to prevent adhesion of dirt such as fingerprints, sebum, sweat, cosmetics, foods and the like.

  Japanese Patent No. 3508342 (Patent Document 1) discloses a method of coating a compound obtained by modifying the end of perfluoropolyether with an alkoxysilyl group. Japanese Patent No. 3622830 (Patent Document 2) and Japanese Patent Application Laid-Open No. 2005-290323 (Patent Document 3) also disclose a method of coating with a compound modified with a terminal alkoxysilyl group of perfluoropolyether. Japanese Patent Application Laid-Open No. 2-248480 (Patent Document 4) and Japanese Patent Application Laid-Open No. 6-184527 (Patent Document 5) show a method for forming a stain-resistant film comprising a fluoroalkylsilane compound layer on the surface of a glass plate. Has been. Furthermore, Japanese Patent Application Laid-Open No. 6-256756 (Patent Document 6) proposes a method of forming a stain-resistant film comprising a fluoroalkylsilane compound and a polysiloxane compound on the surface of a glass plate.

  In order to apply a compound in which the terminal of these fluoroalkylsilanes or perfluoropolyethers is modified with an alkoxysilyl group, it is usually necessary to dissolve in some solvent and perform spin coating or the like. However, due to the high fluorine content, it is soluble only in limited solvents, mainly fluorine-based solvents. Furthermore, since these solvents are not mixed with water, it takes time to use moisture in the air to hydrolyze the alkoxysilyl group.

  In order to avoid this problem, after surface treatment with a silane coupling agent having a basic group that can be used in various solvents, the polar group is reacted with a fluoroalkylcarboxylic acid halide or a perfluoropolyoxyalkylcarboxylic acid halide. A surface modification method for fixing a fluorine-containing group on the surface is known (Patent Document 7). However, since the process is two steps, it is cumbersome and time consuming. In addition, a halide is formed during the reaction of the acid halide, which is not environmentally preferable.

  There is also a method of adding a catalyst in order to promote the decomposition reaction of the alkoxysilyl group. Conventionally known catalysts include organic titanates such as tetrabutyl titanate and tetraisopropyl titanate; organic titanium chelate compounds such as diisopropoxy bis (ethyl acetoacetate) titanium and diisopropoxy bis (ethyl acetoacetate) titanium; Organic aluminum compounds such as aluminum tris (acetylacetonate) and aluminum tris (ethylacetoacetate); organic zirconium compounds such as zirconium tetra (acetylacetonate) and zirconium tetrabutyrate; dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin di ( 2-ethylhexanoate), dioctyltin dilaurate, dioctyltin diacetate, organotin compounds such as dioctyltin dioctoate; naphthe Metal salts of organic carboxylic acids such as tin oxide, tin oleate, tin butyrate, cobalt naphthenate and zinc stearate; amine compounds such as hexylamine and dodecylamine phosphate, and salts thereof; quaternary such as benzyltriethylammonium acetate Ammonium salts; lower fatty acid salts of alkali metals such as potassium acetate and lithium nitrate; dialkylhydroxylamines such as dimethylhydroxylamine and diethylhydroxylamine; guanidyl group-containing organosilicon compounds such as tetramethylguanidylpropyltrimethoxysilane; organic acids (Acetic acid, methanesulfonic acid, etc.), inorganic acids (hydrochloric acid, sulfuric acid, etc.), etc. are mentioned. However, since these catalysts are not dissolved in a fluorine-based solvent or are dissolved very little even if dissolved, the catalyst efficiency is poor. In addition, the metal content may cause deterioration of the characteristics of the cured film.

Japanese Patent No. 3508342 Japanese Patent No. 3622830 JP 2005-290323 A JP-A-2-248480 JP-A-6-184527 JP-A-6-256756 JP-A-10-204421

  Then, an object of this invention is to provide the coating agent composition which can form a cured film rapidly with a simple process.

  As a result of studying to meet the above-described demand, it has been found that the above object can be achieved by using a predetermined carboxylic acid as a curing catalyst.

That is, the present invention is as follows.
(A) At least one of fluorine-containing organosilicon compounds represented by the following formula (1) or (2)

Rf ¹ -QZ ¹ A _α (1)

_{^{A α Z 1 Q-Rf 2}} - (Q-Z 2 -Q-Rf 2) x -QZ 1 A α (2)

[Wherein, Rf ¹ is a perfluoroalkyl group or a perfluorooxyalkyl group, Rf ² is a perfluorooxyalkylene group,
Z ¹ is a single bond or a divalent to 9-valent organic group containing 1 to 15 silicon atoms, Z ² is a divalent polyorganosiloxane group containing 2 to 100 silicon atoms,
Q is a 2-9 valent group having 2 to 12 carbon atoms which may contain an oxygen atom and / or a nitrogen atom, provided that in formula (2), they may be different from each other;
α is an integer of 1 to 8, x is an integer of 0 to 5, and A is a group represented by the following general formula

_{-C b H 2b SiR 3-a} X a

(Wherein R is an alkyl group having 1 to 4 carbon atoms or phenyl group, X is a hydrolyzable group, a is 2 or 3, and b is an integer of 0 to 6)] and (B) A fluorine-containing carboxylic acid having an average molecular weight of 100 to 10,000 and containing a fluorine atom of 25% by weight or more of the molecular weight is 0.001 to 10 parts by mass with respect to 100 parts by mass of the component (A).
A coating agent composition characterized by comprising.

  The surface treatment agent of the present invention cures quickly, adheres firmly to the substrate, and forms a surface excellent in water repellency and the like.

[(A) component]
The fluorine-containing organosilicon compound is represented by the above formula (1) or (2), and may be a mixture thereof. Rf ¹ and Rf ² are fluorine-containing groups. Rf ¹ is a perfluoroalkyl group or a perfluorooxyalkyl group, and may have a branch. Preferably Rf ¹ has 2 to 14 carbon atoms. Examples of the perfluoroalkyl group include the following groups.

_{CF 3} (CF 2) n-
(Where n is an integer from 1 to 13, preferably from 4 to 10)

In addition, examples of the perfluorooxyalkyl group include groups represented by the following formulas.

_{CF 3 (C k F 2k O} ) m-
(K is an integer from 1 to 8, m is an integer from 2 to 200)

Preferably, Rf ¹ is represented by the following formula (3), (4) or 5).

（式中、ｍは２〜２００、ｄは１〜３の整数、ＹはＦ又はＣＦ_３基である）

(In the formula, m is 2 to 200, d is an integer of 1 to 3, Y is F or CF ₃ group)

（式中、ｍは２〜２００の整数、ｄは１〜３の整数である）

(In the formula, m is an integer of 2 to 200, and d is an integer of 1 to 3)

（式中、ｅ、ｆはそれぞれ０〜２００の整数、但しｅ＋ｆ＝２〜２００であり、式中の繰り返し単位、（ＣＦ_２Ｏ）及び（Ｃ_２Ｆ_４Ｏ）、の配列はランダムであってよい）

(In the formula, e and f are each an integer of 0 to 200, where e + f = 2 to 200, and the sequences of the repeating units (CF ₂ O) and (C ₂ F ₄ O) in the formula are random). May be)

Rf ² is a divalent perfluorooxyalkylene group, and it does not matter whether it is linear or branched. Base _is intended (the g of an integer of 1 to 6) -C _g F 2g O- containing multiple repeating units of, for example, the general formula _{- (C g F 2g O)} h - like those shown in It is done. Here, h is an integer of 1 to 500, preferably 2 to 400, more preferably 10 to 200. Moreover, g may differ for every repeating unit.

Examples of the repeating unit -C _g F _2g O- represented by the above formula include the following units, and these repeating units may be a combination of two or more.
—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 CF 2 O-

Rf ² is preferably selected from the groups represented by the following general formulas (6), (7) and (8).

（式中、Ｙはそれぞれ独立にＦ又はＣＦ_３基、ｒは２〜６の整数、ｄは１〜３の整数、ｍ、ｎはそれぞれ０〜２００の整数、但しｍ＋ｎ＝２〜２００、ｓは０〜６の整数であり、各繰り返し単位の配列はランダムであってよい）

(Wherein Y is independently F or CF ₃ group, r is an integer of 2 to 6, d is an integer of 1 to 3, m and n are each an integer of 0 to 200, provided that m + n = 2 to 200, s Is an integer from 0 to 6, and the sequence of each repeating unit may be random)

（式中、ｌは１〜２００の整数、ｄは１〜３の整数である）

(In the formula, l is an integer of 1 to 200, and d is an integer of 1 to 3)

（式中、ＹはＦ又はＣＦ_３基、ｄは１〜３の整数、ｍ、ｎはそれぞれ０〜２００の整数、但しｍ＋ｎ＝２〜２００であり、繰り返し単位の配列はランダムであってよい）

(In the formula, Y is F or CF ₃ group, d is an integer of 1 to 3, m and n are each an integer of 0 to 200, provided that m + n = 2 to 200, and the arrangement of repeating units may be random. )

  More preferably, g is a group having 1 to 4 groups as repeating units. Further, m, p and q are preferably from 1 to 50, most preferably from 10 to 40.

Q is a group for linking the Rf ¹ or Rf ² group and the Z ¹ or Z ² group, and may be different from each other in the formula (2). However, when Z ¹ is a single bond, Q is bonded to A, and Q is a group that bonds R to the Rf ¹ or Rf ² group. Q is a 2-9 valent organic group having 2 to 12 carbon atoms, and may contain an oxygen atom and / or a nitrogen atom. Examples of Q include organic groups containing a hydrocarbon group, amide, ether, ester bond and the like represented by the following formula.

（ｎは０〜４の整数である）

(N is an integer from 0 to 4)

（ｎは１〜６の整数である）

（ｎは１〜５の整数である）

(N is an integer from 1 to 6)

(N is an integer of 1 to 5)

Z ¹ is a single bond or a divalent to 9-valent group containing 1 to 15 silicon atoms, and examples thereof include a group represented by the following formula. As described above, when Z ¹ is a single bond, the hydrolyzable group A is directly bonded to Q.

（ｎは０〜１４の整数）

(N is an integer from 0 to 14)

上式において、ｍは１〜９９の整数、好ましくは９〜４９の整数である。Ｒは、同一又は異なってよい、炭素数１〜４のアルキル基、アリール基又はアラールキル基である。 Z ² is a divalent polyorganosiloxane xylene group containing 2 to 100 silicon atoms, and a linear group represented by the following formula is preferred.

In the above formula, m is an integer of 1 to 99, preferably an integer of 9 to 49. R is the same or different and is a C1-C4 alkyl group, an aryl group, or an aralkyl group.

A is a group represented by the following formula.

_{-C b H 2b SiR 3-a} X a

In formula, X is a hydrolysable group, for example, C1-C10 alkoxy groups, such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, C2-C10, such as a methoxymethoxy group and a methoxyethoxy group. And an oxyalkoxy group, an acetoxy group and the like, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms such as an isopropenoxy group, a halogen group such as a chloro group, a bromo group and an iodo group. Of these, a methoxy group, an ethoxy group, an isopropenoxy group, and a chloro group are preferable. Moreover, a is 2 or 3, that is, there are a plurality of X, but they may be different from each other. From the viewpoint of reactivity and adhesion to the substrate, a is preferably 3.

  In A, R is a lower alkyl group having 1 to 4 carbon atoms or a phenyl group, and a methyl group is particularly preferable. b is an integer of 0 to 6, preferably 0, 2, and 3.

（Ｒ、Ｘ、ａ、ｂについては上述のとおりである）
上記Ｚ^１の各結合手にＨが結合されているオルガノハイドロジェンポリシロキサンと、付加反応触媒、例えば白金化合物、の存在下で、部分付加反応させて、基Ａを有するオルガノハイドロジェンポリシロキサンを生成する。次いで、下記式（ｉ）で示される不飽和基を含む基Ｑ’を有する含フッ素化合物を、上記基Ａを有するオルガノハイドロジェンポリシロキサンの残っているＳｉ−Ｈ結合と付加反応させる。

Ｒｆ^１Ｑ’ （ｉ）

式（ｉ）において、Ｒｆ^１は上で説明したとおりであり、Ｑ’は、例えば下記で示す不飽和基を含む基である。

An example of a method for preparing the fluorine-containing organosilicon compound is shown. In the formula (1), first, a compound having an unsaturated group represented by the following formula:

(R, X, a and b are as described above)
An organohydrogenpolysiloxane having a group A is subjected to a partial addition reaction in the presence of an organohydrogenpolysiloxane in which H is bonded to each bond of Z ¹ and an addition reaction catalyst such as a platinum compound. Generate. Next, a fluorine-containing compound having a group Q ′ containing an unsaturated group represented by the following formula (i) is subjected to an addition reaction with the remaining Si—H bond of the organohydrogenpolysiloxane having the group A.

Rf ¹ Q ′ (i)

In the formula (i), Rf ¹ is as described above, and Q ′ is, for example, a group containing an unsaturated group shown below.

The compound of formula (2) is a compound having an unsaturated group on both sides of Rf ^{2 represented by} the following formula (ii):

Q′Rf ² Q ′ (ii)

(In formula (ii), Rf ² and Q ′ are as described above).

It said ^{Z 2} bonds to cause an addition reaction with the organohydrogenpolysiloxane having a hydrogen atom bonded to ^{Q'-Rf 2 - (Q-} Z 2 -Q-Rf 2) constitutes the x -Q 'moiety, Q The above-described organohydrogenpolysiloxane having a group A is subjected to an addition reaction. The addition reaction may be performed under known reaction conditions, or the group A may be first added.

[Component (B)]
The component (B) that acts as a curing catalyst is a fluorine-containing carboxylic acid having a number average molecular weight of 100 to 10,000, preferably 200 to 8,000, and containing fluorine atoms of 25% by weight or more of the molecular weight. By containing 25% by weight or more of fluorine atoms, the solubility in a fluorine-based solvent is excellent. Furthermore, it exhibits water and oil repellency in the cured film. Preferably perfluoroalkyl carboxylic acids and / or perfluoropolyether carboxylic acids are used.

  More preferably, a structure in which one or more fluorine atoms are bonded to the carbon atom to which the carboxyl group is bonded is preferable. This structure further increases the activity as a catalyst.

（ｎは０〜２０の整数、ｍは１または２である） Preferable examples of the fluorine-containing carboxylic acid containing a fluorine atom having a molecular weight of 25% by weight or more include the following.

(N is an integer from 0 to 20, m is 1 or 2)

（ｎは０〜２０の整数である）

（ｎは０〜２０の整数である）

(N is an integer from 0 to 20)

(N is an integer from 0 to 20)

（ｎは１〜２００の整数である）

(N is an integer from 1 to 200)

（ｎは１〜１０の整数、ｍは１〜１００の整数である）

(N is an integer from 1 to 10, m is an integer from 1 to 100)

（ｌおよびｍはそれぞれ独立に０〜１００の整数、ｎは１〜１０の整数である）

(L and m are each independently an integer of 0 to 100, and n is an integer of 1 to 10)

（ｍ、ｎはそれぞれ独立に１〜２００の整数であり、各繰り返し単位はランダムに結合されていてよい）

(M and n are each independently an integer of 1 to 200, and each repeating unit may be bonded at random)

A derivative of a fluorinated carboxylic acid that generates a carboxylic acid by hydrolysis or the like at the time of use is also suitable. Such carboxylic acid derivatives are acid anhydrides and esters of the corresponding carboxylic acid.

[Mixing ratio of (A) and (B)]
Although the compounding quantity of a component (B) changes depending on desired hardening time and the molecular weight, 0.001-10 mass parts is preferable with respect to 100 mass parts of components (A), More preferably, 0.05- 2 parts by mass. If the addition amount is less than the lower limit, the effect of the catalyst is hardly exhibited, and if it exceeds the upper limit, the surface properties tend to be adversely affected, for example, the water repellency of the cured coating is lowered. The component (A) and the component (B) may be mixed by a known mixing means, and may be mixed after each is dissolved in the following solvent.

これらの溶媒は、例えば、商品名Ｎｏｖｅｃ ＨＦＥ−７１００、Ｎｏｖｅｃ ＨＦＥ−７２００、Ｎｏｖｅｃ ７３００ 、Ｆｌｕｏｒｉｎｅｒｔ ＦＣ−７７（住友３Ｍ 社製）、アサヒクリン ＡＫ−２２５（旭硝子社製）として、市販されている。これらを混合して使用したり、本発明の目的を阻害しない範囲で、非フッ素系の溶媒を添加することもできる。溶媒は、（Ａ）成分と（Ｂ）成分の合計質量％が０．０１〜１％、好ましくは０．０５〜０．５重量％になるように添加することが好ましい。 [solvent]
Although the coating agent composition of the present invention may be diluted with a solvent immediately before use, a fluorine-based solvent may be mixed in advance. Suitable examples of the fluorine-based solvent include 1,3-bistrifluoromethylbenzene and those represented by the following formula.

These solvents are commercially available, for example, under the trade names Novec HFE-7100, Novec HFE-7200, Novec 7300, Fluorinert FC-77 (manufactured by Sumitomo 3M), Asahi Clin AK-225 (manufactured by Asahi Glass). A non-fluorinated solvent can also be added within a range that does not impair the purpose of the present invention. The solvent is preferably added so that the total mass% of the component (A) and the component (B) is 0.01 to 1%, preferably 0.05 to 0.5% by weight.

[Coating method]
The coating agent composition is applied to an object. In the coating, the article to be coated is immersed in the coating agent composition, and then pulled up and dried. The component (B) acts as a catalyst, is hydrolyzed by moisture in the air, then proceeds with a condensation reaction, and a cured coating film is rapidly formed. The coating may be performed by a method such as spraying, brushing or spin coating.

  Curing after coating may be allowed to stand at 20 ° C. to 35 ° C. for about 15 minutes to 2 hours. You may heat at the temperature of 100 degrees C or less. Although it hardens | cures in the range of 10%-90% of relative humidity, the higher one is more preferable.

The substrate to be treated with the above coating agent is not particularly limited, and may be of various materials such as paper, cloth, metal and oxide thereof, glass, plastic, ceramic, and the like. Can be granted.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited by this.

[Examples and Comparative Examples]
A fluorine-containing organosilicon compound and a carboxylic acid shown in Table 1 were mixed and dissolved in Novec HFE-7200 (manufactured by Sumitomo 3M, fluorine-based solvent) at the concentrations shown in the same table to prepare a coating agent solution. A slide glass was immersed in this solution as a test piece, and then pulled up and left in a room at 25 ° C. and a relative humidity of 50%. 30 minutes after applying the coating agent, the contact angle of water on the surface of the slide glass was measured by a sliding method using a contact angle meter (A3 type, manufactured by Kyowa Interface Science Co., Ltd.). The results are shown in Table 1.

A-1 to A-7 in Table 1 are the following fluorine-containing organosilicon compounds.
(A-1)

ｎ＝２４（平均値）

（Ａ−２）

n = 24 (average value)

(A-2)

ｎ＝２４（平均値）

（Ａ−３）

n = 24 (average value)

(A-3)

ｎ＝２４（平均値）

（Ａ−４）

n = 24 (average value)

(A-4)

ｐ＝２５、ｑ＝３５（平均値）

（Ａ−５）

p = 25, q = 35 (average value)

(A-5)

ｐ＝２５、ｑ＝３５（平均値）

（Ａ−６）

p = 25, q = 35 (average value)

(A-6)

ｍ＋ｎ＝３３（平均値）

（Ａ−７）

m + n = 33 (average value)

(A-7)

ａ＝１．４（平均値）

a = 1.4 (average value)

ｎ＝２４（平均値）

n = 24 (average value)

B-1 to B-6 in Table 1 are the following catalysts.
(B-1)

Ｆ量：66.6重量％
（Ｂ−２）

F amount: 66.6% by weight
(B-2)

ｍ＝２４（平均値）、Ｆ量：68.2重量％

（Ｂ−３）

m = 24 (average value), F amount: 68.2% by weight

(B-3)

ｍ＋ｎ＝３３（平均値）、Ｆ量：67.6重量％

（Ｂ−４）

m + n = 33 (average value), F amount: 67.6% by weight

(B-4)

ｐ＝２５ ｑ＝３５（平均値）、Ｆ量：62.4重量％

p = 25 q = 35 (average value), F amount: 62.4% by weight

（Ｂ−６） (B-5)

(B-6)

表１から分かるように、Ｂ−１、Ｂ−２、Ｂ−３、Ｂ−４を硬化触媒として用いた場合は、水の接触角が高い硬化膜が得られ、コーティング剤塗布後３０分の放置にて十分に硬化したことが分かる。しかしＢ−５、Ｂ−６の場合は、水の接触角が低いことから分かるように、３０分では十分に硬化しなかった。

As can be seen from Table 1, when B-1, B-2, B-3, and B-4 were used as the curing catalyst, a cured film having a high water contact angle was obtained, and 30 minutes after the coating agent was applied. It turns out that it hardened | cured enough by leaving. However, in the case of B-5 and B-6, as shown by the low contact angle of water, it did not cure sufficiently in 30 minutes.

  The coating agent composition of the present invention is useful as a surface treating agent for various substrates that require rapid treatment.

Claims (7)

(A) At least one of fluorine-containing organosilicon compounds represented by the following formula (1) or (2)

Rf ¹ -QZ ¹ A _α (1)

_{^{A α Z 1 Q-Rf 2}} - (Q-Z 2 -Q-Rf 2) x -QZ 1 A α (2)

[Wherein, Rf ¹ is a perfluoroalkyl group or a perfluorooxyalkyl group, Rf ² is a perfluorooxyalkylene group,
Z ¹ is a single bond or a divalent to 9-valent organic group containing 1 to 15 silicon atoms, Z ² is a divalent polyorganosiloxane group containing 2 to 100 silicon atoms,
Q is a 2-9 valent group having 2 to 12 carbon atoms which may contain an oxygen atom and / or a nitrogen atom, provided that in formula (2), they may be different from each other;
α is an integer of 1 to 8, x is an integer of 0 to 5, and A is a group represented by the following general formula

_{-C b H 2b SiR 3-a} X a

(Wherein R is an alkyl group having 1 to 4 carbon atoms or phenyl group, X is a hydrolyzable group, a is 2 or 3, and b is an integer of 0 to 6)] and (B) A fluorine-containing carboxylic acid having an average molecular weight of 100 to 10,000 and containing a fluorine atom of 25% by weight or more of the molecular weight is 0.001 to 10 parts by mass with respect to 100 parts by mass of the component (A).
A coating agent composition characterized by comprising.   The coating agent composition according to claim 1, wherein the component (B) is a perfluoroalkyl carboxylic acid or a perfluoropolyether carboxylic acid. The coating agent composition according to claim 1 or 2, wherein the component (B) is represented by any one of the following formulas.

(N is an integer from 0 to 20)

(N is an integer from 0 to 20)

The said (B) component is represented by either of the following formula | equation, The coating agent composition of Claim 1 or 2 characterized by the above-mentioned.

(N is an integer from 1 to 200)

(N is an integer from 1 to 10, m is an integer from 1 to 100)

(L and m are each independently an integer of 0 to 100, and n is an integer of 1 to 10)

(M and n are each independently an integer of 1 to 200, and the arrangement of each repeating unit may be random) 5. The composition according to claim 1, further comprising (C) a fluorine-based solvent in such an amount that the total mass% of the component (A) and the component (B) is 0.01 to 1%. Coating agent composition. In the formula (1), Rf ¹ is represented by the following formula (3), (4) or (5) coating composition of any one of claims 1 to 5, characterized in that indicated by.

(In the formula, m is 2 to 200, d is an integer of 1 to 3, Y is F or CF ₃ group)

(In the formula, m is 2 to 200, and d is an integer of 1 to 3)

(In the formula, e and f are each an integer of 0 to 200, provided that e + f = 2 to 200, and the repeating unit sequence may be random) In the formula (2), Rf ² is represented by the following formula (6), (7) or the coating composition of any one of claims 1 to 6, characterized in that represented by (8).

(Wherein Y is independently F or CF ₃ group, r is an integer of 2 to 6, d is an integer of 1 to 3, m and n are each an integer of 0 to 200, provided that m + n = 2 to 200, s Is an integer of 0 to 6, and the sequence of repeating units in the general formula may be random)

(In the formula, l is an integer of 1 to 200, and d is an integer of 1 to 3)

(Wherein Y is F or CF ₃ group, d is an integer of 1 to 3, m and n are each an integer of 0 to 200, provided that m + n = 2 to 200, and the arrangement of repeating units in the formula is random. May be)