JP2003128991A - Water-repellent film and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-repellent coating enabling low-temperature film formation, easily applicable at low cost, and giving coating film of high wear resistance and hardness, in view of the fact that conventional water-repellent film is not only poor in low-temperature film formability and the adhesion to substrate but also low in film strength such as low wear resistance and low hardness, and to provide improved coating film by using the water-repellent coating. SOLUTION: This water-repellent coating film comprises (a) inorganic microparticles with the surface put to hydrophobicizing treatment, (b) a silicone- modified resin and/or a hydrolysis condensate of a silane compound, and (c) a metal alkoxide substituted and/or coordinated with organic group and/or a hydrolysis condensate of its own or with other component(s).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a water-repellent film,
Specifically, the present invention relates to a water-repellent film having excellent adhesion to a base material and high hardness, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, water repellency is imparted to a substrate by coating the surface of the substrate with a fluorine resin or a silicone resin. For example, when such a coating is applied to a smooth glass plate, water repellency with a water contact angle of about 100 ° to 110 ° is obtained. Further, it is known that the surface of an object having a fractal uneven structure exhibits super water repellency when it is formed of a water repellent substance (water contact angle of 90 ° or more). (For example, “Polymer”, vol.45, p.566 (199
For example, in JP-A-2000-1787, a polycondensate of metal alkoxide, a mixed solution of metal oxide fine particles and a silane compound having a fluoroalkyl group or an alkyl group is applied to a substrate and dried, There is described a method for modifying a surface of glass, which comprises heating to form a porous metal oxide layer having a fine concavo-convex structure in which a fluoroalkyl group or an alkyl group is exposed on the surface of the glass.

Further, in Japanese Patent Laid-Open No. 2000-26844, a fluororesin powder or an inorganic fine powder whose surface is subjected to a hydrophobic treatment, a silicone resin binder, and one or a plurality of kinds of silicone or fluorosilicone oil are used. A paint for a water-repellent coating is described which contains a mixed oil.

Further, JP-A-10-120941 discloses a silicone-based vinyl monomer containing a polyfluoroalkyl group-containing vinyl monomer and at least one hydrolyzable group bonded to a silicon atom in one molecule. A water-repellent coating composition is described in which 100 parts by weight of a copolymer with a monomer are mixed with 50 to 400 parts by weight of a powder having an average particle size of 0.1 to 50 μm. By using these methods and paints, a water-repellent film having a water contact angle of 140 ° or more is obtained.

[0005]

However, Japanese Unexamined Patent Application Publication No.
In the method of Japanese Patent Application No. 00-1787, since the silane compound having a fluoroalkyl group or an alkyl group that exhibits water repellency and the metal oxide fine particles for forming the concavo-convex structure are not bonded, a temperature of 200 ° C or less after coating is applied. There was a problem that sufficient water repellency could not be obtained by baking and the film strength was low. Further, since the polycondensate of metal alkoxide is used as the binder, not only the adhesion to the plastic substrate is poor, but also the baking at a high temperature of 200 ° C. or higher is required for the adhesion to the inorganic substrate such as the glass substrate. Therefore, this method has a problem that it is difficult to apply it to a low temperature film formation or a plastic substrate having no heat resistance.

Further, in the paint of JP-A-2000-26844, there is no strong bond between the fluororesin powder or the inorganic fine powder whose surface is subjected to hydrophobic treatment and the silicone resin binder, and a coating film containing oil is also used. Therefore, there is a problem that not only the adhesion to the substrate is insufficient but also the film strength such as abrasion resistance and hardness of the film is low. Further, the fluorine-based material is expensive and there is a problem that the product cost is increased. Further, the paint described in Japanese Patent Application Laid-Open No. 10-120941 also has the same problem that the film strength such as abrasion resistance and hardness of the film is low.

The present invention solves the above problems,
It is an object of the present invention to provide a water-repellent coating composition which can be formed at a low temperature, can be inexpensively and easily carried out, and is excellent in abrasion resistance and hardness of the film, and a coating film thereof.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present invention has revealed that the surface of the inorganic fine particles has been subjected to a hydrophobic treatment, and a hydrolysis-condensation product of a silicone-modified resin binder and / or a silane compound. , And a metal alkoxide substituted and / or coordinated with an organic group and / or a hydrolyzed condensate thereof with the self or other component, the composition is appropriately combined to cure even at a low temperature and to obtain a water contact angle of 130. Shows water repellency above ℃ and below 5 °
We found that a film with excellent wear resistance and film hardness was obtained,
The present invention has been completed.

That is, the present invention provides (1) (a) inorganic fine particles having a surface subjected to a hydrophobic treatment, (b) a hydrolyzed condensate of a silicone-modified resin and / or a silane compound, and (c).
A water-repellent film comprising a metal alkoxide substituted and / or coordinated with an organic group and / or a hydrolysis-condensation product thereof with self or another component,
(2) The water-repellent film according to (1), which is a coating film having a contact angle of water droplets of 130 ° or more and a sliding angle of 5 ° or less.
(3) The inorganic fine particles are oxides containing at least one selected from the group consisting of silicon, aluminum, titanium and zirconium (1)
Alternatively, the water-repellent film according to (2), and (4) the surface-treated inorganic fine particles are one kind of silyl compound selected from the group consisting of trialkylsilyl compounds, dialkylsilyl compounds, and perfluoroalkylsilyl compounds. Inorganic fine particles treated with (1) to
(3) The water-repellent film according to any one of (3) and (5) The inorganic repellent film according to any one of (1) to (4), which contains 40 to 70% by weight in terms of oxide. Aqueous film (6) The silicone-modified resin has a silyl group-containing vinyl resin having at least one silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group at the terminal or side chain in one molecule of the polymer. And / or a hydrolyzed condensate thereof with itself or another component, wherein the water-repellent film according to any one of (1) to (5), (7)
The water-repellent film according to any one of (1) to (6), wherein the silicone-modified resin is a silyl group-containing vinyl resin containing a fluorine-substituted alkyl group,
(8) The silane compound has the formula (I)

Embedded image R ¹ _n SiX _n1 (R ² ) _4-n-n1 (I) (In the formula, X represents a halogen atom, and R ¹ represents C1 to C2.
0 represents an alkyl group or a C6 to C13 aryl group, R
² represents OR ³ , SR ³ , or NR ³ R ⁴ , and R ³ , R ⁴
Each independently represent a hydrogen atom, a C1-C20 alkyl group, a C6-C13 aryl group, an acyl group, and n is
Represents 0, 1, or 2, n1 represents 0, or an integer of 1 to 4, and n + n1 ≦ 4. ) Is a silane compound represented by (1) to (7)
(9) The metal in the metal alkoxide according to any one of (1) to (8), wherein the metal in the metal alkoxide is at least one metal selected from aluminum, zirconium, and titanium. The water-repellent film described in (1)
0) the organic group has the formula (II)

Embedded image R ⁴ COCH ₂ COR ⁵ (II) (In the formula, R ⁴ and R ⁵ are each independently a C1 to C6 alkyl group, a C1 to C16 alkoxy group, or a C1 substituted with a halogen atom. ~ Represents a C6 alkyl group,
R ⁴ and R ⁵ cannot be alkoxy groups at the same time. ) Represented by β-diketone or β-ketostel, and formula (III)

Embedded image R ⁶ CO ₂ H (III) (wherein, R ⁶ represents a C1 to C6 alkyl group or a C1 to C6 alkyl group substituted with a halogen atom). The water-repellent film according to any one of (1) to (9), which is at least one selected from the group consisting of: (11) The metal alkoxide substituted and / or coordinated with an organic group has the formula (IV)

Embedded image M (OR ⁷ ) _m (R ⁴ COCHCOR ⁵ ) _km (IV) (wherein M represents aluminum, zirconium, or titanium, and R ⁷ represents a C1 to C6 alkyl group,
R ⁴ and R ⁵ have the same meanings as described above, k represents the valence of M, and m represents 0 or an integer of 1 to k. ) The water-repellent film according to any one of claims 1 to 10, which is a compound represented by the formula (1). (12) A metal alkoxide substituted and / or coordinated with an organic group and / or a hydrolyzed condensate thereof with itself or another component occupies 0.5 to 40% by weight in the coating film composition. The water-repellent film according to any one of (1) to (11).

(13) Substituted with (a) inorganic fine particles whose surface is subjected to hydrophobic treatment, (b) silicone modified resin and / or silane compound and / or its hydrolyzed condensate, and (c) organic group. And / or a coating solution containing a coordinated metal alkoxide and / or a hydrolysis-condensation product thereof with itself or another component, (14) (a)
Inorganic fine particles whose surface is subjected to a hydrophobic treatment, (b) a silicone-modified resin and / or a silane compound and / or a hydrolytic condensate thereof, and (c) a metal alkoxide substituted and / or coordinated with an organic group and / or Alternatively, a coating liquid containing a hydrolyzed condensate of the self or other components,
(1) to (1) characterized by being applied and dried on the substrate.
The method for producing the water-repellent film according to any one of 2).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION As the inorganic fine particles whose surface is subjected to a hydrophobic treatment, which are specifically used in the present invention, specifically, Japanese Patent Publication No.
-50882, JP-B-57-2641, JP-A-2-287459, JP-A-9-59533, JP-A-51-14900, JP-A-11-1.
The hydrophobic metal oxide fine particles described in JP-A-244464 and JP-A-11-322329 can be exemplified.

Hydrophobizing agents for treating inorganic surfaces include alkylsilazane compounds such as hexamethyldisilazane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, methyltrimethoxysilane and butyltrimethoxysilane. Chlorosilane compounds such as various alkylalkoxysilane compounds, dimethyldichlorosilane, trimethylchlorosilane,
Alternatively, a reactive functional group-containing silicone varnish, a non-reactive silicone varnish, a reactive functional group-containing silicone oil, a non-reactive silicone oil, or the like can be rubbed, and particularly, a trialkylsilyl compound, a dialkylsilyl compound, and a par Any common one may be used, such as using at least one silyl compound selected from the group consisting of fluoroalkylsilyl compounds. In addition, it is preferable that it has high hydrophobicity.

The addition amount of the hydrophobizing agent is adjusted according to the specific surface area of the fine silica powder and the addition amount of the amino group-containing silane coupling agent, but is preferably about 5 to 50 parts by weight.
If the amount added is less than 5 parts by weight, high hydrophobicity cannot be obtained. On the other hand, if it exceeds 50 parts by weight, the hydrophobicity is not so different and aggregates increase, which is not preferable.

The fine silica powder can be treated with these surface treatment agents by a general method. Specifically, silica fine powder is placed in a container equipped with a stirring device typified by a Henschel mixer, the mixture is stirred under a nitrogen atmosphere, and the above-mentioned hydrophobizing agent is added to uniformly mix, or Spray the hydrophobizing agent onto the silica powder and mix evenly. After uniformly mixing the surface hydrophobizing agent and the silica powder, the mixture is heated at a temperature of less than 300 ° C. for 30 minutes or more.

Specific examples of the inorganic fine particles to be used preferably include oxides of at least one metal selected from the group consisting of silicon, aluminum, titanium and zirconium. These metal oxides may be used in combination of two or more kinds of metal alone selected from the above-exemplified group, and further, a composite oxide of two or more kinds of metal selected from the above-exemplified group. Alternatively, a composite oxide with a metal other than the above-exemplified group can also be used. The metal oxide particles are preferably fine powders in terms of film adhesion and hardness. Specifically, a specific surface area of 5 to 500 m ² / g is preferable, and further 20 to 400 m ² is preferable. The range of / g is preferable. If the specific surface area is less than 5 m ² / g, the water repellency, adhesion and hardness of the film will be reduced, and if it exceeds 500 m ² / g, the cohesive force of the fine particles will be so strong that they will not be sufficiently dispersed in the coating liquid.

The water-repellent film preferably contains 40 to 70% by weight of the inorganic particles whose surface is subjected to the hydrophobic treatment in terms of oxide. If it is less than 40% by weight, the water repellency and water sliding property will decrease, and if it exceeds 70% by weight, the adhesion to the substrate will decrease.

As the silicone-modified resin used in the present invention, specifically, a silyl group-containing vinyl resin can be preferably exemplified. What is a silyl group-containing vinyl resin?
At least one silyl group having a silicon atom whose main chain is composed of a vinyl polymer and having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group at a terminal or a side chain, in one molecule of the polymer,
Preferably, two or more of them are contained, and most of the silyl groups are represented by the following formula:

[0018]

[Chemical 9]

(In the formula, X represents a hydrolyzable group such as a halogen atom, an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group, an amino group and / or a hydroxyl group, and R ⁸ represents a hydrogen atom or a carbon atom. Represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 1 to 10 carbon atoms, and n represents an integer of 1 to 3).

The upper limit of the number of the reactive silyl group represented by the above formula in the copolymer is preferably 5 from the viewpoint that the durability is excellent and the coating film is free from defects such as cracking. The molecular weight per reactive silyl group is 300 to
It is preferably 10,000 from the viewpoint of excellent durability and preventing occurrence of defects such as cracks in the coating film.
000 is more preferable. Further, the reactive silyl group may be bonded to the terminal of the main chain of the copolymer, may be bonded to the side chain, or may be bonded to the terminal and the side chain of the main chain.

The silyl group-containing vinyl resin may be produced by reacting (a) a hydrosilane compound with a vinyl resin having a carbon-carbon double bond, and (b) the following formula:

[0022]

[Chemical 10]

(In the formula, X, R ⁸ and n have the same meanings as described above, and R ⁹ represents an organic group having a polymerizable double bond.)
It may be produced by polymerizing the silane compound represented by and various vinyl compounds, and the production method is not limited.

Examples of the hydrosilane compound used in the production method (a) above include halogenated silanes such as methyldichlorosilane, trichlorosilane and phenyldichlorosilane; methyldiethoxysilane and methyldiethoxysilane. Alkoxysilanes such as dimethoxysilane, phenyldimethoxysilane, trimethoxysilane, triethoxysilane; Acyloxysilanes such as methyldiacetoxysilane, phenyldiacetoxysilane, triacetoxysilane; Methyldiaminosilane, triaminosilane, dimethylaminosilane , Aminosilanes such as triaminosilane.

On the other hand, examples of the silane compound used in the production method represented by (b) include compounds represented by the following formulas.

[0026]

[Chemical 11]

[0027]

[Chemical 12]

(In the figure, p represents an integer of 0 to 22.) As vinyl compounds used in the production method shown in (b), there are methyl (meth) acrylate and (meth) acrylic acid. Ethyl, butyl (meth) acrylate, (meth)
(Meth) acrylic acid esters such as 2-ethylhexyl acrylate and cyclohexyl (meth) acrylate;
Carboxylic acids such as (meth) acrylic acid, itaconic acid and fumaric acid, and acid anhydrides such as maleic anhydride; epoxy compounds such as glycidyl (meth) acrylate; amino compounds such as diethylaminoethyl (meth) acrylate and aminoethyl vinyl ether; Amide compounds such as (meth) acrylamide, itaconic acid diamide, α-ethylacrylamide, crotonamide, fumaric acid diamide, maleic acid diamide, N-butoxymethyl (meth) acrylamide; acrylonitrile, styrene, α-
Vinyl-based compounds selected from methylstyrene, vinyl chloride, vinyl acetate, vinyl propionate, etc., hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyvinyl ether, and N-methylolacrylamide. Examples of the vinyl compound include

Specific examples of the silyl group-containing vinyl resin as described above include, for example:

[0030]

[Chemical 13]

(Where R²⁰ Is a hydrogen atom or methyl
Group, R^{twenty one}Is a methyl group, ethyl group, n-propyl group, n-
Butyl group, i-butyl group, n-pentyl group, n-hexyl
R1 and other alkyl groups having 1 to 6 carbon atoms, R^{twenty two}Is R²⁰ When
The same, R^{twenty three}Is a methylene group, ethylene group, propylene
Alkylene group having 1 to 4 carbon atoms such as benzene group and butylene group,
R ^{twenty four}Is R^{twenty one} And m / (l + m) = 0.01
~ 0.4, preferably 0.02-0.2)
Acrylic polymer containing trialkoxysilyl group
You can This silyl group-containing vinyl resin
The average molecular weight is preferably 2,000 to 100,000,
More preferably, it is 4,000 to 50,000.

Specific examples of the silyl group-containing vinyl resin used in the present invention as described above include Kaneka Zemlac, manufactured by Kanebuchi Chemical Industry Co., Ltd.

Further, the silicone-modified resin used in the present invention is preferably a silyl group-containing vinyl resin having a fluorine-substituted alkyl group in the molecule. In this case, the fluorine-substituted alkyl group is a methyl group, an ethyl group,
A group in which part or all of hydrogen atoms bonded to carbon atoms of an alkyl group such as a propyl group, a butyl group and an octyl group are substituted with a fluorine atom, and can be copolymerized with the above-mentioned vinyl monomer containing a silyl group. It is obtained by copolymerizing a vinyl monomer having a fluorine-substituted alkyl group. The polyfluoroalkyl group-containing vinyl monomer may be a mixture of two or more kinds. Further, the higher the fluorine content is, the higher the water repellency effect is. Therefore, the fluorine-substituted alkyl group is preferably a fluorine-substituted butyl group or more.
Particularly, C ₄ F ₉ , C ₆ F ₁₃ , C ₈ F _17, etc. are preferable.

Vinyl monomer containing polyfluoroalkyl group
Specifically, CH₂= CHCO₂CH₂CF₃, C
H₂= CHCO₂CH₂CF₂CF₂H, CH₂= C (C
H₃) CO ₂CH₂CF₃, CH₂= C (CH₃) CO₂CH
(CF₃)₂, CH₂= CHCO₂CH (CH₃) C₃F₇,
CH₂= CHCO₂CH₂(CF₂)_FourH, CH₂= CHCO
₂CH ₂C_FourF₉, CH₂= C (CH₃) CO₂CH₂C
₆F₁₃, CH₂= C (CH₃) CO₂(CH₂)₂C₈F₁₇,
CH₂= CHCO₂(CH₂)₂C₈F₁₇Compound indicated by
Thing, the following formula CH₂= CHOCH₂CH₂C₈F₁₇, CH₂
= CHCO₂CH₂CH₂OCH₂CF₃, CH₂= CHCO
₂CH₂CH₂O-CO-CO-CF (CF₃)-[OCF
₂CF (CF₃)] NOC₃F₇, CH₂= CHCO₂CH₂
CF (CF₃)-[OCF₂CF (CF₃)] NOC
₃F₇, CH₂= C (CH₃) CO₂CH₂CH₂OCF₂CF
₂H, CH₂= CHCO₂CH₂CH₂OCH₂C_FourF₉Indicated by
Such derivatives can be exemplified.

The method for producing the copolymer represented by (B) is not limited to radical polymerization, anionic polymerization or cationic polymerization, but among them, azo radical polymerization initiation such as azobisisobutyronitrile is initiated. It is preferably produced by a radical solution polymerization method using an agent.

The solvent used in the solution polymerization method is not particularly limited as long as it is non-reactive. For example, hydrocarbons such as toluene, xylene, n-hexane and cyclohexane; ethyl acetate, butyl acetate. Acetate esters such as; cellosolves such as ethyl cellosolve and butyl cellosolve; ether esters such as cellosolve acetate; methyl ethyl ketone, ethyl acetoacetate,
Ketones such as acetylacetone, methyl isobutyl ketone, and acetone; methanol, isopropyl alcohol, n-butanol, isobutanol, hexanol,
Examples include alcohols such as octanol.

In the solution polymerization, if necessary, for example, n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, (CH ₃ O) ₃ Si—S—S—Si (OC
H _{3) 3,} be adjusted _{(CH 3 O) 3 Si-} S 8 -Si (OCH 3) by individually or in combination of two or more chain transfer agents, such as _3, molecular weight of the resulting copolymer Good. Particularly, when a chain transfer agent having an alkoxysilyl group in the molecule such as γ-mercaptopropyltrimethoxysilane is used, a reactive silyl group can be introduced at the terminal of the copolymer, which is preferable. The amount of the chain transfer agent used is 0.05 to 10 based on the total amount of the polymerization components used.
%, Particularly 0.1-8% is preferred.

The silane compound used in the present invention is not particularly limited, but the silane compound represented by the formula (I) can be preferably exemplified.

In the formula (I), X represents a halogen atom, and specific examples thereof include a chloro atom, a bromo atom and an iodine atom. R ¹ is a C1-C20 alkyl group,
Represents a C6-C13 aryl group, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-
Examples thereof include a butyl group, s-butyl group, t-butyl group, isosobutyl group, n-pentyl group, n-hexyl group, n-dodecyl group, phenyl group, benzyl group, naphthyl group and anthracenyl group. R ² is OR ³ , SR
³ or an ^{NR 3 R 4,, R 3} , R 4 , it it independently, a hydrogen atom, C1 to C20 alkyl group, C6～C13
It represents an aryl group or an acyl group, and as R ² , specifically,
Hydroxyl group, methoxy group, ethoxy group, n-propoxy group,
n-butoxy group, isobutoxy group, benzyloxy group,
Phenoxy group, acetoxy group, trifluoroacetyloxy group, benzoyloxy group, methylthio group, ethylthio group, n-propylthio group, n-butylthio group, isobutylthio group, benzylthio group, phenylthio group, methylamino group, dimethylamino group, Examples thereof include ethylamino group, diethylamino group, n-propylamino group, isopropylamino group, n-butylamino group, isobutylamino group, phenylamino group, acetylamino group, trifluoroacetylamino group, benzoylamino group and the like. it can. n represents 0, 1, or 2, n1 represents 0, or an integer of 1 to 4, and when R ² is 2 or more, R ¹ may be the same or different. N + n1 is 0 or an integer of 4 or less.

Of these, OR ³ is preferred as R ² , and in this case R ³ is particularly a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms such as an aryl group, preferably a phenyl group. A monovalent hydrocarbon group selected from aryl groups having 6 to 9 and aralkyl groups, preferably aralkyl groups having 7 to 9 carbon atoms such as benzyl group.

Preferred specific examples of the compound represented by the formula (I) are tetramethyl silicate, tetraethyl silicate, tetra n-propyl silicate and tetra i-.
Tetraalkyl silicates such as propyl silicate, tetra n-butyl silicate, tetra i-butyl silicate, and tetra t-butyl silicate, trimethylchlorosilicate, triethylchlorosilicate, tri-n-propylchlorosilicate, tri-i-propylchlorosilicate, tri-n -Bulkyl chlorosilicate, tri-i-butyl chlorosilicate, tri-t-butyl chlorosilicate, and other trialkoxyhalosilicates, dimethyldichlorosilicate, diethyldichlorosilicate, di-n-propyldichlorosilicate, di-propyldichlorosilicate, di-n- Dialkoxydihalosilicates such as butyldichlorosilicate, di-butyldichlorosilicate, dit-butyldichlorosilicate, trimethylmethylsilicate, Li ethyl methyl silicate, tri n
-Propyl methyl silicate, tri i-propyl methyl silicate, tri n-butyl methyl silicate, tri i
-Butylmethyl silicate, tri-t-butylmethyl silicate, trimethylphenyl silicate, triethylphenyl silicate, dimethylchloromethyl silicate,
Diethyl chloromethyl silicate, di n-propyl chloromethyl silicate, di i-propyl chloromethyl silicate, di n-butyl chloromethyl silicate, di i-
Butyl chloromethyl silicate, di-t-butyl chloromethyl silicate, dimethyl chlorophenyl silicate,
Examples include diethyl chlorophenyl silicate, dimethyl dimethyl silicate, diethyl dimethyl silicate, dimethyl diphenyl silicate, and diethyl diphenyl silicate.

As the silane compound used in the present invention, it is preferable to use not only the above-mentioned monomers but also partial hydrolysis-condensation products thereof as a component of the coating solution. Examples of the partial hydrolyzed condensate of the organosilicate compound include an organosilicate compound such as tetraalkyl silicate, trialkoxysilane, and triaryloxysilane, which is used as a raw material in the usual manner, and a predetermined amount of water is added thereto to form an acid catalyst. The reaction is usually carried out at about room temperature to 100 ° C. while distilling off the by-produced alcohol. By this reaction, the alkoxysilane is hydrolyzed, and further a liquid silicate oligomer having two or more hydroxyl groups (usually an average degree of polymerization of about 2 to 8, preferably 3 to 6) is obtained as a hydrolyzate by a condensation reaction.

The degree of hydrolysis can be appropriately adjusted depending on the amount of water used, but is usually about 40 to 90%,
It is preferably selected from about 60 to 80%.
The hydrolyzate thus obtained usually contains more than 10% of the monomer, and it may be used as it is, but the monomer is removed from the obtained hydrolysis, and preferably 1% or less, By setting it to preferably 0.1% or less, the storage stability of the liquid material can be enhanced. As a method for removing the monomer, any conventional method such as distillation can be used.

The weight average molecular weight of the partially hydrolyzed condensate is 500 to 50,000, preferably 600 to 40,000. When the molecular weight is less than 500, the stain resistance becomes small, and when it exceeds 50,000, the finishability and storage stability are poor.

Preferred specific examples of the partially hydrolyzed condensate include partial hydrolyzed condensate of tetraalkyl silicate such as MS51, MS56, MS56S (manufactured by Mitsubishi Chemical Co., Ltd.), MSI51, ESI40 (manufactured by Colcoat Co., Ltd.). Can be given. Above all, it is preferable that the partially hydrolyzed condensate of the tetraalkyl silicate is further partially hydrolyzed and condensed to have a weight average molecular weight of about 750 to 50,000. These may be used alone 2
You may use together 1 or more types.

The metal alkoxide used in the present invention is
It is not particularly limited as long as it is a metal alkoxide capable of coordination or substitution, but as such a metal, at least one metal selected from aluminum, zirconium and titanium can be preferably used.

The organic group capable of coordinating or substituting specifically includes at least a β-diketone or a β-ketoester represented by the formula (II) and a carboxylic acid represented by the formula (III). One kind of organic compound can be preferably exemplified.

In the compound represented by the formula (II), R ⁴ , R
⁵ are each independently a C1-C6 alkyl group, C1-
C16 alkoxy group or a C1 to C6 alkyl group substituted with a halogen atom, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-
C1-C6 alkyl group such as butyl group, isobutyl group, t-butyl group, n-pentyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, t-butoxy group, lauryl group , C1-C16 alkoxy groups such as stearyl group, trifluoromethyl group, monofluoromethyl group, difluoromethyl group, 2,2,2-
Examples thereof include C1 to C6 alkyl groups substituted with a halogen atom such as a trifluoroethyl group, a chloromethyl group and a trichloromethyl group. However, R ⁴ and R ⁵ do not become an alkoxy group at the same time.

Specific examples of the compound represented by the formula (II) include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetic acid-n-propyl and acetoacetic acid-i-.
Propyl, acetoacetic acid-n-butyl, acetoacetic acid-se
c-Butyl, acetoacetic acid-t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione , 5-methyl-hexane-dione and the like. Of these, ethyl acetoacetate and acetylacetone are preferred. These β-diketones and / or β-ketoesters may be used alone or in combination of two or more.

In the compound represented by the formula (III), R ⁶ is C
1 to C6 alkyl group or a C1 to C6 alkyl group substituted with a halogen atom, specifically, R ⁴ ;
Groups other than the alkoxy group exemplified for R ⁵ can be similarly exemplified, and among them, trifluoroacetic acid can be suitably exemplified. These carboxylic acids may be used alone or in combination of two or more, and
It can also be used in combination with a β-keto ester or a β-diketone represented by the formula (II).

Β-diketone represented by the formula (II) and /
Alternatively, the β-keto ester and the carboxylic acid represented by the formula (III) can be added in an amount of 1 mol or more per mol of the metal alkoxy, though the metal can be coordinated or substituted. Preferably.

Further, as the metal alkoxide substituted and / or coordinated with an organic group used in the present invention, specifically, a compound represented by the formula (IV) can be preferably exemplified. In the compound represented by the formula (IV), M represents aluminum, zirconium, or titanium, and R ⁷
Represents a C1~C6 alkyl group, R ^4, R ⁵ are as defined above, k represents a valence of M, m represents an integer of 0 or 1 to k,. Specific examples of R ⁷ include the same substituents as the alkyl groups exemplified for R ⁴ and R ⁵ .

Specific examples of the compound represented by the formula (IV) include tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium and n-butoxytris (ethylacetoacetate) zirconium. , Zirconium chelate compounds such as tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis ( Titanium chelate compounds such as acetylacetate) titanium and diisopropoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum Diisopropoxy acetylacetonate aluminum, diisopropoxy bis (ethylacetoacetate) aluminum, diisopropoxy bis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, mono-acetylacetonate ·
Examples thereof include aluminum chelate compounds such as bis (ethylacetoacetate) aluminum. These compounds may be used alone or in combination of two or more. It is also possible to use a partial hydrolyzate or a partial hydrolyzed condensate of these compounds as a component of the coating liquid.

The metal alkoxide substituted and / or coordinated with an organic group exists in the coating film alone as it is, in a self-hydrolyzed and condensed state, and in a hydrolyzed and condensed state with other components. In any of these states, it is preferably in the range of 0.5 to 40% by weight during the coating film formation.
If it is less than 0.5% by weight, the curing rate will be slow and the film hardness will be reduced.

The coating liquid used for producing the water-repellent film of the present invention is (a) inorganic fine particles whose surface is subjected to hydrophobic treatment, (b) a silicone-modified resin and / or a hydrolyzed condensate of a silane compound. , And (c) a metal alkoxide substituted and / or coordinated with an organic group are diluted with an applicable solvent. As the organic solvent used for dilution or the like, mainly the components are uniformly mixed to adjust the solid content of the composition of the present invention, and at the same time, it can be applied to various coating methods, and the dispersion stability and the storage stability of the composition are improved. It improves the sex. The organic solvent is not particularly limited as long as it can mix the components uniformly, but for example, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like are preferable.

Of these, examples of alcohols include monohydric alcohols and dihydric alcohols, and of these, saturated monohydric alcohols having 1 to 8 carbon atoms are preferable. Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol. Examples thereof include monobutyl ether and ethylene glycol monoethyl ether acetate.

Specific examples of aromatic hydrocarbons are benzene, toluene, xylene, etc., specific examples of ethers are tetrahydrofuran, dioxane, etc., and specific examples of ketones are acetone, methyl ethyl ketone, methyl. Isobutyl ketone, diisobutyl ketone, etc., specific examples of esters include ethyl acetate,
Examples thereof include propyl acetate, butyl acetate, propylene carbonate and the like. These organic solvents may be used alone or in combination of two or more. The ratio of the organic solvent in the composition is not particularly limited, and an amount that adjusts the total solid content concentration according to the purpose of use is used.

It is also possible to add colloidal silica to the composition for the purpose of improving the hardness of the resulting coating film. Examples of the colloidal silyl include water-dispersed colloidal silica and colloidal silica dispersed in an organic solvent such as methanol or isopropyl alcohol.

In addition, the composition of the present invention is separately provided in order to exhibit various properties such as coloring of the obtained coating film, thickening of the film, prevention of ultraviolet ray transmission to the base, imparting corrosion resistance, and heat resistance. It is also possible to add / disperse the filler. Examples of the filler include water-insoluble pigments such as organic pigments and inorganic pigments, particulates other than pigments, fibrous or scale-like metals and alloys, and oxides, hydroxides, carbides, and nitrides thereof. Examples include sulfides. Specific examples of this filler include particulate, fibrous or scaly iron,
Copper, aluminum, nickel, silver, zinc, ferrite,
Carbon black, stainless steel, silicon dioxide, titanium oxide, aluminum oxide, chromium oxide, manganese oxide, iron oxide, zirconium oxide, cobalt oxide, synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide,
Silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, bentonite, mica,
Zinc green, chrome green, cobalt green, viridian, Guinea green, cobalt chrome green, schele green, green soil, manganese green, pigment green, ultramarine blue, dark blue, pigment green, rock ultramarine blue, cobalt blue, cerulean blue, copper borate, Molybdenum blue, copper sulfide, cobalt purple, mars purple, manganese purple, pigment violet, lead suboxide, calcium leadate, zinc yellow, lead sulfide, chrome yellow, loess, cadmium yellow, strontium yellow, titanium yellow, litharge,
Pigment yellow, cuprous oxide, cadmium red, selenium red, chrome vermillion, red iron oxide, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, lead silicate,
Zircon oxide, tungsten white, lead zinc white, bunchison white, lead phthalate, manganese white, lead sulfate, graphite, bone black, diamond black, thermatomic black, vegetable black, potassium titanate whiskers, molybdenum disulfide, etc. be able to.

The average particle size or average length of these fillers is usually 50 to 50,000 nm, preferably 100.
~ 5,000 nm. The proportion of the filler in the composition is
It is about 10 to 300 parts by weight with respect to 100 parts by weight of other total solids. Further, in curing the composition of the present invention faster, a curing accelerator may be used depending on curing conditions, and in order to cure at a relatively low temperature, it is more effective to use a curing accelerator together. is there.

As such a curing accelerator, naphthenic acid,
Octyl acid, nitrous acid, sulfurous acid, aluminate, carbonic acid, etc.
Alkali metal salt; sodium hydroxide, potassium hydroxide
Which alkaline compound; alkyl titanic acid, phosphoric acid, p
-Toluenesulfonic acid, phthalic acid and other acidic compounds;
Tolylenediamine, Hexanediamine, Diethylenetria
Min, triethylene tetramine, tetraethylene penta
Min, piperidine, piperazine, metaphenylenediami
Amine, ethanolamine, triethylamine, epoxy resin
Various modified amines used as fat curing agents, γ-amido
Nopropyltriethoxysilane, γ- (2-aminoethyl
) -Aminopropyltrimethoxysilane, γ- (2-
Aminoethyl) -aminopropylmethyldimethoxysila
And γ-anilinopropyltrimethoxysilane.
Min compounds, (C_FourH₉)₂Sn (OCOC₁₁H_{twenty three})
₂ , (C_FourH₉)₂Sn (OCOCH = CHCOOCH₃)
₂ , (C_FourH₉)₂Sn (OCOCH = CHCOOC
_FourH₉)₂, (C₈H₁₇)₂Sn (OCOC₁₁H_{twenty three})₂, (C
₈H₁₇)₂Sn (OCOCH = CHCOOCH₃)₂ ,
(C₈ H ₁₇)₂Sn (OCOCH = CHCOOC
_FourH₉)₂, (C₈H₁₇)₂Sn (OCOCH = CHCOO
C₈H₁₇)₂, Sn (OCOCOC₈H₁₇)₂ Carboxylic acids such as
Type organotin compound; (C_FourH₉)₂Sn (SCH₂COOC
₈H₁₇)₂, (C_FourH₉)₂Sn (SCH₂COOC
₈H₁₇)₂, (C₈H₁₇)₂Sn (SCH₂COOC₈H₁₇)
₂ , (C₈H ₁₇)₂Sn (SCH₂CH₂COOC₈H₁₇)
2, (C₈H₁₇)₂Sn (SCH₂COOC₈H₁₇)₂,
(C₈H₁₇)₂Sn (SCH₂COOC₁₂H_{twenty five})₂,

[0062]

[Chemical 14]

Mercaptide type organotin compounds such as;

[0064]

[Chemical 15]

Sulfide type organotin compounds such as; (C
₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO, or (C
Organic tin compounds such as reaction products of organic tin oxides such as ₄ H ₉ ) ₂ SnO and (C ₈ H ₁₇ ) ₂ SnO with ester compounds such as ethyl silicate, dimethyl maleate, diethyl maleate and dioctyl phthalate Is used. The proportion of these curing accelerators in the composition is usually 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the solid content of the composition of the present invention.

In the composition of the present invention, other known dehydrating agents such as methyl orthoformate, methyl orthoacetate and tetraethoxysilane, various surfactants, silane coupling agents other than the above, titanium coupling agents, Additives such as dyes, dispersants, thickeners and leveling agents can also be added.

The coating liquid for forming the water-repellent film of the present invention includes (a) inorganic fine particles whose surface is subjected to a hydrophobic treatment, (b) a silicone-modified resin and / or a hydrolyzed condensate of a silane compound, and (c). ) A coating liquid containing a metal alkoxide substituted and / or coordinated with an organic group and / or a hydrolyzed condensate thereof with itself or another component can be exemplified. Above, the total solid content concentration,
It is preferably 50% by weight or less, and the total solid content concentration is appropriately adjusted and used according to the purpose of use. When the purpose is to impregnate a thin film-forming substrate, the total solid content concentration is usually 5 to 30% by weight. Further, when used for the purpose of forming a thick film or dispersing the above-mentioned filler, the total solid content concentration is usually 20 to 50% by weight, preferably 25 to 40% by weight, and when it exceeds 50% by weight, The storage stability of the composition deteriorates, which is not preferable.

In place of (c) the metal alkoxide substituted and / or coordinated with an organic group, (d) the metal alkoxide, and (e) the β-diketone or β-ketoester represented by the formula (II). And at least one selected from the group consisting of carboxylic acids represented by the formula (III) can be used. In this case, it is preferable to add water to the metal alkoxide (d) so that the substitution or coordination of the compound (e) represented by the formula (II) or (III) is promoted. The amount of water added is not particularly limited as long as it is 1 mol or more with respect to 1 mol of the (d) metal alkoxide, but is not more than the number of mols of the compound represented by the formula (II) or the formula (III) used. Is preferred.

The method for preparing the coating liquid used in the present invention is not particularly limited, but in particular, the method of adding the component (a) to the component (1) and the component (b), and the method of adding the component (b), (2) ) A method of adding the component (b) to the component (a) and further adding the component (c), and (3) adding the component (b) to the component (c).
The method of adding the component and further adding the component (b) can be preferably exemplified.

The water-repellent film of the present invention is applied to the surface of a substrate as an object by a coating means such as brush, spray, dipping, etc., and is applied once to a thickness of about 0.5 to 40 μm, and applied two to three times. Can form a coating film having a thickness of about 2 to 80 μm, and can form a coating film by drying at room temperature or by heating at a temperature of about 30 to 200 ° C. for about 10 to 60 minutes and drying. It is possible. Examples of the base material coated with the composition of the present invention include stainless steel, aluminum, ceramics, cement, paper, glass, plastics, inorganic ceramic substrates and cloths.

When coating this base material, conventionally known acrylic resin, epoxy resin, urethane resin for the purpose of improving the adhesion to the base material, sealing the porous base material, smoothing, film-forming, etc. It is also possible to use a base material on which a primer such as a polyester resin type is previously formed. Further, for the purpose of improving the wear resistance and gloss of a coating film formed using the composition of the present invention containing a filler, US Pat. No. 3,986,997 and US Pat. It is also possible to form a clear layer containing a siloxane resin as an essential component, such as a stable dispersion of colloidal silica and siloxane resin described in JP-A No. 073,073.

The coating film of the present invention obtained as described above is excellent in water repellency, and particularly has a contact angle with water of 130 ° or more and a sliding angle of 5 ° or less. Further, it has a wide range of applications because of its excellent adhesion and hardness and therefore its excellent weather resistance. To list these, heat exchangers, fins for heat exchangers, leather, fibers, paper, paperboard, cardboard for frozen foods, Styrofoam, building materials, roofs,
Treatment of window glass, windshield, various mirrors, plastic lenses, lenses, tires, rubber, magnetic recording media, semiconductor material surfaces, etc .; dry cleaning treatment agents, treatment agents for freezing warehouse walls, refrigerators, blowers in refrigerators, etc. Various treatment agents such as treatment agents or additives to treatment agents; treatment of antennas, steel towers, telecommunications facilities, road traffic signs, traffic lights, etc. in snowy areas; reduction of frictional resistance between ships and water, vehicles It has a wide range of extremely effective applications such as preventing dirt from adhering to aircraft bodies, preventing corrosion of electrodes on various metal materials and battery materials, treating fishnet surfaces, adding sealants, fireproof waterproof sealants, car wax, etc. . In addition, the treatment of fine wire mesh allows the gas to pass through but repels the water, so it can be used for a wide range of purposes.

Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited to the examples.

Production Example 1 (Production of acrylic silicone resin containing fluorine-substituted alkyl group) 2,2,2-trifluoroethyl methacrylate 5
1.2 g (0.3 mol), 3-trimethoxysilylpropyl methacrylate 5.28 g (0.02 mol),
A solution of 0.5 g (3.0 mmol) of 2,2′-azoisobutyronitrile and 96 g of xylene (concentration of solid content: 37% by weight) was stirred and reacted at 60 to 90 ° C. for 4 hours to give 4-methoxyphenol (0.2%). The reaction was stopped by adding 37 g (3.0 mmol) to obtain a resin solution A. When the gel permeation chromatography was measured, the number average molecular weight was 19000, and when the TG-DTA (differential differential thermal balance) was measured, the glass transition point (Tg) was 56.
It was ℃. In addition, when the high frequency plasma emission spectrophotometer was measured, the silicon content was calculated as silicon dioxide.
It was 4.67% by weight.

Production Example 2 (Preparation of component (c)) Tetraisopropoxy titanium isopropanol solution (manufactured by Nippon Soda Co., Ltd., solid content 28.2% by weight in terms of oxide), ethyl acetoacetate (manufactured by Wako Pure Chemical Industries, Ltd.) , Reagent grade),
Ion-exchanged water was mixed at a molar ratio of 1: 2: 1,
A titanium solution C having a solid content of 10% by weight as oxide was diluted to prepare a titanium solution C.

Example 1 (a) Hydrophobic silica particles (RX300, manufactured by Nippon Aerosil Co., Ltd., solid content 5% by weight toluene dispersion) (b-1) Acrylic silicone resin (YC5920, manufactured by Kanebuchi Kagaku, silicon dioxide conversion) Silicon content 12.3% by weight, solid content 10% by weight ethanol / s-butanol / ethyl acetate mixed solution) (b-2) Resin solution A (b-3) Poly (methyl silicate) (MS-51, Colcoat Co., Ltd. (Ethanol solution produced by conversion to silicon dioxide and having a solid content concentration of 10% by weight) (C) Titanium solution C The proportion (% by weight) of the above three components in terms of solid content shown in Table 1.
And then diluted with toluene so that the total solid content concentration in the solution will be 5% by weight, and the coating solution (S1 to
S10) was adjusted. The obtained coating liquid is applied to a glass plate using a bar coater (bar No12),
A film was formed by drying at 0 ° C. for 1 hour. The samples (P1 to P10) obtained as described above were evaluated by the following test methods. The results are summarized in Table 2.

Water repellency (water droplet contact angle) After dropping 5 μl of a water droplet from a microsyringe onto the surface layer of each sample, 80 seconds later, the sample surface was measured using a contact angle measuring device (360S type, manufactured by Elma Co., Ltd.). Was measured. Hardness (Surface Pencil Hardness) JIS K 5400-1900 8.4 Pencil Scratch Value 8.4.1 According to the method described in the tester method, a weight load of 1 kg was used to measure (5) (b) coating film. The pencil hardness was evaluated in the same manner as in the evaluation of scratches. Adhesion (tape peeling test) Cellophane tape was attached to each sample, rubbed multiple times on the ball of the finger, and then when the tape was peeled off, it was visually observed whether the film on the substrate was peeled off. Evaluation ◯: No peeling evaluation ×: Peeling water- sliding water Drop the water droplet on the film surface on the substrate by the same method as the measurement of the contact angle, then slowly incline the substrate to determine the inclination angle when the water droplet slides down. The sliding angle was measured. Evaluation ◯: Sliding angle of 5 ° or less Evaluation ×: Sliding angle of more than 5 °

[0078]

[Table 1]

[0079]

[Table 2]

P-8 to P-10 in Table 2 are included in the scope of the present invention, but are examples of coating films having relatively poor performance.

[0081]

As described above, the coating film of the present invention is excellent in water repellency, adhesiveness and hardness, and can be used for surface treatment of various materials, and has a wide range of properties such as antifouling and snow accretion prevention. Since it has uses, it can be said that it has a great industrial utility value.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J038 DL001 DL002 DL071 DL072                       DM021 DM022 GA15 HA216                       HA446 KA08 KA15 NA07                       NA12 PB05 PB06 PB07 PC02                       PC03 PC06 PC07 PC08 PC10

Claims (14)

[Claims] 1. An inorganic fine particle whose surface is subjected to a hydrophobic treatment, (b) a hydrolysis-condensation product of a silicone-modified resin and / or a silane compound, and (c) an organic group substituted and / or coordinated. A water-repellent film comprising a metal alkoxide and / or a hydrolysis-condensation product thereof with itself or another component. 2. The water-repellent film according to claim 1, which is a coating film having a contact angle of water droplets of 130 ° or more and a sliding angle of 5 ° or less. 3. The inorganic fine particles are silicon, aluminum,
The water-repellent film according to claim 1 or 2, which is an oxide containing at least one selected from the group consisting of titanium and zirconium. 4. The inorganic fine particles whose surface is subjected to a hydrophobic treatment are inorganic fine particles treated with one kind of silyl compound selected from the group consisting of trialkylsilyl compounds, dialkylsilyl compounds and perfluoroalkylsilyl compounds. The water-repellent film according to any one of claims 1 to 3. 5. The inorganic fine particles are 40 to 70 in terms of oxide.
The water-repellent film according to any one of claims 1 to 4, wherein the water-repellent film is contained in a weight percentage. 6. The silyl group-containing vinyl resin, wherein the silicone-modified resin has at least one silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group at the terminal or side chain in one molecule of the polymer. And / or a hydrolysis-condensation product thereof with itself or another component, The water-repellent film according to claim 1. 7. The water-repellent film according to claim 1, wherein the silicone-modified resin is a silyl group-containing vinyl resin containing a fluorine-substituted alkyl group. 8. A silane compound is represented by the formula (I): R ¹ _n SiX _n1 (R ² ) _4-n-n1 (I) (wherein X represents a halogen atom and R ¹ is C1 to C2
0 represents an alkyl group or a C6 to C13 aryl group, R
² represents OR ³ , SR ³ , or NR ³ R ⁴ , and R ³ , R ⁴
Each independently represent a hydrogen atom, a C1-C20 alkyl group, a C6-C13 aryl group, an acyl group, and n is
Represents 0, 1, or 2, n1 represents 0, or an integer of 1 to 4, and n + n1 ≦ 4. ) It is a silane compound represented by these, The water-repellent film in any one of Claims 1-7 characterized by the above-mentioned. 9. The water-repellent film according to claim 1, wherein the metal in the metal alkoxide is at least one metal selected from aluminum, zirconium and titanium. 10. An organic group represented by the formula (II): R ⁴ COCH ₂ COR ⁵ (II) (wherein R ⁴ and R ⁵ are each independently a C 1 to C ⁶ alkyl group, C 1 to C 1 Represents a C16 alkoxy group or a C1 to C6 alkyl group substituted with a halogen atom,
R ⁴ and R ⁵ cannot be alkoxy groups at the same time. ), A β-diketone or β-ketostel, and a compound represented by the formula (III): embedded image R ⁶ CO ₂ H (III) (wherein R ⁶ is a C1 to C6 alkyl group or a halogen atom) A C1 to C6 alkyl group represented by the formula (1), which is at least one selected from the group consisting of carboxylic acids represented by the formula (1). 11. A metal alkoxide substituted and / or coordinated with an organic group has the formula (IV) embedded image M (OR ⁷ ) _m (R ⁴ COCHCOR ⁵ ) _km (IV) (wherein M is Represents aluminum, zirconium, or titanium, R ⁷ represents a C1-C6 alkyl group,
R ⁴ and R ⁵ have the same meanings as described above, k represents the valence of M, and m represents 0 or an integer of 1 to k. ) The water-repellent film according to any one of claims 1 to 10, which is a compound represented by the formula (1). 12. A metal alkoxide substituted and / or coordinated with an organic group and / or a hydrolysis-condensation product thereof with itself or another component occupies 0.5 to 40% by weight in the coating film composition. The water-repellent film according to any one of claims 1 to 11, characterized in that. 13. A surface-modified inorganic fine particle, (b) a silicone-modified resin and / or a silane compound and / or a hydrolyzed condensate thereof, and (c) a substituent and / or an organic group. Coordinated metal alkoxide and /
Alternatively, a coating liquid containing a hydrolyzed condensate of the self or other components. 14. (a) Hydrophobic inorganic fine particles, (b) Silicone-modified resin and / or silane compound and / or its hydrolyzed condensate, and (c) Substituted with an organic group and / or Coordinated metal alkoxide and /
The method for producing a water-repellent film according to any one of claims 1 to 12, wherein a coating liquid containing a hydrolyzed condensate of the self or another component is applied onto a substrate and dried.