WO1999021929A1

WO1999021929A1 - Coating material composition

Info

Publication number: WO1999021929A1
Application number: PCT/JP1998/004784
Authority: WO
Inventors: Haruhiko Mohri; Yasushi Yonei
Original assignee: Daikin Industries, Ltd.
Priority date: 1997-10-29
Filing date: 1998-10-21
Publication date: 1999-05-06
Also published as: JPH11131020A

Abstract

An inexpensive coating material composition capable of forming films which can retain a stainproofing effect and excellent appearances stably for a prolonged period. The composition comprises (A) a co-condensate of a compound of the general formula (1): XSi(OR)3 with a compound of the general formula (2): Si(OR)4 or an oligomer thereof (wherein X is hydrogen or C1-C5 alkyl; and R's are each independently a C1-C10 monovalent organic group optionally containing oxygen, nitrogen or fluorine) which has a fluorine content of less than 5 wt.%, if contained, and (B) a coating resin.

Description

M

Composition technology for paints

Hatsuho relates to a paint composition that can prevent the attachment of stains such as rain streaks. Background art

In recent years, a solvent-soluble fluororefin copolymer having a hydroxyl group or a carboxyl group has been used as a resin for ultra-weatherproof paint, and its results have been growing. are doing . For example, it has been proposed in Japanese Patent Publication No. Sho 60-21686, Japanese Patent Application Laid-Open No. Hei 3-212107, Japanese Patent Application Laid-Open No. Hei 41279612, Japanese Patent Application Laid-open No. Hei 4-28707, etc. The copolymer of phenolic vinyl and vinyl alcohol is soluble in ordinary paint solvents and is soluble in ordinary paint solvents. By combining with a hardener such as rubber, it can be hardened at baking or at room temperature, and forms a coating film that excels in weather resistance and the like. It is known that

However, these coatings tend to accumulate and accumulate airborne soil and rain-stained soil when exposed outdoors (i.e., have poor antifouling stain resistance). ). — To improve the wiping properties (contamination removal property) of power-iron contamination and magic contamination, for example, see JP-A-4-173781. In this regard, a reaction product of a fluororefin copolymer and a Shirani conjugate is being studied. Also, in US Pat. No. 3,429,845, the specification of US Pat. No. 4,279,795, silicate (monomer) and silicate condensation are described. (Oligomer) with water and catalyst (salt) Acid and the like, and hydrolyzed in alcohol to obtain a composition of a hydrolyzate and a hydroxyl group-containing fluorofluorin copolymer. Has been proposed. However, these compositions do not have the effect of improving the anti-staining property.

Other techniques using a silane compound as a hardened site include those described in Japanese Patent Publication Nos. 45-113109, 5-78612, and 5-78612. Japanese Patent Laid-Open No. 61-258852, Japanese Patent Laid-Open No. 62-16673, Japanese Patent Laid-Open No. 64-75575, Japanese Patent Laid-Open No. 2 — 23222-1, Japanese Patent Laid-Open No. 240-153, Japanese Patent No. No. 2 1 1 482, Japanese Patent Application Laid-Open No. 4-654676 and Japanese Patent Application Laid-Open No. 4-2926287 have proposed such methods as alcohol and water. Is contained in a large amount, so that the rigidity is insufficient. In addition, the migration of the silicate to the surface is restricted because the silicate has a hydroxyl group or requires high-temperature baking. However, as mentioned above, the antifouling property has not been improved as in the previous case.

Other paints such as acrylic, acrylic silicone, inorganic materials, etc. are in the same situation, and they are remarkably resistant to stains and stains. Little has been known about the improvements.

In some cases, silane compounds are used as dewatering agents when dispersing polymers or pigments, but most silane compounds are used during production. Can react with water, and the paints produced from them have little effect on improving the antifouling and stainability. There is no such thing.

Further, for the purpose of improving the antifouling adhesion, for example, W094 / 0670, WO95 / 02645, Japanese Patent Publication No. 7-148540, JP-A-7-102211, JP-A-7-136584, JP-A-7-173432, JP-A-7-8250, JP-T Japanese Patent Application Laid-Open No. 7-09435 and Japanese Patent Application Laid-Open No. 7-601184 each disclose techniques using a gay compound. However, these techniques are not compatible with surface hydrophilicity and its reproducibility, antifouling adhesion, curability, compatibility, recoatability, storage stability, pot life, However, it is not satisfactory in terms of prevention of color separation, defoaming property, painting workability, cracking of the coating film surface, flexibility, and anti-alkaline properties.

In order to resolve these issues, the present inventors argue that certain organic metal compounds, oligomers and coligos with a relatively high fluorine content can be used. We have developed a composition for paints that contains マ as an antifouling agent (W097Z11130 pamphlet). However, when the fluorine content is increased, the production price is increased, and not only is the range of use limited, but there is no defect (unevenness) in the appearance of the coating film. In some cases.

Therefore, the purpose of the present invention is to form a coating film that is excellent in antifouling and adhesion, and does not accumulate and accumulate atmospheric contamination and rain streaks. The purpose is to provide such a paint composition at a relatively low cost. Disclosure of the invention

In other words, the present invention

(A) A cocondensate of the formula (1): XSi (OR) ₃ and the formula (2): Si (OR) ₄ or its oligomer (formulas (1) and ( In 2), X is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R is the same or different and is an oxygen atom, a nitrogen atom or a fluorine atom. A monovalent organic group having 1 to 10 carbon atoms which may contain a fluorine atom) and containing less than 5% by weight of fluorine if it contains a fluorine atom. And gallium-containing compounds that are (B) Resin for paint

The present invention relates to a coating composition comprising the composition.

Further, (A) a co-condensate of the formula (1): XS i (OR) ₃ and the formula (2): S i (OR) ₄ or its oligomer and the formula (3): Reaction product with HOR (in the formulas (1), (2) and (3), X is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R is the same. Alternatively, it is a monovalent organic group having 1 to 10 carbon atoms which may contain an oxygen atom, a nitrogen atom, or a fluorine atom. A fluorine-containing compound having a fluorine content of less than 5% by weight, if it contains a fluorine atom, and

(B) Resin for paint

It also relates to a composition for paints consisting of this.

In these compositions, it is preferable that the number average molecular weight of the compound containing a gayne is 2000 to 5000 in terms of GPC (polystyrene conversion).

Further, at least one of the organic groups R in the silicon-containing compound (A) is H (CF ₉ ) ₂ CH ₂ —, H (CH ^ ^ CH n — or CF ₃ CF Preferably, it is ₂ CH ₉ —, and further, it is preferred that X in the amino compound (A) is a methyl group. At least one of R is a methylene group, and the number of methyl groups occupying in all organic groups R (CH ₃ Z total R) is 0.2 to 0.8. Is preferred.

The coating resin (B) may be a homopolymer of futivinylidene, a copolymer of a solvent-soluble fuzivinylidene or a copolymer of vinylidene fluoride. It is preferably a water-soluble polymer dispersion, and the coating resin (B) is a hydroxyl- and / or carboxy-group-containing solvent-soluble fluoropolymer. A resin copolymer, an acrylic resin or an acrylic silicone resin, (c) A curing agent and / or a curing catalyst, or the paint resin (B) contains a hydroxyl-and / or carboxyl-group-soluble tetrafluoro resin. Preferred is a coating composition which is a polyethylene copolymer and contains (C) a hardening agent and / or a curing catalyst. Best form to carry out the invention

The coating composition of the present invention requires (A) a silicon-containing compound containing no or less than 5% by weight of a fluorine-containing compound and (B) a coating resin. (C) It consists of a curing agent and Z or a curing catalyst.

In the present invention, the silicon-containing compound (A) acts as an antifouling agent. That is, when the alkoxy group bonded to the silicon constituting the silicon-containing compound (A) is applied as a paint, it gathers on the surface of the coating film. In addition, it is decomposed and desorbed by the action of rainwater and the like to remove contaminants adhered to the surface of the coating film.

The compound containing a silicon (A)

A co-compound of the trialkoxysilane of the above formula (1) with tetraalkyloxysilane of the formula (2) or a polygomer thereof; It is alright,

The co-condensation product of the trialkyloxysilane of the above formula (1) and tetraalkyloxysilane of the formula 2) or the oligomer thereof and the formula It may be the reaction product with alcohol of (3).

A feature of the present invention is that, even when the silicon-containing compound (A) does not contain a fluorine atom or contains a fluorine atom, it is less than 5% by weight, and is preferable. Is 3% by weight or less.

As the fluorine-containing compound (A) containing no fluorine atom, In the trialkoxysilane of the formula (1), X is a hydrogen atom, methyl, ethynole, propyl, and R is methyl, ethyl, propyl. R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R Is preferred. The tetraalkyloxysilane of the formula (2) may be a 1 to 20-mer, preferably a 1 to 10-mer. When reacting the alcohol of formula (3), it is preferred that R be methyl, ethyl, propyl, or butyl.

Particularly preferred combinations are, for example, the ones that are preferred.

(i) Equation (1): X = CH

Three

RCH ₃ or C ₂ H ₅

Equation (2) R = C _{2 n} 5

) Expression (1) X C H

Three

R = CH ₃ or C ₉ H

Equation (2): R

^C 2 ⁿ 5

Equation (3): R = C H

Three

The condensation ratio of the formula (1) and the Z formula (2) is 1/3 to 20, preferably 1/5 to 15, in terms of the mole ratio of a gay atom unit. When the ratio of equation (1) increases, the surface lyophilicity tends to be insufficient.

Further, in such a co-condensate, at least one of R is a methyl group, and the number of methyl groups occupied by all the organic groups R. When (CH ₃ / all R) is 0.2 to 0.8, especially 0.35 to 0.65, it is superior in the initial lyophilicity, and as a result, the initial It is possible to improve the antifouling adhesion property of the product.

Next, the fluorine-containing compound (A) containing a fluorine atom is represented by the formula (1), the formula (2) and / or the low R in the formula (3). At least one of them is a group containing a fluorine atom (R _f ). R _f is a monovalent fluorinated organic group having 1 to 10 carbon atoms which may contain an oxygen atom or a nitrogen atom. Specific examples include H (CF ₂ ) _m CH ₀ , F (CF ₂ ) _m CH o CH ₀ (m is 2 to 10), and particularly water-decomposability. From H (CF.) ₂ CH ₂ — and H (CF ₂ ) ₄ CH. Short-chain phenolic alkyl groups, such as CF ₃ CF ₂ CH ₂ , etc., are preferred.

R _f may be introduced as at least one of R in the formula (1) or the formula (2).

In addition, the fact that the fluorine content in the silicon-containing compound (A) is less than 5% by weight is based on the formula (1) and the formula (2). This can be easily achieved if the non-fluorine system is a fluorine-containing alcohol including the alcohol of the formula (3). Is a Yo I Do含Fu Tsu containing Anoreko one Norre of its, for example, _{_{_{H (CF 2) m CH 2}}} 0 H, F (CF 2) m CHCH 2 0 H (m is 2~; L 0), etc. , Especially H (CF o) ₂ CH _? OH, H (CF ₂ ) ^ CH. OH or CF. CF ₂ CH ₂₀ H is preferred in terms of water decomposability.

The reaction ratio of the formula (1), the formula (2) and the formula (3) is different depending on which compound has a fluorine atom introduced therein. For example, it is an alkoxysilane non-fluorine system of the formula (1) and the formula (2), and the fluorine-containing alcohol is used as the formula (3). In some cases, the fluorine content in the raw material mixture should be considered. In this case, the non-fluorine-based formula (1) is a co-condensate with a fluorine atom-containing alcohol with a molar ratio of 1Z3 to 20 per unit of a silicon atom in formula (2). The weight fraction of the fluorine atom in the fluorine-containing alcohol is 0.:! It should be charged so that it is 30%, usually 1-10%.

The production of the silicon-containing compound (A) is carried out according to the formulas (1) and (2). If required, the alcohol of formula (3) may be mixed with the formula (2), which may be an oligomer. However, it can be obtained by heating in the presence of a catalyst. Also, a mixture of the formulas (1) and (2) in the formula (2) may be an oligomer. Heating may be carried out in the presence of a catalyst, and if necessary, a distillation operation may be carried out. Then, heating may be carried out by adding the phenol compound of the formula (3).

The catalyst includes, for example, hydrochloric acid, sulfuric acid, acetic acid, paranorenens olenoic acid, ammonia, trimethylamine, triethylamine, and the like. Min, triplamine, 1, 8 — diaza bicyclo (5, 4, 0) ゥ decene 1-7 (DBU), (1) 1 snow, ° Tin, 4 — N, N — Dimethylaminopyrimidine, Monoethanolamine, Triethanolamine, Ν, Ν, Ν ' , Ν ーララララテテテラテテテテテラーテテテテテテテテテテテテテテテテテテテララt — Butoxy, sodium ethoxide, hydroxylated tetramethylammonium, ammonium hydrogen sulfate tetramethylammonium , water Acids / alkalis such as tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, aluminum tris (aluminum tris) Aluminum acetate), aluminum tris (acetone acetate), aluminum monoacetate Tobis (Ethyl acetate acetate), Ethyl acetate acetate, Disposable medium, Disposable medium, Aminore medium Aluminum sulfides such as isoproprates, anore miniatures, anolyme secs and butyls; Butyls Zyllaurate, Dibutyls Acetate, Dioctyls Maleate, Tetraisopropyl Le Chi data ne over door, Te door La blanking Chi Le Chi data conservation over the door, and so on organometallic compounds Roh organic metals salt of Although various types are selected, hydrochloric acid, sulfuric acid, and aluminum sulfide are preferred from the viewpoints of catalytic efficiency and production stability.

Examples of the reaction solvent include methanol, ethanol, and isoprono. No-nore, n-butano-no-re, t-butano-no-no-re, octano-no-re, 2, 2, 2, 2-trif-no-re-hole Etano-no-re, 2, 2, 3 , 3,3 — phenolic and other phenolic alcohols, tetrahydrofuran, 1,4-dioxane, tetra Ethers such as hydroxysilane, acetone, acetic acid 2-ketones / esters such as methoxyethyl, N, N-dimethyl Norehole amide, N, N—Dimethylacetamide, N—Methylacetate amide, N—Methinolepyrrolidon, Polio Amides such as oxazoline, acetic acid, trifluoroacetic acid, power oleonic acids such as F (CF ゥ) g C00H, trifluoromethyl Ben , M — Fluorinated aromatics such as bis (fluorotrifluoromethyl) benzene, etc., but they have high dissolving power. 2,2,2-Trifluorene Nono, 2,2,3,3,3—Pentafluoroethanol, Tetrahydrofuran , 1, 4 — Zoxan, tetrahydropyran is preferred. If phenol is used as the reaction solvent, it is preferable to distill the alcohol after the co-condensation by distillation or the like from the viewpoint of inhibiting the curing reaction. It is better.

Further, it is preferable that the obtained co-condensate does not contain a silane group from the viewpoint of surface hydrophilicity.

In the present invention, the compound containing a compound (A) has a number-average molecular weight measured by GPC (converted to polystyrene using tetrahydrofuran as a solvent). Is preferably from 2000 to 5000, particularly preferably from 2500 to 3500, from the viewpoints of surface hydrophilicity, storage stability of the compound containing silicon and appearance of the coating film. The compounding amount of the silicon-containing compound (A) is 0.1 to 60 parts by weight, preferably 1 to 40 parts by weight, based on 100 parts by weight of the coating resin (B). If the amount is less than 0.1 parts by weight, the anti-staining property tends to decrease.If the amount exceeds 80 parts by weight, the coating film cracks and the compatibility with the resin increases. Degradation may occur.

The coating composition of the present invention comprises (A) the above-mentioned specified compound containing a compound acting as an antifouling agent, (B) a coating resin, and (C) a curing agent, if necessary. And / or curing catalyst power, which imparts to the coating film, such as excellent antifouling adhesion properties, low electrification properties, and anti-fog properties.

The resin for coating (B) is, for example, a solvent-soluble, hydroxyl- and / or carboxyl-containing phenolic olefin resin. Polymer, Acrylic Polyol Resin, Acrylic Silicone Resin, Inorganic Material, Independent Weight of Fushidani Vinylidene Not Having a Functional Group Aqueous or copolymerized polymer, composite aqueous dispersion of fusidani vinylidene copolymer and acrylyl copolymer, or phenolic lipstick An aqueous dispersion of a vinyl ether copolymer is preferred.

As the fluoroolefin copolymer having a hydroxyl group and / or a carboxy group, for example, Japanese Patent Publication No. Sho 60-21686 , JP-A-3-121107, JP-A-4-27961, JP-A-4-28707, JP-A-2-2322221, etc. The number average molecular weight (according to GPC) of the copolymer is from 1,000 to 100,000, preferably from 1,500 to 30,000. No. If the molecular weight is less than 100, the curability and weather resistance tend to be insufficient, and if the molecular weight exceeds 100, there is a problem in workability and paintability. There is a tendency to occur. The hydroxyl value of this copolymer is from 0 to 200 (mg KOH / g), preferably from 0 to 150 (mg KOH / g). If it exceeds 200 (mg K0H / g), there is a tendency to cause a problem in the flexibility of the coating film.

The acid value is from 0 to 100 (mg KOH / g), and more preferably from 0 to 50 (mg KOH). If it exceeds 100 (mg KOH / g), there is a tendency that a problem occurs in the flexibility of the coating film.

In addition, one of the copolymers has a hydroxyl group or a carboxyl group from the viewpoints of anti-staining property, anti-staining property, and anti-staining property. A solvent soluble tetrafluoroethylene copolymer may also be used.

Examples of the copolymer include Zefflu manufactured by Daikin Industries, Ltd., Lumifuron manufactured by Asahi Glass Co., Ltd., and Central Glass Co., Ltd. Marketed products such as Cefral Co., Ltd., Finknet by DINKI INK CHEMICAL INDUSTRIES CO., LTD., And ZAFLON by Toa Kasei Co., Ltd. are available. .

As the acrylic polyol resin, a known resin can be used. The resin may have a hydroxyl group, a carboxyl group, an epoxy group, or an amino group.

The hydroxyl value of the acrylpolyol resin is 0 to 200 (mgKOH / g), and 0 to: L00 (mgKOHZg) is preferable. If it exceeds 200 (mg KOH / g), there is a tendency to cause a problem in the flexibility of the coating film.

The acid value of the acrylic polyol resin is from 0 to: L00 (mgKOH / g), and more preferably from 0 to 50 (mgKOH / g). . If it exceeds 100 (mg KOH / g), there is a tendency that a problem occurs in the flexibility of the coating film. Examples of acrylic resin are Dynal made by Mitsubishi Rayon Co., Ltd. and Acrylic made by Dainippon Ink Chemical Industry Co., Ltd. It is possible to use commercial products such as Dick, Hitaroid manufactured by Hitachi Chemical Co., Ltd., and a hoster manufactured by Mitsui Toatsu Chemicals, Inc.

Examples of the acrylic silicone resin include a hydroxyl group silicone monomer and a hydroxyl group-containing monomer or other polymerizable unsaturated monomer. It only needs to be polymerized with the body. The acrylic silicone resin may have a force II water-decomposable silyl group, hydroxyl group, or epoxy group.

Examples of acrylic silicone resins include Zemlack, manufactured by Kane-Fuchi Ridakaku Industry Co., Ltd., and Kryama, manufactured by Sanyo Chemical Industry Co., Ltd. Commercial products can be used.

Examples of the inorganic material include non-fluorine-containing non-hydrolyzable group-containing metals (such as Si, Ti, and A1), and non-fluorine-containing non-fluorine-containing metals. Water-decomposable group-containing organopolysiloxanes, non-fluorine-containing metals (Si, Ti, A1, etc.) Alkoxyides, etc. As a commercial product, Gunze Industries Co., Ltd. launched Ecotone, Nihon Gosei Gum Co., Ltd.'s glass power, Tobebe

Poserin Co., Ltd., Nippon Oil & Fats Co., Ltd. Berclean, Belhard, Toray Dow Corning 'Silicone Co., Ltd. SH, SR and DC series manufactured by Shin-Etsu Chemical Co., Ltd., KR series manufactured by Shin-Etsu Chemical Co., Ltd., plan manufactured by Ajinomoto Co., Ltd., organic titanium manufactured by Nihon Soda Co., Ltd. Net, Kawaken Fine Chemicals Co., Ltd., Aluminum Aluminum Collate, Aluminum Chemicals, Hokuko Chemical Zirconium Alcoxide manufactured by Industrial Co., Ltd., Compound Modified Silicone Oil manufactured by Japan Nikka Co., Ltd., and MMCA It is. In addition to the above-mentioned resin for paint, a fluorine resin having no functional group (Japanese Patent Publication No. 43-10363, Japanese Patent Application Laid-Open No. 3-28206, Japanese Patent Publication No. The homopolymers and copolymers of Futsidani vinylidene described in each official gazette and the like are exposed, and the resin having the above-mentioned functional group is used as a resin. It can also be rendered. In addition, as long as a resin having no functional group is used, it is not always necessary to use a curing agent or a hard catalyst in the coating composition of the present invention. .

Further, as the composite aqueous dispersion of the above-mentioned fluorinated vinylidene copolymer and acrylyl copolymer, for example, JP-A-3-7784 and Japanese Unexamined Patent Publication No. Hei 8-12201 has been elaborated. Examples of commercially available products include Zeffle manufactured by Daikin Industries, Ltd., and Japan. Floren made by Synthetic Rubber Industry Co., Ltd. is required.

Further, as the aqueous dispersion of the above-mentioned phenolic vinous vinyl-vinyl ether copolymer, for example, Japanese Unexamined Patent Publication No. 3-372252 is described. Some of the products sold are Lumifront manufactured by Asahi Glass Co., Ltd., and Fumino manufactured by Ink Chemicals Co., Ltd. of Japan. You will be able to get more information.

The coating composition of the present invention may contain a hardening agent and a curing catalyst, as long as the present invention does not impair the antifouling adhesion property.

Examples of the curing agent include an isocyanate compound, a block isocyanate compound, a melamine resin, a dibasic acid, and a non-hydrated water. Degradable group-containing silane compounds, epoxy resins, or acid anhydrides can be used, but from the viewpoints of weather resistance, acid resistance, and rain resistance, it is possible to use iso- Lock isocyanate and epoxy resin are preferred. The above-mentioned isocyanate compound and block isocyanate compound are, for example, 2,41 tri-range isocyanate. , Diphenylene methane, 4, 4'-di-isolated, xili-di-isolated, iso-hollo-diso Units, resin mediums, resin containers, methyl cyclone devices, resin cells, trimethyl nets Shark Residential Isolate, Hexa Residue Isolate, n-Pentane 11, 4-Solid Isolate, These trimers, their adducts / viewlets, and their polymers have more than one dissociate group thing In addition, there are various types of blocked isocyanates and the like, but the present invention is not limited to these.

The mixing ratio of the resinate and the resin for paint is preferably 0.5 to 5.0 in terms of NC0 to 0H (molar ratio), and more preferably 0.8 to 1.2. Is more preferred. Also, if the iso- nate is of a moisture-hardening type, it is preferred that the strength be 1.1 to 1.5 force.

The above-mentioned melamin resin includes, for example, the strength of the melamin resin, and the methylolated polymer obtained by squeezing the melamin into the mouth. Min tree month, melody, and alcohol are classified into alcohol, such as methanol, ethanol, butyl, and so on. The power that can be used to derive the alkinoleate and melamine resin is not limited to these.

For the epoxy compound mentioned above, for example, CH ₂ -CH-CH2 -0-CH ₂ CH ₂ 0- CH2 -CH-CH2

\ Z \ /

0 0

0

C

CH ₂ -CH-CH2 N N-CH2 -CH-CH2,

0 c c 〇

0 〇

N I

CH

I

CH

0

C H,

It is not limited to these, but it is not limited to these.

Examples of the acid anhydride include, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and anhydrous anhydride. Examples include, but are not limited to, dicarboxylic acid, succinic anhydride, anhydrous maleic acid, and the like.

In addition, fumaric acid, succinic acid, adipic acid, azelinic acid, cenocinic acid, dodecanedioic acid, 1,2-cyclohexyl Dibasic acids such as rudicarboxylic acid are also used as curing agents.

The curing agent is used in an amount of 100 parts by weight or less, preferably 5 to 40 parts by weight, per 100 parts by weight of the coating resin (B).

Curing catalysts include, for example, organic tin compounds, organic acid phosphoric acid esters, organic titanate conjugates, acid phosphoric acid esters and a Reactant with min, saturated or unsaturated polyvalent Carboxylic acid or its anhydride, organic sulfonate, amide-based conjugate, aluminum chelate, titanium conjugate It can be used for chelate compounds, zirconium compounds, etc.

Specific examples of the above-mentioned organic tin compounds include dibutyl tin glaurate, dibutyl tin maleate, and dioctinole tin. For example, mallet, dibutyls jiacetate, etc. are required.

Examples of the organic acid phosphoric acid ester include:

0 0 〇

II II II

(CH 30) 2 P OH, CH3 OP (0H) 2, (C 2 H 5 0) 2 P OH

〇 O

II II

C 2 H 50 P (0H) 2, [(C H3) 2 CH0] 2 P OH, etc.

The above-mentioned organic titanium compounds include, for example, tetrabutyl titanate, tetraisopropinolate titanate, and tritium titanate. Titanate esters such as ethanol monoamine titanate are exposed.

Further, examples of the above-mentioned amide-based compounds include, for example, petitamine, octylamine, dibutylamine, and monomono. Ethanol Amin, Genoa Nore Amin, Triethanol Amin, Diethylene Triamin, Triethylentra Min, Orea, Minor, Cyclone, Minor, Miner, Minor, Minor, Minor, Minor Diamine, triethylene diamine, guanidine, diphenyl guanidine, 2, 4, 6 — tris (dimethino oleamino) Mech Le) phenol, mono hollin, N-methyl mono hollin, 1, 8-diazabicyclo (5.4.0) デ(DBU) and other amide-based compounds, as well as their salts, such as oleonic acid, and excess polyamine and polybasic acid. Low molecular weight polyamid resin, excess polyamine and reaction products of epoxy conjugates.

Specific examples of the chelate compounds include aluminum tris (ethyl acetate acetate) and anoluminium tris (ethyl acetate). Acetate Acetate), Gil Conteum Tetrax (Acetate Acetate), Jiso Propoxy Business (Acetate) (Ruacet acetate) Titanium, etc.

One hardening catalyst may be used, or two or more hardening catalysts may be used in combination. Preferred hardening catalysts include organic tin compounds and anoluminum metal chelate compounds.

In the present invention, the combination of the resin for coating and the hardener and / or hardener catalyst is not particularly limited. A combination that is not preferred is the one that is as follows.

In the case of phenolic lipophilic copolymers or acryl-polyol resins containing hydroxyl and / or carboxy groups When these compounds have a hydroxyl group, as stiffening agents such as isopropylate compounds and blockisoate anilide compounds Or melamine resin, and as a stiffening agent when it has a carboxinole group, it may be melamine resin or epoxy resin. It is a compound. In these systems, a hardening catalyst can also be used.

In the case of acrylic silicone resin, fluorine silicone resin, or inorganic materials, it is only necessary to use a hardened silica catalyst. The curing catalyst is used in an amount of 50 parts by weight or less, preferably 0.0001 to 10 parts by weight, based on 100 parts by weight of the coating resin (B).

In the present invention, an organic solvent can be mixed into the coating composition.

Examples of the organic solvent include charcoal such as xylene, toluene, sonolesso 100, solubeso 150, and hexane. Hydrogen solvents, methyl acetate, ethyl acetate, ethyl acetate, ethylene glycol acetate monomethyl ether, ethyl alcohol glycol Monomethyl ether, ethylene glycol monobutyrate, monoethyl alcohol ft, monoethylene glycol ft acid Monoethyl ether, diethylene glycol monoethyl ether, diethyl acetate acetate monobutyl ether, ethyl acetate Ester-based solvents such as glycol alcohol, diethyl acetate glycol, dimethyl ether, dimethyl ether, etc. -Ethyl glycol, mono-ethyl ether, ethylene glycol mono-methyl ether, ethylene glycol mono-methyl ether , Ethylene glycol monobutyral ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether Rutiles, ethylene glycol, nozzles, ethylene glycol, monomethyl ethers, ethylene glycol Re-collection mono-ethyl ether, polyethylene glycol mono-butyl ether, di-ethylene glycol total methyl ether Terre, ethylene glycol, etil ether, jele lentico reno jibutino tele, tetrahi Acetonitrile-based solvents such as lofrane, ketone-based solvents such as methylethylenoketone, methylisobutylketone, and acetate; N, N — Dimethyl acetate amide, N — Methyl acetate amide, acetate amide, N, N — Dimethyl phenol home amide, N , N—Jetil Amido-based solvents such as formamide, N-methylformamide, etc.Sulfonate ester-based compounds such as dimethyl sulfoxide Solvents, methanol, ethanol, isopanol, butano, ethylene glycol, polyethylene glycol, poly Ethylene glycol (degree of polymerization: 3 to 100), CF ₃ CH. OHF (CF ₂ ) ₂ CH ₂ OH (CF) ₉ CH 0 H. F (CF ₀ ) ₀ CH 0 H, F (CF ₂ ) ₄ C ₂ H ₅ 0 H. H (CF ₂ ) CH ₂ 0 H. H (CF ₂ > ₃ CH ₂₀ H, H (CF.) ₄ CH ₂ OH and other anosol-based solvents can be removed, but only at the point of pot life. Alcohol-based solvents are preferred.

As the fluorinated solvent, a liquid at room temperature is desired, and trichlorofluorophenol, tetrachlorofluorene, etc. Tan, trichlorene trifluorene, jibromote rafurorotan, HCFC-123 HCFC-141 b HCFC-225, jikuroro Safluorocyclobutane, Tetraclorohexafluorobutane, Perfluoropentane, ⁰ — Fluoro mouth , One-fluoroheptane, perfluorooctane, and the like, but the above-mentioned compounds containing a gay compound, resin for paints, and curing agents It is desirable to simultaneously contain a fluorine atom, a chlorine atom, and a carbon atom in order to dissolve the HCFC-123 HCFC. — 141 b HCFC — 225, Tetrachloro is preferred.

It is also possible to combine two or more of these fluorinated solvents or to combine them with a hydrocarbon organic solvent.

The blending ratio of the paint resin and the alcohol-based solvent is 150 parts by weight with respect to 100 parts by weight of the paint resin, which indicates curability and appearance of the coating film. From 1 to 25 parts by weight Is even more preferred.

The coating composition of the present invention further includes, for example, a pigment, a pigment dispersant, a thickener, a leveling agent, a defoaming agent, a film-forming auxiliary, an ultraviolet absorber, HALS, anti-glazing agent, filler, colloidal silica, anti-fungal agent, silane coupling agent, anti-skinning agent, antioxidant, flame retardant, For paints such as anti-sagging agents, antistatic agents, antioxidants, water-soluble resins (polyvinyl alcohol, polyethylene oxide, etc.) Additives can also be incorporated.

The coating composition of the present invention is suitable for coating materials such as metals, ceramics, plastics, cement, wood, and old coatings. Then, if necessary, the undercoat layer and the intermediate coat layer can be provided, and the coating can be performed. There are no particular restrictions on the method of painting, such as the mouth-coating method, spraying method, brush-coating method, roller method, flow-coating method, and date. Bing method can be adopted. The thickness of the coating film is usually from l to 100 zm, preferably from l to 50 ^ m.

The preferred combinations of each component of the paint composition of the present invention are shown below, but the present invention is not limited to such combinations. No.

(1) (A): Co-condensation product of methyltriethoxysilane and tetraethyloxirane (or its oligomer) 40 parts Fluorine content: Zero or less than 5% Number average molecular weight: 2000-5000

(B): Solvent-soluble Fusidani vinylidene copolymer

1 00 copies

(Effect): Anti-contamination adhesion, weather resistance, flexibility, acid-resistant rain Excellent in properties and appearance of coated film.

(2) (A) Co-condensation product of methyltrimethylsilan and tetramethylsilan (or its oligomer) 5 to 4 0 parts Fluorine content: Zero or less than 5% Number average molecular weight: 200 000 to 500 000

(B) Solvent-soluble vinylidene fluoride copolymer

1 0 0 copy

(Effect) It is excellent in antifouling adhesion property, weather resistance, flexibility, acid resistance rain resistance, and appearance of coating film.

(3) (A) Co-condensation product of methylentrimethoxymethan and tetraethoxysilane (or its oligomer) 5 to 40 Partial fluorine content: Zero or less than 5% Number average molecular weight: 200 000 to 500 000

(B): Solvent-soluble vinylidene fluoride copolymer

1 0 0 copy

(Effect): Excellent in antifouling adhesion, weather resistance, flexibility, acid resistance, rain resistance, and coating film appearance.

(4) (A): Co-compounded product of methylentriol ethoxylan and tetratoxirane (or its oligomer) 40 parts Fluorine content: Zero or less than 5% Number average molecular weight: 200 000 to 500 000

(B): Hydroxyl and / or carboxyl group-containing solvent-soluble fluororefin copolymer

1 0 0 copy

(C): Isolation compound or block issue Anetoi-Daizo or epoxy resin

5 to 50 copies

(Effect) Excellent in antifouling stain adhesion, stain removal properties, weather resistance, acid rain resistance, alkaline resistance, and coating film appearance.

(5) (A) Co-condensation product of methylentrimethoxysilane and tetramethyloxylan (or its oligomer) 5 to 4 0 parts Fluorine content: Zero or less than 5% Number average molecular weight: 200 000 to 500 000

(B) Soluble Fluororefin Copolymer Containing Hydroxyl and / or Carboxyl Group-Containing Solvent

1 0 0 copy

(C) Isolate compound or block resin compound or epoxy resin

5 ~ 50 copies

(Effect): Excellent in antifouling adhesion, stain removal, weather resistance, acid rain resistance, alkaline resistance, and coating film appearance. (6) (A): co-compounded product of methyltrimethylsilan and tetraethyloxylan (or its oligomer) 40 parts Fluorine content: Zero or less than 5% Number average molecular weight: 200 000 to 500 000

(B): Hydroxyl or carboxyl group-containing solvent-soluble fluorinated fluorinated copolymer

1 0 0 copy

(C): Dispersion compound or block resin compound or epoxy resin

5 to 50 copies (Effect): Excellent in anti-staining property, stain removal property, weather resistance, acid resistance, rain resistance, alkaline resistance, and coating appearance. (7) (A): co-condensation product of methyltriethoxysilane and tetraethyloxysilane (or its oligomer) 5 to 40 parts Fluorine content: Zero or less than 5% Number average molecular weight: 200 000 to 500 000

(B) Acrylic Polyol

1 0 0 copy

(C) 5 to 50 copies of the esoteric compound or the blocky sidney compound.

(Effect) Excellent in anti-staining property, stain removal property, and appearance of coating film.

(8) (A) Co-condensation product of methylentrimethyl silane and tetramethyl silane (or its oligomer) 5 to 4 0 parts Fluorine content: Zero or less than 5% Number average molecular weight: 200 000 to 500 000

(B) Acrylic Polyol 100 parts (C) Isocene compound or blocky compound 5 to 50 Department

(Effect) Superior in antifouling stain adhesion, stain removal properties, and appearance of coating film.

(9) (A): Co-compounded product of methylentrimethoxysilane and tetraethyloxirane (or its oligomer) 40 parts Fluorine content: Zero or less than 5% Number average molecular weight: 200 000 to 500 000 (B) 100% copy of the poly (P) (C) Isolation of the compound or block of the compound 5 to 5 0 copies

(Effects) Excellent in antifouling adhesion, stain removal, and coating film appearance.

(10) (A) Co-condensation product of methylentritoethoxylan and tetratokinskiran (or its oligomer) 5 to 4 0 parts Fluorine content: Zero or less than 5% Average molecular weight: 200 0 0 to 500 0 0

(B) Acrylic silicone resin 100 parts (C) Hardening catalyst 0.01 to 1 part (effect) Anti-stain adhesion, stain removal property, weather resistance, Excellent acid rain resistance and excellent film appearance.

(11) (A) Co-condensation product of methyltrimethylsilan and tetramethylsilan (or its oligomer) 5 to 4 0 parts Fluorine content: Zero or less than 5% Number average molecular weight: 200 000 ~ 500 000

(B) 100 parts of acrylic silicone resin (C) Curing catalyst 0.01 ~ :! Part (Effect) Excellent in antifouling adhesion, weather resistance, acid resistance rain resistance, and appearance of coating film.

(12) (A): Co-condensation product of methyltrimethoxysilane and tetraethyloxysilane (or its oligomer) 5 ~ 40 parts Fluorine content: Zero or less than 5% Number average molecular weight: 200 000 to 500 000 (B): Acrylic resin 100 parts

(C): Curing catalyst 0.01 to 1 part

(Effect): Superior in anti-staining property, weather resistance, acid rain resistance, and appearance of coating film.

The articles coated with the coating composition of the present invention may be used for, for example, waterproof sheets for construction, waterproof sheets for tunnels, and agricultural vinyls. Roll sheet, agricultural vinyl film, curing sheet, construction protection sheet, vehicle protection sheet, mesh sheet, mesh sheet Clean, Polycarbonate roof, Acrylic board wall, Polycarbonate wall, Guard rail, Traffic light, Tunnel inner wall, Tunnel interior panels, road signs, billboards, highway side walls, highway noise barriers, road lights, bridges, bridge girders, piers, chimneys, wallpaper, tatami mats, mats, tables Loss, ventilation fan, marking film, geomembrane, billboard, postal mail box, telephone pole, telephone They can be mounted, cars, aircraft, ships, trains, etc.

The present invention will be described based on the embodiments, but the present invention is not limited to only the embodiments.

Synthesis example 1

4 liters of four-necked nose-shaped flasks are fitted with methyl pentamethyl silicate 45.6 g and ethyl silicates 40 (tetraethyl) Tokishiran's average pentamer oligomer, manufactured by Corcode Co., Ltd.) 500 g and ALMIKIRATE D (Kawaken Fine Chemical ( Co., Ltd.), a Le mini-c-time mono § cell Chi Le § Seto ne one door bi-scan (76% Lee Seo profile Roh of E Ji Le § Seto a cell tape over the door), ⁰ node on Norre Solution) was added and stirred well. A mixture of 21.7 g of water and 500 g of methanol was gradually applied thereto. This is heated under reflux for 3 hours, and then volatile components such as methanol are distilled off, and the residue is recovered in a flask. The number average molecular weight (Mn) by GPC of the product obtained in 390 g of the product was 3,100. 1 丄 H — CH by NMR measurement

Three

/ The value of all R was 0.56. In addition, the number average molecular weight (Mn) of the ethyl silicate 40 measured in the same manner was 1,500.

Synthesis example 2

HCF ₂ CF ₉ CH was added to 100 g of a co-condensate of methyltrimethoxysilane and ethyl silicate 40 synthesized in the same manner as in Synthesis Example 1. OH was added thereto, and the mixture was heated under reflux for 1 hour. Then, low boiling components such as methanol and ethanol were distilled off using a rectification column to obtain 106 g of a product. The number average molecular weight by GPC was 3,300, and the fluorine content measured by elemental analysis was 4.8% by weight. Synthesis example 3

1000.0 g of HCF ₂ CF ₂ CH ₂ OH was added to 100 g of a co-condensate of methyltrimethoxysilane and ethyl silicate 40 synthesized in the same manner as in Synthesis Example 1. And heated to reflux for 1 hour. Using a rectification column, low boiling components such as methanol and ethanol were distilled off to obtain 176 g of a product. The number average molecular weight by GPC was 3500 and the fluorine content was 30.5% by weight.

Synthesis example 4

4 liters of four-hole nose-shaped flask with 45.6 g of methyl methacrylate and 40 liter of ethyl silicate 500 g of a pentamer oligomer of Sicilan (manufactured by Collcoat Co., Ltd.) and 0.07 g of a 35% hydrochloric acid aqueous solution were vigorously mixed and stirred. To this, a mixture of 18.1 g of water and 500 g of methanol was gradually added. This was heated under reflux for 3 hours, and then volatile components such as methanol were distilled off. 425 g of the product were obtained in a flask. The molecular weight by GPC was M n = 1700. i fi — NMR measurements As a result, the value of CH ₃ / total R was 0.53.

Synthesis example 5

Three liters of four-hole nose-shaped flasks have 92.3 g of methyl retitol oxysilane and 9 g of ethyl iris ligate 28 Tokishiran, Monomer) 1000 g and ANOMI KIRATE D (manufactured by Kawaken Fine Chemical Co., Ltd.) Add 4.80 g of 76% isopropanol solution of acetylacetonate bis (ethyl acetate acetate) and mix well. did . To this was gradually added a mixture of 114.2 g of water and 100 g of ethanol. This was heated under reflux for 3 hours, and then volatile components such as ethanol were distilled off. 51.7 g of the product were obtained in a flask. The molecular weight by GPC was Mn = 370.

Synthesis example 6

3 liters of four-mouthed NAS-type flasks are fitted with methyltrimethylsilicon 11.5.6 g and methyl resilient gel 5 1 (tetra 1000 g of average tetramer oligomer of methoxysilane (manufactured by Colcoat Co., Ltd.) and aluminum silicate D (Kawaken Fine Chemical A 76% solution of aluminum monoacetate bis- (ethyl acetate acetate) manufactured by Co., Ltd.) 0.80 g was added and the mixture was stirred well. To this, a mixture of 50.9 g of water and 1000 g of methanol was gradually added. This was heated under reflux for 3 hours, and then the volatile components such as methanol were distilled off. 898.7 g of the product was obtained in a flask. The molecular weight by GPC was Mn = 4900.

Synthesis example 7

Three liters of four-mouthed N-shaped flasks are fitted with a retinosilicate 40 (average pentamer oligomer, tetramer, tetramer) 1000 g and 1.44 g of 35% hydrochloric acid aqueous solution Stir well with force. This was followed by the gradual addition of methanol. This was heated under reflux for 3 hours, and then volatile components such as methanol were distilled off. 866.8 g of the product were obtained in a flask. The molecular weight by GPC was M n = 3300.丄 ^!-The value of CH ₃ / total R determined by NMR measurement was 0.43. Example 1

Zeffl LC-1974 White paint (Paint consisting of vinylidene fluoride copolymer and acryl resin manufactured by Daikin Industries, Ltd .: Resin solid content 30%) Then, 100 parts by weight (hereinafter referred to as “parts”) of the above and 150 parts of butylacetate are mixed, and 12.0 parts of the silicon-containing compound obtained in Synthesis Example 1 is added thereto. After stirring well, the coating composition of the present invention was obtained. This paint composition was pre-painted (spray coating) using a fluorine paint (white) as an undercoat paint (film thickness 50 // m). Luminium plates (7 x 15 x 0.5 cm) were painted, dried at room temperature for 1 week, and coated with a 40 m film thickness. The following tests were performed. The results are shown in Table 1.

Water contact angle:

One week after outdoor exposure, they were measured by the liquid drop method in air. Antifouling stain adhesion and appearance:

After the above coated plate was exposed outdoors for 3 power months and 6 power months on the 3rd floor rooftop of a building in Osaka Prefecture at a slope of 30 ° on the south side, the antifouling stain adhesion and appearance were evaluated. did . That is, the antifouling property was measured by measuring the difference (AL *) between the initial lightness of the coated plate and the lightness after exposure, and setting the AL * force, ', 0 or less than 0 to A , B when less than 1 to 2, C when less than 2 to 4, D when less than 4 to 6, and E when more than 6.

Regarding the external appearance, if there is no abnormality by visual inspection, B was evaluated when there was some dullness and C when there was an abnormality, and the contents were also described. '

Appearance (biased): A composition obtained by further adding 100 parts of butyric acetate to the above-mentioned coating composition was applied on a tin plate with a doctor blade of 10 mi1. The coating was then applied smoothly and allowed to stand at room temperature for 8 hours, after which the coating was visually inspected for deviations. Here, the term “bias” refers to a phenomenon in which a coating film becomes wave-like after painting and drying, and the thickness of the coating film is not constant. When there was no abnormality, A was evaluated, when there was some deviation, B was evaluated, and when there was significant deviation, C was evaluated. Example 2 to 4

A coating composition of the present invention was prepared in the same manner as in Example 1 except that the components shown in Table 1 were used, and evaluated in the same manner as in Example 1. The results are shown in Table 1. Note that LC-1941 in Table 1 is Zeffl LC—941 manufactured by Daikin Industries, Ltd., and it means that it is a copolymer of Fuzihi vinylidene and an acrylic resin. It is a varnish for paint.

Example 5

Zeffl GK-500 White paint (Daikin Industries, Ltd., a solvent-soluble fluorinated fluorinated copolymer butylene acetate solution: resin solid component 30 %) 100 parts and 150 parts of butyric acetate are mixed, and the mixture is mixed with Taken D-140 N (Isophorone ISO, manufactured by Takeda Pharmaceutical Co., Ltd.). 12.9 parts (NCO / OH-1.0) with the compound-based curing agent and dibutyltin dilaurate (12.0 parts) , And the mixture was thoroughly stirred to obtain a coating composition of the present invention. This coating composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 6 A coating composition of the present invention was prepared in the same manner as in Example 1 except that the components shown in Table 1 were used, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Examples 1 to 6

A coating composition for comparison was prepared in the same manner as in Example 1 except that each component shown in Table 1 was used, and evaluated in the same manner as in Example 1. In Comparative Example 6, LF-200 (a hydroxyl group-containing solvent-soluble fluorine resin) manufactured by Asahi Glass Co., Ltd. was used as the resin. The results are shown in Table 1.

100 parts of resin

Initial contact angle to water Stain adhesion Appearance Appearance to coating film addition Resin Curing agent

Compound of compound

1 3 3 5 7 2 weeks 1 month 3 months 6 months 12 months 6 months 12 months Addition amount (parts)

1 LC-974 None Synthetic example 1 40 63 45 32 30 A A A A A A A A A Actual 2 IX— 974 None Synthetic example 2 40 60 43 28 25 A A A A A A A A A

3 LC-971 None Synthesis example 1 40 61 46 31 31 A A A A A A A A A

4 IX— 971 None Synthesis example 2 40 78 42 25 23 A A A A A A A A A A Example

5 GK-500 D140N Synthesis example 1 40 68 48 33 32 A A A A A A A J A

A A A A

D140N Synthesis example 2 40 80 47 24 23 A A A A

1 GK-500 D140N Synthesis example 3 40 90 51 46 22 A A A A A A A A C

2 GK-500 D140N Synthesis example 4 40 77 75 76 73 B C D D E A A A Ratio

3 GK-500 D140N Synthesis example 5 40 78 75 72 43 B B B B C A A A

4 GK-500 D140N Synthesis example 6 40 76 78 70 65 B C C D D A A A Example A A A A C Crack A

5 GK-500 D140N Synthesis example 7 40 75 44 28 25 A A

C minute

A A C crack A

6 LF-200 D140N Synthesis example 1 40 72 53 30 27 A A A

Crack

As is evident from Table 1, when the fluorine content of the silicon-containing compound increases, the bias of the coating film increases and the stability of the coating film decreases. In addition, when the trialkoxysilane of the formula (1) is not co-condensed (Comparative Example 3), the coating film will be cracked. Industrial availability

According to the present invention, there is provided a coating composition which is effective in preventing adhesion of rain streaks and the like, and which can maintain the appearance of a coating film stably for a long period of time. It can be provided at a low price.

Claims

The scope of the claims

1. (A) A co-condensate of the formula (1): XSi (OR) ₃ and the formula (2): Si (0R) ₄ or its oligomer (formula (1) In (2), X is a hydrogen atom or an alkylene group having 1 to 5 carbon atoms, R is the same or different, and is an oxygen atom, a nitrogen atom or A monovalent organic group having 1 to 10 carbon atoms which may contain a fluorine atom) and containing a fluorine atom, and having a fluorine content of 5% by weight. And less than g-containing compounds

(B) Resin for paint

A coating composition comprising the composition.

2. (A) Formula (1): XS i (OR) ₃ and Formula (2): Co-condensate of S i (OR) ₄ or its oligomer and formula (3): Reactant with HOR (in formulas (1), (2) and (3), X is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R is the same as Or a monovalent organic group having 1 to 10 carbon atoms, which may contain an oxygen atom, a nitrogen atom or a fluorine atom). Ga-containing compounds having a fluorine content of less than 5% by weight, if they contain atoms, and

(B) Resin for coating

A coating composition comprising the composition.

3. The coating composition according to claim 1 or 2, wherein the number-average molecular weight of the silicon-containing compound is from 2,000 to 5,000 in terms of GPC (polystyrene conversion).

4. One also small Do rather the organic group R of gate Lee-containing compound _{(A), H (CF 9} ) 2 CH 2 -, H (CH 9) 4 CH 2 - or the CF ₃ CF Claims that are ₂ CH ₂ — No claims 1 to 3 The coating composition according to any one of the above.

5. The coating composition according to any one of claims 1 to 4, wherein X in the silicon-containing compound (A) is a methyl group.

6. At least one of the organic groups R in the silicon-containing compound (A) is a methylene group, and the number of methyl groups (CH The coating composition according to any one of claims 1 to 5, wherein QZ (all R) is from 0.2 to 0.8.

7. The resin for coating (B) is a homopolymer of fusinivinylidene, a solvent-soluble vinylidene fluoride copolymer or a fusidani vinylidene. The coating composition according to any one of claims 1 to 6, which is an aqueous dispersion of a copolymer.

8. The coating resin (B) is a hydroxyl- or carboxy-group-containing solvent-soluble fluorinated olefin copolymer, or an acryl-poly-mono resin. Or (C) a curing agent and / or a curing catalyst, wherein the resin comprises a curing agent and / or a curing catalyst. Composition for paint.

9. The coating resin (B) is a solvent-soluble tetrafluoroethylene copolymer containing a hydroxyl group and a Z or carboxyl group, and (C) The coating composition according to any one of claims 1 to 6, which includes a curing agent and / or a curing catalyst.