WO1999037725A1 - Coating composition - Google Patents

Abstract

An inexpensive coating composition capable of forming films whose stainproofing effects and surface appearances can be retained stably for a prolonged period. The composition comprises (A) a silicon compound represented by general formula (1), wherein at least one of R?1, R2, R3 and R4¿ is methyl, while the others are each independently a C¿1?-C10 organic group, and the ratio of the number of methyl groups to the sum total of R?1, R2, R3 and R4¿ is 0.05 to 0.95; and n is an integer of 2 to 100, and (B) a coating resin.

Description

 Akira — m

Technical field for paint

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

 In recent years, a soluble fluoropolymer copolymer containing a hydroxyl group or a carboxyl group has been used as a resin for ultra-weatherproof coatings. It is growing. For example, phenols proposed in Japanese Patent Publication No. Sho 60-21686, Japanese Patent Application Laid-Open No. f3-121107, Japanese Patent Application Laid-Open No. Hei 4-279612, and Japanese Patent Application Laid-Open No. Hei 4-28707 have been proposed. Copolymers such as vinyl olefins and vinyl olefins are soluble in ordinary paint solvents, and are not soluble in common paint solvents. When combined with a hardener such as lamin, it can be hardened at baking or at room temperature, and forms a coating film that is excellent in weather resistance and the like. And are known.

However, when these coatings are exposed outdoors, they tend to accumulate dirt and rain stains in the air and accumulate easily (that is, antifouling stains). Poor in wearability). In order to improve the wiping properties (contamination removal properties) of carbon stains and magic stains, for example, Japanese Patent Application Laid-Open No. 4-173881 discloses a technique for improving the properties. A reaction between a phenolic dextrin refine copolymer and a silane compound is being studied. Also, in the specification of US Pat. No. 3,342,845, Japanese Patent Application Laid-Open No. 4-275379, there are disclosed a silicate (monomer) and a silicate condensate (oligoma).ー) water and catalyst (salt) Acid and the like, and hydrolyzed in the alcohol to produce a composition of a hydrolyzate and a hydroxyl-containing fluoropolymer copolymer. It has been. However, these compositions do not have the effect of improving the antifouling adhesion property.

 Other technologies that use silane compounds as hardening sites are described in Japanese Patent Publication Nos. 41-111309 and 5-78612. JP-A-61-258852, JP-A-62-116673, JP-A-64-75575, JP-A-2-2322, JP-A-2-2415-3 Japanese Patent Publication Nos. 4-214, 82, 416, 746 and 219, 267, have each been proposed. Anorakol and water contain a large amount of water, and the stiffness is insufficient. Or, the silicate has a hydroxyl group or requires high-temperature baking, so migration to the surface of the silicate is suppressed. However, there are some problems, such as restrictions, and the antifouling and stainability has not been improved as described above.

 Other paints such as acrylic, acrylic silicone, inorganic materials, etc. are in the same condition, and they have remarkable antifouling and adhesion properties. Little is known about the improvements.

 In addition, silane compounds are sometimes used as a dehydrating agent during polymerization or pigment dispersion, but almost all silane compounds are used during production. Can react with water, and the paints produced from them have little effect on improving the antifouling adhesion. This is the current situation.

Also, for the purpose of improving the antifouling adhesion, for example, W094680, WO95Z02645, Japanese Patent Publication No. 7-148540, Japanese Patent Application Laid-Open No. 7-102211, Japanese Patent Application Laid-Open No. 7-136584, Japanese Patent Application Laid-Open No. 7-173842, Japanese Patent Application Laid-open No. Kaikai Hei 7-1094 35, Tokai Kaihei 7-61084, Tokai Hei 8-12922, Tokkai Hei 8-113755, Tokkai Hei 8-319448, Tokai Kaihei No. 9 — 40 9 11 1, Tokuhei Hei 9 — 40908, Tokuhei 9 — 40909, Tokkai Hei 9 — 40907, Tokkai Hei 9 — 165550, Tokai Kaihei 9 — 1655549 , Japanese Patent Publication No. 9-165555, Japanese Patent Publication No. 9-220870, etc., have proposed techniques using a gay compound. . However, these technologies have been developed for the initial surface hydrophilicity and its reproducibility, antifouling adhesion, curability, compatibility, reproducibility, storage stability, and storage stability. It is not satisfactory in terms of cut life, prevention of color separation, defoaming, painting workability, and cracking of the paint film surface.

 Therefore, the purpose of the present invention is to remarkably excel in air pollution and rain streaks, which do not accumulate and accumulate, antifouling adhesion, and especially initial hydrophilicity. The purpose of the present invention is to provide a coating composition for forming a coated film. Disclosure of the invention

 The present invention

 (A) Formula (1):

 OR2

R ¹ O ^ S i-0 R ⁴ (1)

 OR3

(Wherein, scale ^1, R ^2, R ³ Contact good beauty also one small Do rather with the Chi sales of R ⁴ but main switch group, or One rest but, respectively Re its independently 1 to carbon atoms 1 0 organic group, the number ratio against the total of the main ¹ Ji Le group, R ^2, R ³ Contact good beauty R ⁴ of 0 05~ 0 9 5, n is 2 ~:.. L 0 0 of A) a compound containing a compound represented by

(B) Resin for paint It relates to a composition for coatings consisting of this.

 In this case, the organic group having 1 to 10 carbon atoms is an ethyl group, a port pill group, a glycidinole group, a butyl group, or a 2-ethylhexyl group. It is preferred that at least one of the octyl groups be at least one.

 In addition, as a coating resin, a fluoropolymer having a hydroxyl group and / or a hydroxyl group is soluble in a solvent. Unique combination of acrylic resin, acrylic resin, acrylic silicone resin, inorganic materials, and vinylidene fluoride that does not have a functional group Preference is given to a composite aqueous dispersion of a polymer and an acrylic copolymer, or an aqueous dispersion of a fluoroolefin-vinyl ether copolymer. No. Best Forms for Carrying Out the Invention The paint composition of the present invention comprises (A) a compound containing a

(B) Consists of resin for paint.

In the present invention, the gayne-containing compound (A) contains a methyl group as an essential component and acts as an antifouling agent. Usually, in a coating film coated with a coating material, easily removable substituents such as a methyl group are hardly collected on the coating film surface, and the ethyl group, Substituents that are difficult to remove, such as propyl groups, tend to collect on the surface of the coating film. On the other hand, in the present invention, the alkoxy group bound to the gay component constituting the gay component-containing compound (A) is collected on the surface of the coating film. In addition, it is decomposed and desorbed by the action of rainwater and other water, and can remove contaminants adhering to the surface of the coating film. Furthermore, in the present invention, the time required to reach hydrophilicity is shorter than that of a conventional coating film, that is, the initial hydrophilicity is superior. Excellent antifouling adhesion It is intended to provide a coating.

 The silicon-containing compound (A) in the present invention is:

Equation (1):

 OR2

R 丄 O-iS i-1 0 R ⁴ (1)

 OR3

(In the formula, at ^{least one} of R ¹ R, R rio and R ^{4 is} a methyl group, and the rest are each independently a C ¹ -C 10) organic group, scale ^1, RR ³ number ratio against the total of your good beauty R ⁴ of main switch Le group have you to equation (1) is 0. 0 5~ 0. 9 5 , n is 2-1 0 (An integer of 0).

 The silicon-containing compound (A) represented by the formula (1) is represented by the formula (2):

 OR2

R ¹ 0— S i -OR ⁴ (2)

 I

OR3

It is obtained by condensing tetraalkyloxysilane and / or its oligomer represented by the formula (1).

In the formula (1), at least one of R ¹ , R, R ³ and R ⁴ is a methylene group from the viewpoint of the initial hydrophilicity, and the remaining is And each independently represents an organic group having 1 to 10 carbon atoms. Further, the organic group having 1 to 10 carbon atoms may contain an oxygen atom or a nitrogen atom.

Examples of the organic group include an alkyl group, an alkoxyalkyl group, an acyl group, an aryl group, an aryl group, an oxym group, and an amino group. Alkylene groups and glycidyl groups are preferred. The organic group having 1 carbon atom is, for example, a methyl group or a holmyl group, and the organic group having 2 carbon atoms is, for example, an ethyl group. As an organic group having 3 carbon atoms, such as an acetyl group, a methoxymethyl group, and the like, there are, for example, a propynole group, a methoxyethyl group, and a glycine group. An organic group having 4 carbon atoms such as a zir group is, for example, a butyl group such as a butyl group, and a pentyl group as an organic group having 5 or more carbon atoms, for example. , Hexyl group, octyl group, 2-ethylhexyl group, phenyl group, benzyl group, benzyl group, etc. .

 Among these, from the viewpoint of a balance between hydrolyzability and hydrophobicity, an ethyl group, a methylenol group, a propynolene group, a butyryl group, Glycidyl, 2—ethylhexyl and octyl groups are preferred, as well as ethyl, methyl and butyl groups. Is especially preferred.

One technique to, In its us to gain Lee Moto含chromatic of compounds to the onset bright that you only (A), versus the sum of the main switch scale ¹ of Honoré group, R ^2, R ³ Contact good beauty R ⁴ The ratio of the number of particles is 0.05 to 0.95, preferably 0.2 to 0.8, and more preferably 0.35 to 0.65. .

The control of the number ratio of the methyl group to the sum of R ¹ R ² , R ³ and R ⁴ is performed, for example, by controlling the content of the gallium-containing compound represented by the above formula (1). By appropriately selecting the tetraalkyloxysilane and its oligomer and the reaction solvent, which are the raw materials of the compound, changing the value of n It is easy for a person skilled in the art to do this.

 It is sufficient that n is an integer of 2 to L 0, but it is preferably 4 to 30 from the viewpoint of surface hydrophilicity. It is particularly preferred that the value be 5 to 20 in terms of storage stability of the compound containing iodine.

The production of the compound (A) containing a gallium compound is carried out by mixing tetraalkoxysilane (which may be an oligomer) with a catalyst. It is obtained by heating in the presence.

 The catalyst may be, for example, hydrochloric acid, sulfuric acid, acetic acid, paranorenens olenoic acid, ammonia, trimethinoleamine, trietinophenol. Amin, tributylamine, 1, 8 — diaza bicyclo (5, 4, 0) ゥ デ デ (DBU), (1) — snow. Noretin, 41 N, N — dimethylaminopyrimidine, monoethanolamine, triethanolamine, N, N, N ', N' — Tetramethylethylamine, sodium hydroxide, sodium hydroxide, sodium bicarbonate, sodium bicarbonate T—butoxide, sodium ethoxide, hydroxylated tetramethylammonium, hydrogensulfate tetramethylammonium Acid / anoramic powers such as hydroxylated tetrabutylammonium, hydrogenated tetrabutyltinoleammonium, and anolymium trim (Ethyl acetate acetate), Anominium Trim (Acetyl Acetate), Aluminium Monoacetile Acetate Business (Ethanol Acetate Acetate), Ethanol Acetate Acetate Luminium isopro-propylate, aluminum luminate, aluminum sec-butyl, etc. Compounds, dibutyltin dilaurate, dibutyltin acetate, dioctylles maleate, tetraisopropionate Organic metal compounds / organic metal salts, such as noretitanate and tetraplatine, are exaggerated, but their catalytic efficiency and manufacturing safety are high. Therefore, hydrochloric acid, sulfuric acid, and aluminum conjugate are preferred.

Examples of the reaction solvent include methanol, ethanol, and isoprono. No-nore, n-butano-no-no, t-butano-no-o-no-no-no-re, 2,2,2-trino-nore-no-e-no-no-re, 2, 2,3,3,3—Pentafole nozzles, alcohols such as ethanol, tetrahydrofuran, 1,4-dioxan , Ethers such as tetrahydropyran, acetone, acetic acid 2-ketones / esters such as methoxymethyl, N, N — Dimethylformamide, N, N — dimethylaminoacetamide, N—methylamineacetamide, N—methylamine pyrrolide, a mi de ethers etc. port the Rio key support zone Li down, acetic acid, Application Benefits full O b acetate, F (CF _{2) 8} COOH, etc. mosquito Le Bonn acid such, Application Benefits off Honoré O b Fluorine-containing aromatics such as methylbenzene, m-bistriolenomethylbenzene, etc., can be obtained, but the dissolving power is high. To say Pressurized et al METHANOL Norre, error data node on Norre, profile Bruno,. Preference is given to knore, butanore, tetrahydrofuran, 1,4—dioxan, tetrahydropyran. If alcohol is used as the reaction solvent, alcohol is distilled off after co-condensation, for example, from the viewpoint of inhibiting the curing reaction. Is preferred.

 In the present invention, the silicon-containing compound (A) has a number-average molecular weight measured by GPC (converted to polystyrene using tetrahydrofuran as a solvent). 500 or more: L 0000, particularly preferably 2,000 to 6000, is preferable from the viewpoints of hydrophilicity, storage stability of the compound containing a Ga, and appearance of the coating film.

 The compounding amount of the silicon-containing compound (A) is 0.:! With respect to 100 parts by weight of the coating resin (B). It is up to 80 parts by weight, preferably 1 to 30 parts by weight. If the amount is less than 0.1 part by weight, there is a tendency that the anti-fouling property is reduced, and if the amount exceeds 80 parts by weight, the coating film is poor and the compatibility with the resin is reduced. May occur.

The composition for paints of the present invention comprises (A) the above-mentioned specified compound containing a compound which acts as a pollution control agent and (B) a resin for paints. And (C) if necessary, a hardener and / or a hard catalyst. The coating has a good antifouling, low antistatic and antistatic property. It gives properties such as reliability.

 The resin for paint (B) is, for example, a fluorene resin which is soluble in a solvent and has a hydroxyl group and / or a carboxyl group. Fin copolymers, acrylic resin, acrylic resin, inorganic materials, and non-functional functional plastics Or dispersion of a vinylidene fluoride copolymer and an acrylyl copolymer, or a fluoropolymer or a homopolymer or copolymer of An aqueous dispersion of a fin-vinyl ether copolymer is preferred.

 As the above-mentioned fluorinated olefin copolymer having a hydroxyl group or a carboxyl group, for example, Japanese Patent Publication No. Sho 60-21686, Such publications as those described in Japanese Unexamined Patent Publication Nos. Hei 3-121107; As a result, the number average molecular weight (according to GPC) of the copolymer is from 1,000 to 100,000, and preferably from 1,500 to 300,000. If the molecular weight is less than 1,000, the curability and weather resistance tend to be insufficient, and if it exceeds 100,000, the workability and paintability tend to cause problems. There is.

 The hydroxyl value of this copolymer is from 0 to 200 (mg K 0 H

/ g) and preferably 0 to 150 (mg KOH / g). If the amount of the hydroxyl group is reduced, the curing tends to be poor, and if it exceeds 200 (mg KOH / g), a problem arises in the flexibility of the coating film. There is a tendency to be.

The acid value is preferably from 0 to 100 (mg KOHZ g), more preferably from 0 to 50 (mg KOH / g). Said When the acid value decreases, curing tends to be poor, and the acid value tends to decrease.

If it exceeds 100 (mgK0H / g), there is a tendency that a problem occurs in the flexibility of the coating film.

 In addition, as one of the above-mentioned copolymers, a hydroxyl group and / or a carboxy resin are considered from the viewpoints of stain-proofing adhesion, stain-removing properties, and dust-proofing properties. It is also possible to use a solvent-soluble tetrafluoroethylene copolymer having a group.

 Examples of the above-mentioned 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., Fluoronet by Ink Chemical Industry Co., Ltd. of Japan, 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 acrylic polyol resin is 0 to 200 (mgKOH / g), and preferably 0 to 100 (mgKOH / g). If the hydroxyl value is too small, curing tends to be poor, and if it exceeds 200 (mg KOH g), there is a problem with the flexibility of the coating film. There is a tendency to be.

 The acid value of the acrylic polyol resin is from 0 to 100 (mgKOH / g), and more preferably from 0 to 50 (mgKOH / g). If the acid value is too low, curing tends to be poor, and if the acid value exceeds 100 (mg KOH / g), there is a problem in the flexibility of the coating film. There is a tendency to be.

Examples of acrylic resins include, for example, Mitsubishi Rayon Co., Ltd.'s Dianal, and Dainippon Ink Chemical Industry Co., Ltd.'s Atari Co., Ltd. Dick, Hitaroid manufactured by Hitachi Chemical Co., Ltd. Commercial products such as Mitsui Toatsu Chemical Co., Ltd.'s register can be used.

 As the acrylic resin, for example, the acrylic silicone monomer may be a hydroxyl group-containing monomer or other polymerizable unsaturated resin. What is necessary is just that it is polymerized together with the monomer. The acrylic silicone resin may have a hydrolyzable silyl group, hydroxyl group, or epoxy group.

 Acrylic silicone resins include, for example, Zemrack manufactured by Kaneka Kagaku Kagyo Co., Ltd. and Krymarmer manufactured by Sanyo Kasei Kogyo Co., Ltd. You can use commercial products.

 Examples of the inorganic material include non-hydrolyzable group-containing metals (such as Si, Ti, and A1), alcohols, and non-hydrolyzable fluorine-containing organo-organic organos. Nopoloxixan, metals (Si, Ti, A1, etc.), anorecoxide, etc. are exempt, and if they were commercial products, the Gunze industry Ecoleton Co., Ltd., Gloss Power manufactured by Nippon Synthetic Gum Co., Ltd., Poserin manufactured by Tobe Co., Ltd., Belcuri manufactured by Nippon Yushi SH, SR and DC series manufactured by Silicone Corporation, and KR manufactured by Shin-Etsu Chemical Co., Ltd. Series, Plan manufactured by Ajinomoto Co., Ltd., Organic titanium manufactured by Soda Nihon Co., Ltd., A manufactured by Kawaken Fine Chemical Co., Ltd. Aluminum alloy and aluminum alloy compounds, Hino Chemical Industry Co., Ltd.'s Ginore Aluminum Alcoxide, Nihon Rikiichi Co., Ltd.'s complex denatured silicone oil and MMCA are among the best.

In addition to the above-mentioned paint resins, fluorine resins having no functional group (Japanese Patent Publication No. 43-103, No. 3-8282, No. Fluoride described in each gazette such as Kaihei 4 — 1 8 9 8 7 9 A vinylidene homopolymer or copolymer, etc.) can be obtained, and can be blended with the resin having the above-mentioned functional group. In addition, if a resin having no functional group is used, it is not necessary to use a curing agent or a curing catalyst in the paint composition of the present invention. Absent .

 Further, as the composite aqueous dispersion of the vinylidene fluoride copolymer and the acryl copolymer, for example, Japanese Patent Application Laid-Open No. 3-77884 is disclosed. Japanese Patent Application Laid-Open No. 8-122021 is disclosed, and as a commercially available product, for example, Zeffl manufactured by Daikin Industries, Ltd. In addition, Floren manufactured by Nihon Gosei Gum Kogyo Co., Ltd. is mentioned.

 Further, the aqueous dispersion of the fluororefin-1-vinylinole-ester copolymer is described in, for example, Japanese Unexamined Patent Publication No. Some of the commercially available products are, for example, Lumifront manufactured by Asahi Glass Co., Ltd., and Fumino manufactured by Dainippon Ink Chemicals Co., Ltd. You will be able to get more information.

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

 As the curing agent, for example, a dicocyanate compound, a block isocyanate compound, a melamine resin, a dibasic acid, a non-hydrolyzed Although silane compounds containing functional groups, epoxy resins, or acid anhydrides are required, iso-cane from the viewpoints of weather resistance, acid resistance, and rain resistance , Block isocyanate and epoxy resin are preferred.

Examples of the above-mentioned isocyanate compound and the block isocyanate compound include, for example, 2, 4 — tri-range isocyanate. , Diphenylene methane 4, 4 '— Resilience, iso-reagent, iso-holo-zoni-so-zen, re-silient methyl ester Chromatic resiliency isolators, trimethyl resilience isolators, resilience isolators, trimmers Anet, n — pentane-1,4-diisocyanate, these trimers, these adducts ゃ biuret Although these polymers have two or more isocyanate groups, they are also blocked and further isolated. It is not limited to these, but is limited to these.

 The mixing ratio of the isolation to the resin for coating is preferably 0.5 to 5.0 in NC0Z0H (Mono ratio), and more preferably 0.8. ~ 1.2 is more preferred. Also, if the iso- nate is of the moisture-hardening type, then 1.:! ~ 1.5 is preferred.

 The above-mentioned melamin resin may be, for example, besides the melamin resin, the melamin is a methylo-zole-i-i-d-a-r Laminate resin, methylated monomethylated Melamin is etherified with alcohols such as methanol, ethanol, butanol, etc. There are various types of resin such as buttery but not limited to melamin resin.

 For example, the above-mentioned Epoxy Dagger compound is, for example,

CH ₂ -CH-CH ₂ one _{0- CH 2 CH 2 - 0 -} CH 2 _CH- CH 2,

\ Z \

0 o 0

C

CH-CH-CH2 -N N-CH2 CH-CH ₂

 \ Z I I \ /

 o c c 0

 0 ヽ. 0

 N

な ど が あ げ ら れ る が こ れ ら に 限 定 さ れ る も の で は な い 。 CH H2

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

 The acid anhydrides include, for example, phthalic anhydride, tri-U-methritic anhydride, pyromellitic anhydride, and anhydrides 1, 2-cis-hexyl. Examples include, but are not limited to, dicarboxylic acid, anhydrous succinic acid, maleic anhydride, etc.

 Also, fumaric acid, succinic acid, adipic acid, azelanic acid, seno 《cinnamic acid, dodecanedioic acid, 1,2-cyclohexyl Dibasic acids such as oleic 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 (塗料).

Curing catalysts include, for example, organic tin compounds, organic acid phosphate esters, organic titanate compounds, acid phosphate esters and a Reaction with min, saturated or unsaturated polyvalent carboxylic acid or its anhydride, organic sulfonic acid, amide Compounds, aluminum chelates, titanium chelates, quinolone chelates, etc. It is terrible.

 Specific examples of the above-mentioned organic tin compounds include dibutyl tin glaurate, dibutyl tin maleate, dioctinoles maleate, and the like. Eighth, dibutyls, jiacetate, etc. are given.

 有機 Specific examples of the organic acid phosphoric acid ester include:

0 0

 II

(CH ₃ 0) 2 P OH, CH3 OP (0H) 2 (C ₂ H ₅ 0) ₂

0

 II

C ₂ H ₅ OP (0H) 2 [(C H3) 2 CH0] 2 o P = OH.

 Examples of the organic titanate conjugate include, for example, tetrabutyl titanate, tetraisopropinolate titanate op = o Ethanol titanate, such as lithium amine aluminate, is removed.

Further, specific examples of the above-mentioned aminic compound include, for example, butinoreamin, octylamine, dibutinoreamin, mononoamine. Ethanol Amin, Jethanol Amin, Triethanol Amin, Diethylen Amin, Triethylentra Min, olive, min, cyclohexamine, benzilamine, methylamine, propynoleamine, xylene Diamine, triethylene diamine, guanidine, diphenyl guanidine, 2,4,6—tris (dimethino olemino) (Methnole) Pheno-no-Mole, Morholin, N-Methine-Moleholin, 1, 8—Diazabicyclo (5.4.0) Amine-based conjugates such as i7 (DBU), and their salts such as carboxylic acid, and excess polyamine and polybasic acid. Such a low-molecular-weight polyamide resin, a reaction product of an excess of polyamine and an epoxy conjugate, and the like are obtained.

 Specific examples of the chelate compounds include aluminum tris (ethyl acetate acetate) and aluminum tris (acetate). (China acetate), Ginore Consortium Textrax (Acetinolacetonate), Jisopro Box Services (Echilwa) Settlement) Titanium etc. are required.

 One curing catalyst may be used, or two or more curing catalysts may be used in combination. Preferred curing catalysts include an organic tin compound and an anoluminium chelate compound.

 In the present invention, the combination of the coating resin and a curing agent and a Z or a hardening catalyst is not particularly limited. A better combination would be something like the following.

 In the case of fluoro or olefin olefin copolymers containing hydroxy and / or Z or carboxyl groups. When these compounds have a hydroxyl group, examples of the hardening agent include an isopropylate compound, a blockisomate compound and the like. Is a melamine resin, and as a hardener when having a carboxyl group, a melamine resin or an epoxy compound is used. . In these systems, a curing catalyst can be used in combination.

 In the case of acrylic silicone resin, fluorine silicone resin, or inorganic materials, a curing catalyst may be used.

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 resin for coating (B). In the present invention, an organic solvent can be mixed into the coating composition.

Examples of the organic solvent include hydrocarbons such as xylene, toluene, solvesso 100, solvesso 150, and hexane. Solvents, methyl acetate, ethyl acetate, ethyl acetate, ethyl acetate alcohol monomethyl ether, ethyl acetate alcohol, monoethyl acetate Tile ether, alcoholic acid ethyl alcohol, butyric acid monoethyl ether, diethyl ethyl alcohol monomethyl ether, acid Diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethyl acetate acetate Solvents such as toluene, diethyl acetate glycol, etc., dimethyl ether ether, dimethyl alcohol, etc. Ethereum, Djiboutinoretenoe, Echirengurikoremononoteru, Echirengurikorenonoteruoteru , Ethylene glycol monobuty ether, ethylene glycol dimethyl ether, ethylene glycol phenol Chill eater, ethylene glycol, jibutino ter, polyethylene teremono, methane tere, ethylene Glycolate monobutyrate, polyethylene glycol monobutyrate, diethylene glycol total methylateテ, リ リ リ リ 、 テ テ テ 、 、 、, ジ レ リ リ コ 、 、 、 テEther solvents such as urea, tetrahydrofuran, etc., methane urea phenol, methinoolesobutyl phenol, acetate, etc. Ketone-based solvent, N, N—dimethyl acetate amide, N—methyl acetoamide, acetate amide, N, N—dimethyl methyl amide Amide-based solvents such as norem amide, N, N-methyl hol amide, and N-methyl hol arn amide; Snorrephonic acid such as Ester-based solvents, methanol, ethanol, isopropanol, butanol, ethylene glycol, diethylene grayed Li co Lumpur, Po Li et Chi les in g Li co over Honoré (polymerization degree _{3~ 100), CFCH 2 0 H} . F (CF 2) CH 2 0 H. (CF) 2 CHOH, F (CF 9 _{) 3 CH 2 OH, F (} CF 2) 4 C 2 H 5 0 H, H (CF) 2 CH 0 OH, H (CF 2) 3 CH 2 OH, H (CF) 4 CH 9 0 H a throat of Although phenolic solvents are required, alcohol solvents are preferred from the viewpoint of pot life.

As the above-mentioned fluorinated solvent, a liquid at room temperature is desired, and the trichloro-opening fluorene and the tetrachloride fluorene are preferred. , Tri-fluoro mouth, Fluoro-Rotan, Jibromote, Fluoro-Rotan, HCFC-123, HCFC-141B.HCFC-22 5, Jikro-hexafluorocyclobutane, Tetracro mouth to xafluoro-butane, perfluoropentane, no, ⁰ — Fluoro-hexa, perforated heptane, perfluoro-octane, etc. In order to further dissolve the paint resin and the hardener, it is desirable to include a fluorine atom, a chlorine atom, and a carbon atom at the same time. It is preferable to use HCFC-123, HCFC-141b, HCFC-225, and Texa-fluoride.

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

The mixing ratio of the coating resin and the alcohol-based solvent is 1 to 50 parts by weight with respect to 100 parts by weight of the coating resin, and the curability and the appearance of the coating film are poor. It is even more preferred that the amount be 1 to 25 parts by weight from the point of view. The coating composition of the present invention further includes, for example, a pigment, a pigment dispersant, a thickener, a repelling agent, a defoamer, a film-forming aid, an ultraviolet absorbing agent, and the like. Agents, HALS, anti-glazing agents, fillers, colloidal silica, anti-fungal agents, silane coupling agents, anti-skinning agents, antioxidants, difficult Paints such as flame retardants, anti-sagging agents, antistatic agents, anti-oxidants, water-soluble resins (polyvinyl alcohol, polystyrene oxide, etc.) Excipients can also be incorporated.

 The coating composition of the present invention can be used for coating objects such as metals, ceramics, plastics, cement, wood, and old coatings. If necessary, the undercoat layer and the middle coat layer can be provided as appropriate. There are no particular restrictions on the coating method, and the roll coating method, spraying method, brush coating method, roller method, flow coating method, and date method are not particularly limited. It is possible to adopt a tubing method. The thickness of the coating film is usually from 1 to 100 m, preferably from l to 50; tm.

 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. .

Uses of the articles coated with the coating composition of the present invention include, for example, waterproof sheets for construction, waterproof sheets for tunnels, and agricultural vinyls. Roll sheet, agricultural vinyl film, curing sheet, architectural protection sheet, vehicle protection sheet, mesh sheet, mesh sheet Inside the screen, Polycarbonate roof, Acrylic board wall, Polycarbonate wall, Gardanore, traffic light, Tunnel Walls, tunnel interior panels, road signs, billboards, high-speed road side walls, high-speed road noise barriers, road lights, bridges, bridge girders, piers, chimneys, wallpaper, tatami, mats, te -Blue Cross, Ventilation fans, marking finolems, geomembrane, billboards, postal posts, telephone poles, tents, cars, airplanes, ships, electric cars, etc. can give .

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

Synthesis example 1

Two liter four-neck flat-panel type flasks are equipped with a resilient resin 40 (Konorecoat's Tetra Ethoxylan Oligo Marker) 500 g, ANORE MIKIRATE D (Anore Minimonacetate Acetate manufactured by Kawaken Fine Chemicals Co., Ltd.) 3.68 g of bis (ethyl acetate acetate) solution in isopropanol (3.68 g) and 14.5 g of water and 5 ml of methanol 100 g of the mixture was added and stirred, and the mixture was heated under reflux for 3 hours to evaporate volatile components to obtain 374 g of a product. When this was analyzed by ¹ H-NMR, it was found that methyl group / (methyl group + ethynole group) (number ratio) = 0.45. The number average molecular weight by GPC was 480.

Synthesis example 2

Two liters of four-port flasks with plastic nozzles 48 (Coltcourt, Tetra Tokishiran Oligomer) 500 g, 0.72 g of a 35% hydrochloric acid aqueous solution and 500 g of methanol were added, and the mixture was stirred and heated under reflux for 1 hour to evaporate volatile components to obtain 433 g of a product. When this was analyzed by ¹ H-NMR, it was found that the methyl group (methyl group + ethyl group) (number ratio) was 0.43. The number average molecular weight determined by GPC is 330,000.

 Example 1

Zeffle LC — 9 7 4 (a product manufactured by Daikin Industries, Ltd.) 100 parts by weight (hereinafter referred to as “parts”) of vinylidene fluoride copolymer and acrylic resin for paints: 100 parts by weight of resin solids: 38%) and acetic acid Mix 150 parts of butyl, 3.8 parts of the compound containing the compound obtained in Synthesis Example 1 and mix well, and then stir well to obtain the paint composition of the present invention. I got it. This coating composition was pre-painted (spray coating) with a fluorine coating (white) as the undercoating paint (film thickness 50 m). The following tests were performed after painting on a metal plate (7 x 15 x 0.5 cm), drying at room temperature for 1 week, and applying a 40 / m-thick coated plate. . The results are shown in Table 1.

Water contact angle (initial water affinity):

 One week after outdoor exposure, they were measured by the liquid drop method in air. Stain resistance:

 The painted board was exposed outdoors for 1 week, 2 weeks and 1 month on the 3rd floor rooftop of a building under Osaka Prefecture in the rainy season on a 3rd-floor roof at a slope of 30 ° on the south side. The adhesion was evaluated. In other words, the contamination resistance is measured by measuring the difference (ΔL *) between the initial lightness of the coated plate and the lightness after exposure. When AL * is less than 0 or less than L, A is 1 to 1 or less. A value of less than 2 was evaluated as B, a value of 3 to less than 5 as C, a value of 6 to less than 10 as D, and a value of 10 or more as E.

 The appearance was evaluated as A when there was no abnormality by visual inspection, B when there were a few irregularities, and C when there was abnormality. The contents are also described.

Example 2

Other than using the silicon-containing compound obtained in Synthesis Example 2, the coating composition of the present invention was prepared in the same manner as in Example 1 and the same as in Example 1. It was evaluated as follows. The results are shown in Table 1. Example 3 The use of each of the components shown in Table 1 was carried out in the same manner as in Example 1 to prepare the coating composition of the present invention, and the evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1. Note that LC-941 in Table 1 is Zeffl LC-941 manufactured by Daikin Industries, Ltd., which is a copolymer of vinylidene fluoride and a polymer. It is a paint varnish made of lily resin.

Example 4

 A coating composition of the present invention was prepared in the same manner as in Example 3 except that the compound containing the gay obtained in Synthesis Example 2 was used. It was evaluated in the same way as above. The results are shown in Table 1. Comparative Examples 1 to 3

 A coating composition for comparison was prepared in the same manner as in Example 1 or Example 5 except that the components shown in Table 1 were used, and the same as Example 1 was carried out. It was evaluated as follows. The results are shown in Table 1. In Table 1, Et 40, Et 48 and Me 56 are Eno Resilient 40 (manufactured by Konorecoat Co., Ltd.) Pentamer), ethyl silicate 48 (a tetramer of tetraethoxysilane) and a methyl silicate manufactured by Mitsubishi Kagaku Co., Ltd. — To 56 (the tetramer of tetramethyl silane). Example 5

Zeffl GK — 500 White paint (a solvent-soluble fluorophorefin copolymer from Daikin Industries, Ltd., butyric acetate acetate solution: resin solids content 30) %, Titanium oxide 25%), and 100 parts of butyric acid acetate, and then mixed with Takenate D- 14 ON (Isoho, manufactured by Takeda Pharmaceutical Co., Ltd.). 25.4 parts (NCO / 0H = 1.0) of the diisotinate-based curing agent and dibutyltin dilaurate combined with the gallium-containing compound obtained in Synthesis Example 1. A mixture with 6 parts of a coating material is added, and the mixture is sufficiently stirred to obtain a coating composition of the present invention. I got it. 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 5 except that the compound containing the gallium obtained in Synthesis Example 2 was used. And evaluated. The results are shown in Table 1. Comparative Examples 4 to 6

 Using each of the components shown in Table 1, a paint composition for comparison was prepared in the same manner as in Example 1 or Example 5, and the composition for Example 1 was used. It was evaluated in the same way. The results are shown in Table 1.

Example 7

 LC — 974: 100 parts of Zeff Nore GK — A mixture of 66 parts of 500 and Zeffle GK — 34 parts of 501 (Either Daikin Industries, Ltd.) The solvent was replaced with a solvent-soluble fluorofluorene copolymer (butyl acetate solution) manufactured by Co., Ltd. in the same manner as in Example 1 to obtain the paint of the present invention. The composition for use was obtained. This paint composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 8

The same procedure as in Example 7 was repeated except that the composition containing a gay element obtained in Synthesis Example 2 was used to prepare the coating composition of the present invention. It was evaluated in the same way as above. The results are shown in Table 1. Methyl group / Contact angle of water of compound (Α) (degree)

 Stain adhesion resin for paint 5 * Scarlet II or Λ- っ

 (100 parts of all substituent resins are hydrophilic)

 (B) is a curing catalyst compound (A) (, IiISJl X H nosing power π 畺 ("SO 1 3 5 5 7 1 week 2 weeks 1 month

1 No LC Π Κ

 One 974 Synthetic 1 U .4 ο 1 on n U 60 40 25 24 A A A

2 LC-974 Length Synthesis Example 2 ϋ.4ο 1 1π U 65 37 24 24 A A A

3 LC 941 None Synthesis example 丄 0.45 1 υ 67 43 26 25 A A A

4 LC 941 し * *-synthetic fii example 20 Λό 1 1 υ 63 42 24 24 A A A

 5 GK-500 D140N Synthesis example 1 U.45 55 40 27 23 A A A Example

 τ- Q

 6 GK-500 D140N Synthesis example 2 U.4 Q Π υ 60 42 24 25 A A A

7 GK500 / 510 (7/3) D140N Synthesis example 1 U.45 丄 U 64 40 25 24 A A A

Q GK500 / 510 (7/3) 4

 J R¾r example 9 ο 57 38 23 23 A A A

1 LC 1 974 None Ε t40 0 10 82 80 80 79 B B C

2 LC-1 974 None Ε t48 0 10 87 85 65 45 B B B ratio

 3 LC 974 None Me56 1.0 10 89 88 88 85 B B C

 4 GK-500 D140N E t40 0 20 85 82 81 80 B B C Example

 5 GK-500 D140N E t48 0 20 84 80 70 55 B B B

6 GK-500 D140N Me56 1.0 20 90 89 89 88 BBC

As is evident from Table 1, the coating film containing the compound containing silicon according to the present invention is superior in the initial hydrophilicity and the stain resistance. Industrial availability

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

Claims

The scope of the claims 1. (A) Equation (1):  0R2 R ¹ O-iS i — 0 R ⁴ (1)  0R3 (Wherein at ^{least one} of R ¹ R ² , R ³ and R ⁴ One is a methyl group, and the rest are each independently an organic group having 1 to 10 carbon atoms, except for the total of R ² , R ³ and R ⁴ of the methylene group And n is an integer of from 2 to 100), and the ratio of the number to the compound is 0.05 to 0.95, and n is an integer of 2 to 100). (B) Resin for paint  A coating composition comprising the composition.  2. When the organic group having 1 to 10 carbon atoms is an ethyl group, a propyl group, a glycidyl group, a butyl group, a 2 — ethynol hexinole group or an organic group having 2 to 10 carbon atoms. The paint composition according to claim 1, wherein the composition is at least one of cutinole groups.  3. Fluoroolefin copolymers in which the coating resin is soluble in the solvent and has a hydroxyl group and / or a zirconium group. Single or co-polymer of vinyl resin, acrylic silicone resin, inorganic material, vinylidene fluoride which does not have any functional groups , A complex aqueous dispersion of a vinylidene fluoride copolymer and an acrylyl copolymer, or a fluorinated vinyl-vinyl ether copolymer The paint composition according to claim 1 or 2, which is a combined aqueous dispersion.