JPH11131020A - Composition for coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition for coating materials capable of stably retaining fouling anti-adhesion effects and the appearance of a coating film for a long period at a low cost. SOLUTION: This composition for coating materials comprises (A) a silicon- containing compound which is a cocondensate of formula (1): XSi(OR)3 with formula (2): Si(OR)4 or an oligomer thereof (X is hydrogen atom or a 1-5C alkyl group; R's are each same or different and a 1-10C monovalent organic group which may contain oxygen atom, nitrogen atom or fluorine atom) with <=5 wt.% fluorine content thereof when the fluorine atom is contained and (B) a resin for the coating materials. The number-average molecular weight of the silicon-containing compound is 2,000-5,000 determined by a gel permeation chromatography(GPC) (expressed in terms of polystyrene).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paint composition capable of preventing the adhesion of stains such as rain streaks.

[0002]

2. Description of the Related Art In recent years, a solvent-soluble fluoroolefin copolymer having a hydroxyl group or a carboxyl group has been used as a resin for a super-weather resistant paint, and its results have been growing. For example, JP-B-60-21686, JP-A-3-121107
JP, JP-A-4-279612 and JP-A-4-4-2
Copolymers of fluoroolefins and vinyl ethers and vinyl esters proposed in JP 8707 and the like are soluble in ordinary paint solvents, and can be baked or cured at room temperature by combining with a curing agent such as isocyanate or melamine. It is known to form a coating film having excellent weather resistance and the like.

[0003] However, these coating films have a problem that when exposed outdoors, dirt in the atmosphere and rain streaks adhere to them and are easily deposited (ie, poor in anti-soil adhesion). In order to improve the wiping properties (contamination removal properties) of carbon stains and magic stains, see Japanese Patent Application Laid-Open No.
In 3881, a reaction product of a fluoroolefin copolymer and a silane compound is studied. Also, U.S. Pat. No. 3,429,845 and JP-A-4-275379.
In the publication, a composition of a hydrolyzate obtained by adding water and a catalyst (such as hydrochloric acid) to a silicate (monomer) or a silicate condensate (oligomer) and hydrolyzing the same in an alcohol, and a hydroxyl group-containing fluoroolefin copolymer is disclosed. Has been proposed. However, these compositions do not have the effect of improving the antifouling adhesion.

[0004] As a technique using a silane compound as a curing site, Japanese Patent Publication No. 45-11309 discloses another technique.
JP-A-5-78612, JP-A-61-25885
No. 2, JP-A-62-116673, JP-A-64-75
575, JP-A-2-232221, JP-A-2-24
No. 0153, JP-A-4-21482, JP-A-4-6
No. 5476, Japanese Patent Application Laid-Open No. 4-292677, etc., but the curing is insufficient because it contains a large amount of alcohol and water. Alternatively, since the silicate has a hydroxyl group in advance or requires high-temperature baking, there is a problem that migration to the surface of the silicate is suppressed, and the stain resistance is not improved as described above.

[0005] The situation is the same in the case of other paints such as acrylic, acrylic silicon, inorganic materials, etc., and there is hardly any known material having remarkably improved antifouling adhesion.

In some cases, silane compounds are used as a dehydrating agent during polymerization or pigment dispersion. However, most of the silane compounds react with moisture during the production, and the paint itself produced therefrom is resistant to contamination. At present, little effect has been obtained in improving the adhesion.

For the purpose of improving the anti-staining property, for example, WO 94/06870, WO 95 /
02645, JP-A-7-48540, JP-A-7-1
No. 02211, JP-A-7-136584, JP-A-7-
173429, JP-A-7-82520, JP-A-7-825
Techniques using a silicon compound have been proposed in, for example, JP-A-109435 and JP-A-7-60184. But,
These technologies include surface hydrophilicity and its reproducibility, antifouling adhesion, curability, compatibility, recoatability, storage stability, pot life, color separation prevention, defoaming, painting workability, coating surface Cracking, flexibility and alkali resistance are not satisfactory.

In order to solve these problems, the present inventors have developed a coating composition containing a specific organometallic compound, oligomer, or co-oligomer having a relatively high fluorine content as an antifouling agent (WO 97). / 11130 pamphlet). However, when the fluorine content is increased, the production cost increases, and not only the range of use is limited, but also a problem (unevenness) may occur in the appearance of the coating film.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a paint composition which is capable of forming a coating film which is extremely excellent in antifouling adhesion and which does not adhere and accumulate dirt and rain streaks in the air. To provide a low cost.

[0010]

That is, the present invention provides:
(A) Formula (1): XSi (OR) ₃ and Formula (2): Si
(OR) ₄ or a cocondensate thereof with an oligomer thereof (in the formulas (1) and (2), X is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R is the same or different, and an oxygen atom, a nitrogen atom Or a silicon-containing compound which is a monovalent organic group having 1 to 10 carbon atoms which may contain a fluorine atom and has a fluorine content of less than 5% by weight when containing a fluorine atom; The present invention relates to a coating composition comprising a resin.

(A) Formula (1): XSi (OR) ₃
And a reaction product of a cocondensate of the formula (2): Si (OR) ₄ or an oligomer thereof and a formula (3): HOR (formula (1)
In (2) and (3), X is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R is the same or different and has 1 to 10 carbon atoms which may contain an oxygen atom, a nitrogen atom or a fluorine atom. A silicon-containing compound having a fluorine content of less than 5% by weight when containing a fluorine atom, and a coating composition comprising (B) a coating resin.

In these compositions, the number average molecular weight of the silicon-containing compound is 20 in GPC (polystyrene conversion).
It is preferably from 00 to 5000.

Further, at least one of the organic groups R in the silicon-containing compound (A) is H (CF ₂ ) ₂ CH ₂ —, H (C
It is preferably H ₂ ) ₄ CH ₂ — or CF ₃ CF ₂ CH ₂ —, and more preferably, X in the silicon-containing compound (A) is a methyl group. Furthermore, it is preferable that at least one of R is a methyl group, and the number of methyl groups occupying in all the organic groups R (CH ₃ / total R) is 0.2 to 0.8.

The coating resin (B) is preferably a vinylidene fluoride homopolymer, a solvent-soluble vinylidene fluoride copolymer or an aqueous dispersion of a vinylidene fluoride copolymer, and the coating resin (B). Is a hydroxyl group- and / or carboxyl group-containing solvent-soluble fluoroolefin copolymer, an acrylic polyol resin or an acrylic silicone resin, and (C) contains a curing agent and / or a curing catalyst, or the coating resin (B) contains a hydroxyl group and / or Alternatively, a coating composition which is a carboxyl group-containing solvent-soluble tetrafluoroethylene copolymer and contains (C) a curing agent and / or a curing catalyst is preferable.

[0015]

DETAILED DESCRIPTION OF THE INVENTION The coating composition of the present invention comprises (A)
It comprises a silicon-containing compound containing no fluorine atom or containing less than 5% by weight, and (B) a resin for a coating material, and if necessary, (C) a curing agent and / 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 silicon constituting the silicon-containing compound (A) is applied as a paint, it collects on the surface of the coating film, and is further hydrolyzed and desorbed by the action of rainwater and contaminates the coating film surface. The substance can be removed.

The silicon-containing compound (A) has the formula (1)
May be a cocondensate of a trialkoxysilane of the formula (2) and a tetraalkoxysilane of the formula (2) or an oligomer thereof, or a trialkoxysilane of the formula (1) and a tetraalkoxysilane of the formula (2) or an oligomer thereof May be a reaction product of a co-condensate of the formula with an alcohol of the formula (3).

The feature of the present invention is that the silicon-containing compound (A)
Does not contain a fluorine atom, or even if it contains a fluorine atom, the content is less than 5% by weight, preferably 3% by weight or less.

As the silicon-containing compound (A) containing no fluorine atom, as the trialkoxysilane of the formula (1), X is a hydrogen atom, methyl, ethyl, propyl, and R is methyl, ethyl, propyl, butyl; As the tetraalkoxysilane of the formula (2), R is preferably methyl, ethyl, propyl or butyl. The tetraalkoxysilane of the formula (2) may be a 1 to 20 mer, preferably a 1 to 10 mer. When reacting the alcohol of the formula (3), R is preferably methyl, ethyl, propyl or butyl.

Particularly preferred combinations include, for example, the following.

[0021]

The condensation ratio of the formula (1) / formula (2) is 1/3 to 20, preferably 1/5 to 1 in terms of the molar ratio of silicon atom units.
5 When the ratio of the formula (1) increases, the surface hydrophilicity tends to be insufficient.

In the cocondensate, at least one of R is a methyl group, and the number of methyl groups in the total organic groups R (CH ₃ / total R) is 0.2 to 0.8, especially 0.1 to 0.8. When it is 35 to 0.65, it is excellent in initial hydrophilicity,
As a result, the initial anti-staining property can be improved.

Next, the silicon-containing compound (A) containing a fluorine atom is a group (R _f ) in which at least one of R in the formulas (1), (2) and / or (3) contains a fluorine atom. There is something. R _f is a monovalent fluorinated organic group having 1 to 10 carbon atoms which may contain an oxygen atom or a nitrogen atom. As a specific example, H (CF ₂ ) m
CH ₂ , F (CF ₂ ) mCH ₂ CH ₂ (m is 2 to 10) and the like, and particularly, H (CF ₂ ) ₂ CH
_{2 -, H (CF 2)} 4 CH 2 - or CF ₃ CF ₂ CH ₂ - is a short-chain fluoroalkyl group such preferred.

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

In order to reduce the fluorine content in the silicon-containing compound (A) to less than 5% by weight, the alkoxysilanes of the formulas (1) and (2) must be non-fluorinated, and the formula (3)
This can be easily achieved if the alcohol is a fluorine-containing alcohol. Examples of such a fluorinated alcohol include H (CF ₂ ) mCH ₂ OH and F (CF ₂ ) mCH ₂ C
H ₂ OH (m is 2 to 10);
(CF ₂ ) ₂ CH ₂ OH, H (CF ₂ ) ₄ CH ₂ OH or C
F ₃ CF ₂ CH ₂ OH is preferred in terms of hydrolyzability.

The reaction ratio of the formulas (1), (2) and (3) differs depending on which compound has a fluorine atom introduced. For example, when the alkoxysilanes of the formulas (1) and (2) are non-fluorinated and a fluorinated alcohol is used as the formula (3), the fluorine content in the starting compound may be considered. In this case, the fluorine atom in the fluorinated alcohol is based on the total weight of the non-fluorinated cocondensate having a silicon atom unit molar ratio of 1/3 to 20 of the formula (1) / formula (2) and the fluorinated alcohol. Weight fraction 0.1-30
%, Usually 1 to 10%.

In the production of the silicon-containing compound (A), if an alkoxysilane of the formula (1) and the formula (2) (the formula (2) may be an oligomer) is required, an alcohol of the formula (3) And heating in the presence of a catalyst. Equations (1) and (2)
(Or an oligomer for formula (2)) may be mixed and heated in the presence of a catalyst, and if necessary, a distillation operation is performed, followed by adding an alcohol of formula (3) and heating. You may.

As the catalyst, for example, hydrochloric acid, sulfuric acid,
Acetic acid, paratoluenesulfonic acid, ammonia, trimethylamine, triethylamine, tributylamine, 1,
8-diazabicyclo (5,4,0) undecene-7 (D
BU), (−)-sparteine, 4-N, N-dimethylaminopyridine, monoethanolamine, triethanolamine, N, N, N ′, N′-tetramethylethylenediamine, sodium hydroxide, potassium hydroxide, Acids such as sodium hydrogencarbonate, potassium t-butoxide, sodium ethoxide, tetramethylammonium hydroxide, tetramethylammonium hydrogensulfate, tetrabutylammonium hydroxide, tetrabutylammonium hydrogensulfate, etc.
Alkali, aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), aluminum monoacetylacetate bis (ethyl acetoacetate), ethyl acetoacetate aluminum diisopropylate, aluminum isopropylate, aluminum ethylate, aluminum sec-
Aluminum compounds such as butyrate; organometallic compounds / organic metal salts such as dibutyltin dilaurate, dibutyltin acetate, dioctyltin maleate, tetraisopropyl titanate, and tetrabutyl titanate. Hydrochloric acid is preferred from the viewpoint of catalyst efficiency and production stability. , Sulfuric acid and aluminum compounds are preferred.

Examples of the reaction solvent include alcohols such as methanol, ethanol, isopropanol, n-butanol, t-butanol, octanol, 2,2,2-trifluoroethanol and 2,2,3,3,3-pentafluoroethanol. , Ethers such as tetrahydrofuran, 1,4-dioxane, and tetrahydropyran; ketones / esters such as acetone and 2-methoxyethyl acetate; N, N-dimethylformamide; N, N-dimethylacetamide; N-methylacetamide; Amides such as N-methylpyrrolidone and polyoxazoline; carboxylic acids such as acetic acid, trifluoroacetic acid and F (CF ₂ ) ₈ COOH; and fluorine-containing aromatics such as trifluoromethylbenzene and m-bistrifluoromethylbenzene. But dissolution 2,2,2-trifluoroethanol in terms of high, 2,2,3,3,3-pentafluoro-ethanol, tetrahydrofuran, 1,4-dioxane, tetrahydropyran are preferred. When alcohol is used as a reaction solvent, from the viewpoint of inhibiting the curing reaction,
After the co-condensation, the alcohol is preferably distilled off by distillation or the like.

The obtained co-condensate preferably does not contain a silanol group from the viewpoint of surface hydrophilicity.

In the present invention, the silicon-containing compound (A)
Has a number average molecular weight of 2,000 to 500, as measured by GPC (in terms of polystyrene using tetrahydrofuran as a solvent).
0, especially 2500-3500, is a surface hydrophilicity,
The storage stability of the silicon-containing compound and the appearance of the coating film are preferred.

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 part by weight, the antifouling property tends to be low. If the amount is more than 80 parts by weight, cracking of the coating film, reduction in compatibility with the resin and the like may occur.

The coating composition of the present invention comprises (A) the above-mentioned specific silicon-containing compound acting as an antifouling agent and (B)
It is composed of a coating resin and, if necessary, (C) a curing agent and / or a curing catalyst, and imparts excellent antifouling adhesion, low electrification, antifogging and the like to the coating film.

Examples of the coating resin (B) include a solvent-soluble fluoroolefin copolymer having a hydroxyl group and / or a carboxyl group, an acrylic polyol resin, an acrylic silicone resin, an inorganic material, and a fluorine-free material having no functional group. A homopolymer or copolymer of vinylidene fluoride, a composite aqueous dispersion of a vinylidene fluoride copolymer and an acrylic copolymer, or an aqueous dispersion of a fluoroolefin-vinyl ether copolymer is preferred.

Examples of the fluoroolefin copolymer having a hydroxyl group and / or a carboxyl group include JP-B-60-21686 and JP-A-3-121107.
JP-A-4-279612, JP-A-4-28707
And those described in JP-A-2-232221 and the like. The number average molecular weight (by GPC) of the copolymer is 1000 to 100000
And 1500 to 30000 is preferred. If the molecular weight is less than 1,000, the curability and weather resistance tend to be insufficient, and if it exceeds 100,000, problems tend to occur in workability and coatability.

The hydroxyl value of this copolymer is from 0 to 2
00 (mgKOH / g) and 0 to 150 (mgKO
H / g). 200 (mgKOH /
If the value exceeds g), a problem tends to occur in the flexibility of the coating film.

The acid value is from 0 to 100 (mgKOH /
g), and more preferably 0 to 50 (mgKOH / g). If it exceeds 100 (mgKOH / g), a problem tends to occur in the flexibility of the coating film.

As one of the above-mentioned copolymers, hydroxyl groups and / or
Alternatively, a solvent-soluble tetrafluoroethylene copolymer having a carboxyl group can be used.

Examples of the copolymer include Zeffle manufactured by Daikin Industries, Lumiflon manufactured by Asahi Glass Co., Ltd., Cefral Coat manufactured by Central Glass Co., Ltd., Fluonate manufactured by Dainippon Ink and Chemicals, Toa Gosei Co., Ltd. Commercial products such as Zaflon manufactured by the company are listed.

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

The acrylic polyol resin has a hydroxyl value of 0 to 200 (mgKOH / g),
(MgKOH / g). 200 (m
(gKOH / g), there tends to be a problem in the flexibility of the coating film.

The acid value of the acrylic polyol resin is as follows:
0 to 100 (mg KOH / g), and 0 to 50 (mg KOH / g).
KOH / g). 100 (m
(gKOH / g), there tends to be a problem in the flexibility of the coating film.

Examples of the acrylic polyol resin include Dianal manufactured by Mitsubishi Rayon Co., Ltd., Acridic manufactured by Dainippon Ink and Chemicals, Hitaloid manufactured by Hitachi Chemical Co., Ltd., and Olester manufactured by Mitsui Toatsu Chemicals, Inc. Commercially available products can be used.

The acrylic silicone resin may be any resin obtained by polymerizing an acrylic silicone monomer together with a hydroxyl group-containing monomer or another polymerizable unsaturated monomer. The acrylic silicone resin may have a hydrolyzable silyl group, a hydroxyl group, or an epoxy group.

As the acrylic silicone resin, for example, Zemurac manufactured by Kanegafuchi Chemical Industry Co., Ltd. and Sanyo Chemical Industry Co., Ltd.
Commercially available products such as Cleamar can be used.

Examples of the inorganic material include a non-fluorinated non-hydrolyzable group-containing metal (Si, Ti, Al, etc.) alkoxide, a non-fluorine-containing non-hydrolyzable group-containing organopolysiloxane, and a non-fluorine-containing metal. (Si, Ti, Al, etc.) alkoxides and the like. Commercially available products include, for example, Ekolton, released by Gunze Sangyo Co., Ltd., Glasca manufactured by Nippon Synthetic Rubber Co., Ltd., porcelain manufactured by Toupe Co., Ltd., and Bellclean manufactured by Nippon Yushi Co., Ltd. , Bellhard, SH, SR and DC series manufactured by Dow Corning Toray Silicone Co., Ltd., KR series manufactured by Shin-Etsu Chemical Co., Ltd., Plenact manufactured by Ajinomoto Co., Ltd., organic titanate manufactured by Nippon Soda Co., Ltd., Kawaken Fine Chemicals Aluminum alcoholate and aluminum chelate compound manufactured by Co., Ltd., zirconium alcohol manufactured by Hokuko Chemical Industry Co., Ltd. Kisaido, etc. manufactured by Nippon Unicar Company Limited composite modified silicone oil and MMCA the like.

Other examples of the coating resin include vinylidene fluorides having no functional group (for example, vinylidene fluoride described in JP-B-43-10363, JP-A-3-28206, JP-A-4-189879). And a homopolymer or a copolymer of the above), and can be blended with the resin having the above functional group. When a resin having no functional group is used, it is not always necessary to use a curing agent or a curing catalyst in the coating composition of the present invention.

The composite aqueous dispersion of the vinylidene fluoride copolymer and the acrylic copolymer is disclosed in, for example, JP-A-3-7784 and JP-A-8-120221.
And commercially available products include, for example, Zeffle manufactured by Daikin Industries, Ltd. and Floren manufactured by Nippon Synthetic Rubber Industry Co., Ltd.

Further, as the aqueous dispersion of the fluoroolefin-vinyl ether copolymer, for example,
And commercially available products such as Lumiflon manufactured by Asahi Glass Co., Ltd., and Fluorate manufactured by Dainippon Ink and Chemicals, Inc.

The coating composition of the present invention may contain a curing agent and a curing catalyst as long as the desired antifouling property of the present invention is not impaired.

Examples of the curing agent include isocyanate compounds, blocked isocyanate compounds, melamine resins, dibasic acids, non-hydrolyzable group-containing silane compounds, epoxy resins and acid anhydrides. Isocyanates, blocked isocyanates and epoxy resins are preferred from the viewpoint of rain.

Examples of the above isocyanate compound and blocked isocyanate compound include 2,4-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyl diisocyanate, and trimethylhexamethylene. Diisocyanate, hexamethylene diisocyanate, n-pentane-1,4-diisocyanate, trimers thereof, adducts and burettes thereof, polymers having two or more isocyanate groups, and further blocked Examples include isocyanates, but are not limited thereto.

The mixing ratio of the isocyanate and the coating resin is preferably 0.5 to 5.0, more preferably 0.8 to 1.2, in NCO / OH (molar ratio). When the isocyanate is of a moisture-curable type, it is 1.1 to 1.5.
Is preferred.

Examples of the melamine resin include, in addition to melamine resin, methylolated melamine resin obtained by converting melamine to methylol, alkyl etherified melamine resin obtained by etherifying methylolated melamine with alcohols such as methanol, ethanol and butanol. However, the present invention is not limited to these.

As the epoxy compound, for example,

[0057]

Embedded image

And the like, but not limited thereto.

Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 1,2-cyclohexyldicarboxylic anhydride, succinic anhydride,
Examples thereof include maleic anhydride, but are not limited thereto.

Further, fumaric acid, succinic acid, adipic acid,
Dibasic acids such as azelaic acid, sebacic acid, dodecanedioic acid and 1,2-cyclohexyldicarboxylic 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, based on 100 parts by weight of the coating resin (B).

Examples of the curing catalyst include organic tin compounds, organic acid phosphates, organic titanate compounds, and the like.
A reaction product of an acidic phosphoric acid ester and an amine, a saturated or unsaturated polycarboxylic acid or an acid anhydride thereof, an organic sulfonic acid, an amine compound, an aluminum chelate compound,
Titanium chelates, zirconium chelates and the like can be mentioned.

Specific examples of the organotin compound include dibutyltin dilaurate, dibutyltin maleate, dioctyltin maleate, dibutyltin diacetate and the like.

As specific examples of the organic acid phosphate,

[0065]

Embedded image

And the like.

Examples of the organic titanate compound include titanates such as tetrabutyl titanate, tetraisopropyl titanate and triethanolamine titanate.

Further, specific examples of the amine compound include butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, and the like.
Triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N
-Methylmorpholine, 1,8-diazabicyclo (5.
4.0) Amine compounds such as undecene-7 (DBU), salts thereof such as carboxylic acids, low molecular weight polyamide resins obtained from excess polyamine and polybasic acid, and reaction formation between excess polyamine and epoxy compound Things.

Specific examples of the chelate compound include aluminum tris (ethyl acetoacetate), aluminum tris (acetyl acetonate), zirconium tetrakis (acetyl acetonate), and diisopropoxy bis (ethyl acetoacetate) titanate. .

One type of curing catalyst may be used, or two or more types may be used in combination. Preferred curing catalysts include organotin compounds and aluminum chelate compounds.

In the present invention, the combination of the coating resin and a curing agent and / or a curing catalyst is not particularly limited, but preferred combinations include the following.

In the case of a fluoroolefin copolymer having a hydroxyl group and / or a carboxyl group or an acrylic polyol resin, when these have a hydroxyl group, the curing agent is an isocyanate compound, a blocked isocyanate compound or a melamine resin. As a curing agent when it has, it is a melamine resin or an epoxy compound. In these systems, a curing catalyst can be used in combination.

In the case of an acrylic silicone resin, a fluorine silicone resin or an inorganic material, 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, per 100 parts by weight of the coating resin (B).
Parts by weight.

In the present invention, an organic solvent can be blended with the coating composition.

Examples of the organic solvent include xylene, toluene, Solvesso 100, Solvesso 150,
Hydrocarbon solvents such as hexane, methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate,
Ester solvents such as ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, ethylene glycol acetate, diethylene glycol acetate, dimethyl ether, diethyl ether, dibutyl ether, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Ether solvents such as diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and tetrahydrofuran; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and acetone; N, N-dimethylacetamide;
Amide solvents such as methylacetamide, acetamide, N, N-dimethylformamide, N, N-diethylformamide, N-methylformamide, sulfonic acid ester solvents such as dimethylsulfoxide, methanol,
Ethanol, isopropanol, butanol, ethylene glycol, diethylene glycol, polyethylene glycol (degree of polymerization: _{3 to} 100), CF ₃ CH ₂ OH, F (C
F ₂ ) ₂ CH ₂ OH, (CF ₃ ) ₂ CHOH, F (CF ₂ ) ₃
CH ₂ OH, F (CF ₂ ) ₄ C ₂ H ₅ OH, H (CF ₂ ) ₂ C
H ₂ OH, H (CF ₂ ) ₃ CH ₂ OH, H (CF ₂ ) ₄ CH ₂
Examples thereof include alcoholic solvents such as OH, and alcoholic solvents are preferred from the viewpoint of pot life.

The chlorofluorocarbon-based solvent is preferably a liquid at room temperature, and may be trichlorofluoroethane, tetrachlorodifluoroethane, trichlorotrifluoroethane, dibromotetrafluoroethane, HCFC-12.
3, HCFC-141b, HCFC-225, dichlorohexafluorocyclobutane, tetrachlorohexafluorobutane, perfluoropentane, perfluorohexane, perfluoroheptane, perfluorooctane, and the like. In order to dissolve the resin for resin and the curing agent well, it is desirable to simultaneously contain a fluorine atom, a chlorine atom, and a carbon atom,
HCFC-123, HCFC-141b, HCFC-2
25, tetrachlorohexafluorobutane is preferred.

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

The mixing ratio of the coating resin and the alcohol solvent is 1 to 100 parts by weight of the coating resin.
50 parts by weight, from 1 to 25 in terms of curability and coating film appearance.
More preferably, it is part by weight.

The coating composition of the present invention further includes, for example, a pigment, a pigment dispersant, a thickener, a leveling agent, a defoaming agent,
Film-forming aid, UV absorber, HALS, matting agent, filler, colloidal silica, antifungal agent, silane coupling agent, anti-skinning agent, antioxidant, flame retardant, anti-sagging agent,
Coating additives such as an antistatic agent, a rust preventive, and a water-soluble resin (such as polyvinyl alcohol and polyethylene oxide) can also be blended.

The coating composition of the present invention may be provided with an undercoat layer and an intermediate coat layer, if necessary, on an object to be coated such as metal, ceramics, plastics, cement, wood, or an old coating film. Can be painted with. The coating method is not particularly limited, and a roll coating method, a spray method, a brush coating method, a roller method, a flow coating method, a dipping method and the like can be adopted. The thickness of the coating film is usually 1 to 100 μm, preferably about 1 to 50 μm.

Next, preferred combinations of the respective components of the coating composition of the present invention will be exemplified, but the present invention is not limited to such combinations.

(1) (A): co-condensate of methyltriethoxysilane and tetraethoxysilane (or an oligomer thereof) 5 to 40 parts Fluorine content: zero or less than 5% Number average molecular weight: 2000 to 5000 (B) : Solvent-soluble vinylidene fluoride copolymer 100 parts (Effect): Excellent in stainproof adhesion, weather resistance, flexibility, acid rain resistance, and coating film appearance.

(2) (A): 5-40 parts of co-condensate of methyltrimethoxysilane and tetramethoxysilane (or oligomer thereof) Fluorine content: zero or less than 5% Number average molecular weight: 2000-5000 (B) : Solvent-soluble vinylidene fluoride copolymer 100 parts (Effect): Excellent in stainproof adhesion, weather resistance, flexibility, acid rain resistance, and coating film appearance.

(3) (A): 5 to 40 parts of a cocondensate of methyltrimethoxysilane and tetraethoxysilane (or an oligomer thereof) Fluorine content: zero or less than 5% Number average molecular weight: 2000 to 5000 (B) : Solvent-soluble vinylidene fluoride copolymer 100 parts (Effect): Excellent in stainproof adhesion, weather resistance, flexibility, acid rain resistance, and coating film appearance.

(4) (A): 5 to 40 parts of a cocondensate of methyltriethoxysilane and tetraethoxysilane (or an oligomer thereof) Fluorine content: zero or less than 5% Number average molecular weight: 2000 to 5000 (B) : 100 parts of a solvent soluble fluoroolefin copolymer containing a hydroxyl group and / or a carboxyl group (C): 5 to 50 parts of an isocyanate compound or a blocked isocyanate compound or an epoxy resin Excellent acid rain resistance, alkali resistance, and excellent film appearance.

(5) (A): 5 to 40 parts of cocondensate of methyltrimethoxysilane and tetramethoxysilane (or an oligomer thereof) Fluorine content: zero or less than 5% Number average molecular weight: 2000 to 5000 (B) : 100 parts of a solvent soluble fluoroolefin copolymer containing a hydroxyl group and / or a carboxyl group (C): 5 to 50 parts of an isocyanate compound or a blocked isocyanate compound or an epoxy resin Excellent acid rain resistance, alkali resistance, and excellent film appearance.

(6) (A): 5 to 40 parts of a cocondensate of methyltrimethoxysilane and tetraethoxysilane (or an oligomer thereof) Fluorine content: zero or less than 5% Number average molecular weight: 2000 to 5000 (B) : 100 parts of a solvent soluble fluoroolefin copolymer containing a hydroxyl group and / or a carboxyl group (C): 5 to 50 parts of an isocyanate compound or a blocked isocyanate compound or an epoxy resin Excellent acid rain resistance, alkali resistance, and excellent film appearance.

(7) (A): 5 to 40 parts of a cocondensate of methyltriethoxysilane and tetraethoxysilane (or an oligomer thereof) Fluorine content: zero or less than 5% Number average molecular weight: 2000 to 5000 (B) : Acrylic polyol 100 parts (C): Isocyanate compound or blocked isocyanate compound 5 to 50 parts (Effect): Excellent in anti-stain adhesion, stain removal properties, and coating film appearance.

(8) (A): co-condensate of methyltrimethoxysilane and tetramethoxysilane (or an oligomer thereof) 5 to 40 parts Fluorine content: zero or less than 5% Number average molecular weight: 2000 to 5000 (B) : Acrylic polyol 100 parts (C): Isocyanate compound or blocked isocyanate compound 5 to 50 parts (Effect): Excellent in anti-stain adhesion, stain removal properties, and coating film appearance.

(9) (A): co-condensate of methyltrimethoxysilane and tetraethoxysilane (or an oligomer thereof) 5 to 40 parts Fluorine content: zero or less than 5% Number average molecular weight: 2000 to 5000 (B) : Acrylic polyol 100 parts (C): Isocyanate compound or blocked isocyanate compound 5 to 50 parts (Effect): Excellent in anti-stain adhesion, stain removal properties, and coating film appearance.

(10) (A): co-condensate of methyltriethoxysilane and tetraethoxysilane (or an oligomer thereof) 5 to 40 parts Fluorine content: zero or less than 5% Number average molecular weight: 2000 to 5000 (B) : Acrylic silicone resin 100 parts (C): Curing catalyst 0.01 to 1 part (Effect): Excellent in anti-staining property, stain removal property, weather resistance, acid rain resistance, and coating film appearance.

(11) (A): co-condensate of methyltrimethoxysilane and tetramethoxysilane (or an oligomer thereof) 5 to 40 parts Fluorine content: zero or less than 5% Number average molecular weight: 2000 to 5000 (B) : Acrylic silicone resin 100 parts (C): Curing catalyst 0.01 to 1 part (Effect): Excellent in stainproof adhesion, weather resistance, acid rain resistance, and coating film appearance.

(12) (A): 5 to 40 parts of a cocondensate of methyltrimethoxysilane and tetraethoxysilane (or an oligomer thereof) Fluorine content: zero or less than 5% Number average molecular weight: 2000 to 5000 (B) : Acrylic silicone resin 100 parts (C): Curing catalyst 0.01 to 1 part (Effect): Excellent in stainproof adhesion, weather resistance, acid rain resistance, and coating film appearance.

Articles coated with the coating composition of the present invention include, for example, architectural waterproof sheets, tunnel waterproof sheets, agricultural vinyl sheets, agricultural vinyl films, curing sheets, architectural protective sheets, vehicles. For protection sheet, mesh sheet, mesh screen, polycarbonate roof, acrylic board wall, polycarbonate wall, guardrail, traffic light, tunnel inner wall, tunnel interior board, road sign, information board, highway side wall, highway noise barrier, road light, bridge , Bridge girders, piers, chimneys, wallpapers, tatami mats, mats, tablecloths, ventilation fans, marking films, geomembranes, billboards, post boxes, telephone poles, tents, automobiles, aircraft, ships, trains and the like.

[0096]

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

Synthesis Example 1 45.6 g of methyltrimethoxysilane, 500 g of ethyl silicate 40 (an average pentamer oligomer of tetraethoxysilane, manufactured by Colcoat Co., Ltd.) and 500 g of aluminum chelate D (river) were placed in a two-liter four-neck eggplant-shaped flask. 0.339 g of a 76% isopropanol solution of aluminum monoacetylacetonate bis (ethylacetoacetate) manufactured by Ken Fine Chemicals Co., Ltd. was added, and the mixture was stirred well. To this, a mixture of 21.7 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 to obtain 390 g of a product in the flask. The number average molecular weight (Mn) of this product by GPC was 3,100. CH ₃ / total R by ¹ H-NMR measurement
Was 0.56. The number average molecular weight (Mn) of ethyl silicate 40 measured in the same manner was 1500.

Synthesis Example 2 100 g of a co-condensation product of methyltrimethoxysilane and ethylsilicate 40 synthesized in the same manner as in Synthesis Example 1 was added to HCF ₂
10.0 g of CF ₂ CH ₂ OH was added, 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. GPC
And the fluorine content measured by elemental analysis was 4.8% by weight.

Synthesis Example 3 100 g of a co-condensate of methyltrimethoxysilane and ethyl silicate 40 synthesized in the same manner as in Synthesis Example 1 was added to HCF ₂
100.0 g of CF ₂ CH ₂ OH was added, and the mixture was heated under reflux for 1 hour. Next, low boiling components such as methanol and ethanol were distilled off using a rectification column to obtain 176 g of a product. GP
The number average molecular weight by C is 3,500, and the fluorine content is 30.
It was 5% by weight.

Synthesis Example 4 45.6 g of methyltrimethoxysilane, 500 g of ethyl silicate 40 (an average pentamer oligomer of tetraethoxysilane, manufactured by Colcoat Co., Ltd.) and 500 g of a 35% hydrochloric acid aqueous solution were placed in a 2-liter four-necked eggplant-shaped flask. 07 g was added and stirred well. 18.1 g of water and 50 of methanol
0 g of the mixture was added slowly. This was heated under reflux for 3 hours, and then volatile components such as methanol were distilled off. 425 g of product was obtained in the flask. The molecular weight by GPC is M
n = 1700. CH ₃ / by ¹ H-NMR measurement
The total R value was 0.53.

Synthesis Example 5 92.3 g of methyltriethoxysilane, 1000 g of ethylsilicate 28 (tetraethoxysilane, monomer) and aluminum chelate D (manufactured by Kawaken Fine Chemical Co., Ltd. 4.80 g of a 76% solution of acetylacetonate bis (ethylacetoacetate) in isopropanol was added, and the mixture was stirred well. 114.2 g of water and 1 part of ethanol
000 g of the mixture was slowly added. This was heated under reflux for 3 hours, and then volatile components such as ethanol were distilled off. 531.7 g of product was obtained in the flask. The molecular weight by GPC was Mn = 3700.

Synthesis Example 6 115.6 g of methyltrimethoxysilane, 1000 g of methyl silicate 51 (an average tetramer oligomer of tetramethoxysilane, manufactured by Colcoat Co., Ltd.) and 1000 g of aluminum chelate D (Kawaken) 0.80 g of a 76% isopropanol solution of aluminum monoacetylacetonate bis (ethylacetoacetate) manufactured by Fine Chemicals Co., Ltd. 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 volatile components such as methanol were distilled off. 89 product in flask
8.7 g were obtained. The molecular weight by GPC was Mn = 4900.

Synthesis Example 7 Ethyl silicate 40 (an average pentamer oligomer of tetraethoxysilane,
1000 g of Colcoat Co., Ltd.) and 1.44 g of a 35% hydrochloric acid aqueous solution were added, and the mixture was stirred well. Add methanol 1
000 g was gradually added. This was heated under reflux for 3 hours, and then volatile components such as methanol were distilled off. 866.8 g of product was obtained in the flask. The molecular weight by GPC is Mn
= 3300. The value of CH ₃ / total R by ¹ H-NMR measurement was 0.43.

Example 1 100 parts (parts by weight; hereinafter the same) of Zeffle LC-974 white paint (paint consisting of a vinylidene fluoride copolymer and an acrylic resin manufactured by Daikin Industries, Ltd .; resin solid content: 30%) 150 parts of butyl acetate were mixed, 12.0 parts of the silicon-containing compound obtained in Synthesis Example 1 was added thereto, and the mixture was stirred well to obtain a coating composition of the present invention. This coating composition was applied to an AM-712 treated aluminum plate (7 × 15 × 0.5 cm) previously coated (film thickness: 50 μm) with a fluorine coating (white) as an undercoat coating by spray coating.
After drying over a week, a coated plate having a thickness of 40 μm was obtained, and the following tests were performed. Table 1 shows the results.

Water contact angle : One week after outdoor exposure, the contact angle was measured in air by a droplet method.

Stain resistance and appearance : The coated board was exposed outdoors for 3 months and 6 months on the third floor rooftop of a building in Osaka Prefecture at a slope of 30 ° on the south side, and then evaluated for stain resistance and appearance. . That is, the stain resistance was measured by measuring the difference (ΔL *) between the initial lightness of the coated plate and the lightness after exposure, and
When L * is 0 to less than 1 A, B is less than 1 to 2, C is less than 2 to 4, D is 4 to less than 6,
The above time was evaluated as E.

The appearance was evaluated as A when there was no abnormality visually, B when there was some dullness, and C when there was abnormality, and the contents were also described.

Appearance (bias) : A composition obtained by further adding 100 parts of butyl acetate to the above coating composition was applied on a tin plate with a 10 mil doctor blade, and the coating was allowed to stand at room temperature for 8 hours. Observed visually. When there was no abnormality, A was evaluated, when there was some deviation, B was evaluated, and when it was extremely deviated, C was evaluated.

Examples 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. Table 1 shows the results. In addition, LC- in Table 1
941 is Zaffle LC-941 manufactured by Daikin Industries, Ltd.
And a paint varnish comprising a vinylidene fluoride copolymer and an acrylic resin.

Example 5 100 parts of Zeffle GK-500 white paint (butyl acetate solution of a solvent-soluble fluoroolefin copolymer manufactured by Daikin Industries, Ltd .; resin solid content: 30%) and 150 parts of butyl acetate were mixed. 12.9 parts (NCO / OH) with Takenate D-140N (containing isophorone diisocyanate curing agent and dibutyltin dilaurate manufactured by Takeda Pharmaceutical Co., Ltd.)
= 1.0) and the silicon-containing compound 12.0 obtained in Synthesis Example 1.
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. Table 1 shows the results.

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. Table 1 shows the results.

Comparative Examples 1 to 6 A coating composition for comparison 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. In Comparative Example 6, LF-200 (a hydroxyl group-containing solvent-soluble fluororesin) manufactured by Asahi Glass Co., Ltd. was used as the resin. Table 1 shows the results.

[0113]

[Table 1]

As is clear from Table 1, when the fluorine content of the silicon-containing compound increases, the unevenness of the coating film increases and the stability of the coating film decreases. When the trialkoxysilane of the formula (1) is not co-condensed (Comparative Example 3), the coating film is cracked.

[0115]

According to the present invention, it is possible to provide an inexpensive coating composition which has an excellent effect of preventing adhesion of rain streaks and the like, and can stably maintain the appearance of a coating film for a long period of time.

Claims (9)

[Claims] (A) a cocondensate of the formula (1): XSi (OR) ₃ and the formula (2): Si (OR) ₄ or an oligomer thereof (in the formulas (1) and (2), X is A hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R is the same or different, and 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 coating composition comprising a silicon-containing compound having a fluorine content of less than 5% by weight when containing atoms, and (B) a coating resin. 2. A reaction product of a cocondensate of formula (1): XSi (OR) ₃ and formula (2): Si (OR) ₄ or an oligomer thereof and formula (3): HOR (formula (2)) (1), (2)
In (3) and (3), X is a hydrogen atom or a group having 1 to 1 carbon atoms.
5 alkyl groups, R are the same or different, an oxygen atom,
A silicon-containing compound, which is a monovalent organic group having 1 to 10 carbon atoms which may contain a nitrogen atom or a fluorine atom) and has a fluorine content of less than 5% by weight when containing a fluorine atom, and (B ) A paint composition comprising a paint resin. 3. The silicon-containing compound having a number average molecular weight of GP
The coating composition according to claim 1 or 2, wherein C (polystyrene equivalent) is 2,000 to 5,000. 4. The method according to claim 1, wherein at least one of the organic groups R in the silicon-containing compound (A) is H (CF ₂ ) ₂ CH ₂ — or H (CH ₂ ).
₄ CH ₂ — or CF ₃ CF ₂ CH ₂ —.
The coating composition according to any one of the above. 5. The coating composition according to claim 1, 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 methyl group, and the number of methyl groups in all R (CH ₃ / total R) is 0.2 to 0.1. 8
The coating composition according to any one of claims 1 to 5, wherein 7. The coating resin (B) is a vinylidene fluoride homopolymer, a solvent-soluble vinylidene fluoride copolymer or an aqueous dispersion of a vinylidene fluoride copolymer.
7. The coating composition according to any one of claims 6 to 6. 8. The coating resin (B) is a solvent-soluble fluoroolefin copolymer containing a hydroxyl group and / or a carboxyl group, an acrylic polyol resin or an acrylic silicone resin, and contains (C) a curing agent and / or a curing catalyst. Item 7. The coating composition according to any one of Items 1 to 6. 9. The coating resin (B) is a solvent-soluble tetrafluoroethylene copolymer containing a hydroxyl group and / or a carboxyl group, and contains (C) a curing agent and / or a curing catalyst. The composition for a coating according to the above.