JP2002265865A - Method for producing aqueous dispersion of fluorine- containing olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for water-based coating material having a long pot life, a balanced and an excellent non-staining property and weather resistance, and capable of forming a coating film having high luster and hardness. SOLUTION: The resin composition for water-based coating material is composed of (A) 100 pts.wt. of a synthetic resin emulsion (weight of the solid component of the emulsion), (B) 1-50 pts.wt. of a silane compound expressed by formula (I) : (R<1> O)4-a SiR<2> a (R<1> groups are each same or different 1-20C organic group; R<2> groups are each same or different 1-20C organic group; and (a) is 0 or 1) and/or its partially hydrolyzed condensation product and (C) 0.1-50 pts.wt. of a polymer and/or oligomer having a group expressed by formula (II): -N(-R)-C(=O)- (R is H or a 1-20C organic group).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic resin aqueous coating composition which is excellent in pot life and which has excellent non-staining adhesion and can form a high gloss coating film.

[0002]

2. Description of the Related Art Attempts to improve the non-staining property and weather resistance of a coating film by adding a silane compound to a coating material are already known.

For example, JP-A-6-506632 and WO95 / 02462 disclose a paint composition in which a tetrafunctional silicate compound is blended in an organic paint. These publications disclose that a tetrafunctional silicate compound is applied to a water-based paint, and also include examples in which the compound is added to an acrylic emulsion paint.

Further, a technique in which various silane compounds are added to a synthetic resin emulsion is disclosed in Japanese Patent Application Laid-Open No. H11-148019.
JP-A-10-110078, JP-A-10-254
No. 46, JP-A-8-259892, JP-A-2000-4
4836, USP-5686523, JP-A-2000-
No. 212513, and US Pat. No. 5,714,532.

[0005]

However, the techniques described in these publications cannot be said to have sufficient performance in terms of the pot life of the coating composition, non-staining adhesion of the coating film, gloss and hardness. .

[0006]

The present inventors have made intensive studies to solve these problems, and as a result, have found that 100 parts by weight of the synthetic resin emulsion (A) (parts by weight of solid content of the emulsion; hereinafter the same). ), the formula ^{(I): (R 1 O} ) in _{^{4-a SiR 2 a (I}} ) ( wherein, R ¹ are the same or different, from 1 to 20 carbon atoms
R ² is the same or different and has 1 to 2 carbon atoms
An organic group of 0; a is an integer of 0 or 1) and / or a partial hydrolysis condensate thereof (B) 1
To 50 parts by weight and a group represented by the formula (II): -N (-R) -C (= O)-(II) (wherein R is a hydrogen atom or an organic group having 1 to 20 carbon atoms). That the resin composition for water-based coatings comprising 0.1 to 50 parts by weight of a polymer and / or oligomer (C) having the following formula (1) is excellent in pot life and is capable of forming a highly glossy coating film with excellent non-staining adhesion. And completed the present invention.

In the present invention, the component (C) is preferably water-soluble or water-dispersible, and more preferable examples are polyvinylpyrrolidone, polyoxazoline,
At least one selected from the group consisting of polyamide, polypeptide, polyurethane, polyimide, and polyacrylamide is used.

Further, the synthetic resin emulsion (A)
The emulsion is preferably (1) an emulsion of a fluororesin or (2) an emulsion of an acrylic resin. Examples of the fluororesin include (1a) a homopolymer of fluoroolefin or a copolymer of fluoroolefins, or (1)
b) A copolymer of a fluoroolefin and a non-fluorinated monomer is preferred.

Further, as the silane compound and / or the partial hydrolysis condensate thereof in the component (B), tetramethoxysilane, tetraethoxysilane, tetra-
Preferred are n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane and / or a partially hydrolyzed condensate thereof.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The synthetic resin emulsion (A) used in the present invention is not particularly limited as long as it is a commercially available emulsion-type water-based resin for a paint or a paint. For example, acrylic resin, fluorine resin,
Melamine resins, silicone resins, epoxy resins, polyester resins, polyether resins and the like can be mentioned.

The vinyl monomer used in the synthesis of the polymer of the component (A) is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate,
Vinyl monomers such as butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, and cyclohexyl (meth) acrylate; styrene, α-methylstyrene, chlorostyrene, 4-hydroxystyrene, and vinyltoluene Aromatic hydrocarbon-based vinyl monomers; α, β-ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, crotonic acid, fumaric acid, and citraconic acid An acid having a polymerizable carbon-carbon double bond such as styrene sulfonic acid and vinyl sulfonic acid; or a salt thereof (such as an alkali metal salt, an ammonium salt or an amine salt); an acid anhydride such as maleic anhydride; They are combined with straight-chain or branched alcohols having 1 to 20 carbon atoms. Ester; (meth) acrylate having an amino group such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate; (meth) acrylamide, α-ethyl (meth) acrylamide, N- Butoxymethyl (meth) acrylamide, N, N-dimethylacrylamide, N-methylacrylamide, acryloylmorpholine or their hydrochloric acid and acetate; vinyl esters such as vinyl acetate, vinyl propionate and diallyl phthalate; and allyl compounds; Vinyl monomers containing a nitrile group such as acrylonitrile; vinyl monomers containing an epoxy group such as glycidyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, hydroxystyrene, Alonix 5700 (Toa Gosei Chemical Co., Ltd.)
), PlacelFA-1, PlacelFA-
4, PlacelFM-1, PlacelFM-4
(The above are manufactured by Daicel Chemical Industries, Ltd.), HE-10, HE-
20, HP-10, HP-20 (all manufactured by Nippon Shokubai Chemical Co., Ltd.), Blemmer PP series, Blemmer PE
Series, Blemmer PEP Series, Blemmer AP
-400, Blemmer AE-350, Blemmer NKH
-5050, Blemmer GLM (Nippon Oil & Fats Co., Ltd.)
MA-30, MA-50, MA-100, MA-
150, RA-1120, RA-2614, RMA-5
64, RMA-568, RMA-1114, MPG13
0-MA (all manufactured by Nippon Emulsifier Co., Ltd.), hydroxyl group-containing vinyl monomers such as hydroxyl group-modified vinyl hydroxyalkyl vinyl monomers; α, β- such as hydroxyalkyl esters of (meth) acrylic acid; Hydroxyalkyl esters of ethylenically unsaturated carboxylic acids and vinyl compounds containing a phosphoric ester group or vinyl compounds such as (meth) acrylates containing urethane bonds or siloxane bonds; AS-macromonomer manufactured by Toa Gosei Chemical Co., Ltd. 6, AN-6, AA-6, AB-6, AK-5
And other vinyl monomers such as vinyl methyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene and N-vinylimidazole.

Further, a monomer containing a silyl group can also be used. Specific examples include, for example, 3-triethoxysilylpropyl methacrylate, 3-trimethoxysilylpropyl methacrylate, and the like, which are preferable in terms of good stability.

The fluorine-containing acrylic monomers include trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, β- (perfluorooctyl) ethyl (meth) acrylate and the like can be used.

In addition to the resin of the synthetic resin emulsion (A), a coating film formed using the obtained curable resin composition is particularly excellent in weather resistance and chemical resistance, and has a wide range of resin designs. For this reason, the fluororesin (1) or the acrylic resin (2) is preferable.

The fluororesin (1) is preferably (1a) a homopolymer of fluoroolefin or a copolymer of fluoroolefins, or (1b) a copolymer of fluoroolefin and a non-fluorinated monomer. A blend resin of these polymers and a resin containing no fluorine atom,
Composite resins can also be used.

Examples of the fluoroolefin include vinyl fluoride, vinylidene fluoride (VdF),
C2-C4 such as tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), and trifluoroethylene
A degree of fluoroolefin is used. As the non-fluorinated monomer copolymerizable with the fluoroolefin,
For example, ethylene; α such as propylene and isobutylene
-Olefins; vinyl ethers such as ethyl vinyl ether (EVE), cyclohexyl vinyl ether (CHVE), hydroxybutyl vinyl ether (HBVE), butyl vinyl ether, isobutyl vinyl ether, methyl vinyl ether and polyoxyethylene vinyl ether; polyoxyethylene allyl ether and ethyl allyl ether Alkenyls such as, hydroxyethyl allyl ether, allyl alcohol, allyl ether;
Vinyl acetate, vinyl lactate, vinyl butyrate, vinyl pivalate, vinyl benzoate, VEOVA9, VEOVA10
(All are product names of Shell Chemical Company); and ethylenically unsaturated carboxylic acids such as itaconic anhydride, succinic anhydride, crotonic acid and the like.

The fluoroolefin copolymer includes VdF / TFE copolymer, VdF / HFP copolymer, VdF / CTFE copolymer, and VdF / TFE / CT copolymer.
VdF copolymers such as FE copolymers and VdF / TFE / HFP copolymers; and TFE / HFP copolymers.

Examples of the copolymer of a fluoroolefin and a non-fluorine-based monomer include a copolymer of CTFE and a vinyl ether.

Examples of the blended resin or composite resin of the fluororesin (1) and the resin containing no fluorine include α, α in an aqueous medium in the presence of particles of a VdF copolymer.
Examples include a fluorine-based composite resin obtained by seed polymerization of a monomer having a β-unsaturated group.

The solid content of the synthetic resin emulsion (A) is from about 20 to 70% by weight, preferably from about 30 to 60% by weight, from the viewpoint of stability during coating. The average particle size of the synthetic resin particles is 50 to 3 in view of the stability of the aqueous dispersion.
It is about 00 nm, preferably about 100 to 200 nm. The pH of the synthetic resin emulsion (A) is usually in the range of 5 to 10.

The synthetic resin emulsion (A) used in the present invention and its production method are described, for example, in WO 95/08.
No. 582 pamphlet, JP-A-2-70706, JP-A-3-37252 and JP-A-8-259892 can be used.

The component (B) is the formula ^{(I): (R 1 O} ) 4-a SiR silane compound and / or partial hydrolytic condensate thereof represented by ² _a (I) is, in the resulting coating film It is a component that gives non-staining adhesion and high gloss.

Specific examples thereof include, for example, tetramethyl silicate, tetraethyl silicate, tetra-n-
Propyl silicate, tetra-i-propyl silicate, tetra-n-butyl silicate, tetra-i-butyl silicate, tetra-t-butyl silicate, MSi
Tetraalkyl silicates and / or partial hydrolysis condensates thereof, such as 51, ESi28, ESi40 (all manufactured by Colcoat); methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane,
Ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane hexyltriethoxysilane, heptyltrimethoxysilane, heptyl Triethoxysilane,
Phenyltrimethoxysilane, phenyltriethoxysilane, octadecyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- (meth) acryloxypropylpyroxytrimethoxysilane, 3- (meth) acryloxypyropyltriethoxysilane, methyltrimethylsilane se
Examples include trialkoxysilanes such as c-octyloxysilane, methyltributoxysilane, and AFP-1 (manufactured by Shin-Etsu Chemical Co., Ltd.) and / or partially hydrolyzed condensates thereof.

The silane compound (B) is usually compounded in the form of an emulsion using an emulsifier. Emulsifiers can be emulsified by using any of nonionic, anionic, cationic and amphoteric emulsifiers.However, nonionics can be used because the stability of the silane compound, the water resistance of the dried coating film, and the durability are improved. Preference is given to using emulsifiers. From the viewpoint of dispersion stability of the emulsion, an anionic emulsifier can be used in combination.

The nonionic emulsifier is not particularly limited. For example, polyoxyethylene alkylaryl ethers such as polyoxyethylene dodecyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether; polyoxyethylene lauryl ether; Polyoxyethylene alkyl ethers such as polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and polyoxyethylene cetyl ether; polyoxyethylene fatty acid esters such as polyoxyethylene stearate, polyoxyethylene oleate and polyoxyethylene laurate Glycerin fatty acid esters such as glycerol monostearate and glycerol monooleate;
Sorbitan monoesters, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan fatty acid esters such as sorbitan monosesquioleate;
Polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate; poly such as polyoxyethylene sorbitol tetraolate Oxyethylene sorbitol fatty acid esters and the like can be mentioned.

Also, a fluorine-based or silicone-based nonionic emulsifier can be used. Examples of the fluorine-based nonionic emulsifier include nonionic perfluoroalkyl-containing polyoxyethylene oxide such as perfluoroalkylsulfonic acid amide-modified polyalkylene oxide. Is raised.

The silicone-based nonionic emulsifier includes, for example, nonionic polyalkylene oxide-modified polydimethylsiloxane in which one end and / or both ends and / or side chains of polydimethylsiloxane are modified with polyalkylene oxide. As specific examples, KF-351, KF-352, KF-353, KF
-354, KF-355, KF-615, KF-61
8, KF-945, KF-907, X-22-6008
(Above, manufactured by Shin-Etsu Chemical Co., Ltd.).

The anionic emulsifier is not particularly limited as long as it is a commonly used emulsifier. Sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate,
Sulfonates such as sodium isooctylbenzenesulfonate; Newcol-723SF, Newcol-
707SN, Newcol-707SF, Newcol
Anionic emulsifiers containing a (poly) oxyethylene group, such as -740SF and Newcol-560SN (all manufactured by Nippon Emulsifier Co., Ltd.).

The method of using these emulsifiers is described in JP-A-8-259892 and JP-A-10-2544.
The method described in each of JP-A No. 6 can be preferably employed.

The amount of the silane compound (B) is 1 to 50 parts by weight, preferably 5 to 20 parts by weight, per 100 parts by weight of the synthetic resin emulsion (A). If the amount of the silane compound (B) is too large, the pot life is shortened. If the amount is too small, the hardness and gloss of the obtained coating film are reduced.

An important feature of the resin composition for water-based paints of the present invention is that the component (C) is represented by the formula (II): -N (-R) -C (= O)-(II) The point is that a polymer and / or an oligomer having a hydrogen atom or an organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group) is further blended.

By blending this component (C), the pot life can be prolonged and a coating film having a high gloss can be formed.

In the present invention, the component (C) is preferably a water-soluble or water-dispersible polymer and / or oligomer. Preferred examples thereof include polyvinylpyrrolidone and polyoxazoline having a group represented by the formula (II). ,
One or more of polyamide, polypeptide, polyurethane, polyimide, and polyacrylamide may be used. In addition to these polymers, polyvinyl alcohol, polyethylene oxide, polyamine, polycarboxylic acid and the like can also be used.

The amount of the component (C) is 0.1 to 50 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 1 to 1 part by weight, per 100 parts by weight of the synthetic resin emulsion (A).
0 parts by weight. If the amount of the component (C) is too large, the water resistance is lowered. If the amount is too small, the pot life is shortened and the gloss becomes low.

Although the mechanism by which the aqueous coating composition of the present invention exerts the above effects has not been completely elucidated,
Possibly due to the localization of the component (B) on the surface of the coating film during drying of the coating film, the hardness and hydrophilicity of the coating film surface (non-staining adhesion)
Is applied to the coating film, and -N (-R)-of the above formula (II) is further added.
Interaction (compatibility) occurs between the component (C) having a C (＝ O) — group and the resin component of the synthetic resin emulsion (A) and / or the silane compound (B), and the pot life of the paint It can be considered that the effect of increasing the gloss of the coating film is exhibited. Further, as a result, it is presumed that the hardness of the obtained coating film is increased, whereby a further effect of preventing contamination is exhibited.

Further, if necessary, 100 parts by weight (solid content) of the component (B) may be added to the resin composition for water-based paint of the present invention.
On the other hand, the curing catalyst (D) may be blended in an amount of 0.1 to 50 parts by weight. Specific examples of the curing catalyst include, for example, organic tin compounds such as dibutyltin dilaurate, dibutyltin malate, dioctyltin dilaurate, dioctyltin malate, and tin octylate; phosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monooctyl Phosphate or phosphate esters such as phosphate, monodecyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dioctyl phosphate, didecyl phosphate; propylene oxide, butylene oxide, cyclohexene oxide, glycidyl methacrylate, glycidol,
Acrylic glycidyl ether, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Cardura (E) manufactured by Yuka Shell Epoxy Co., Ltd. , Epicoat 828, Epicoat 1001, etc. and phosphoric acid and / or
Or addition reaction product with acidic monophosphate; organic titanate compound; organic aluminum compound; organic zirconium compound; maleic acid, adipic acid, azelaic acid, sebacic acid, itaconic acid, citric acid, succinic acid, trimellitic acid, pyromellitic acid Acids, acid anhydrides thereof, acidic compounds such as paratoluenesulfonic acid; amines such as hexylamine, di-2-ethylhexylamine, N, N-dimethyldodecylamine and dodecylamine; these amines and acid phosphate esters And a reaction product thereof; alkaline compounds such as sodium hydroxide and potassium hydroxide; and imidazole compounds such as 2-ethyl-4-methylimidazole.

Although the resin composition for water-based coatings of the present invention has good film-forming ability as it is, the film-forming ability can be further enhanced by using an auxiliary solvent. Specific examples of the co-solvent include, for example, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, n
Alcohols such as butyl alcohol, isobutyl alcohol, hexyl alcohol, octyl alcohol;
Cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol isobutyl Ethers such as ether, tripropylene glycol monoethyl ether, tripropylene glycol monobutyl ether, and tripropylene glycol monoisobutyl ether; butyl cellosolve acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monobutyl ether acetate, and trip Propylene glycol monobutyl ether acetate, glycol ether esters, such as tripropylene glycol mono isobutyl ether acetate.

These solvents may be added during the polymerization of the synthetic resin emulsion (A) or after the polymerization.

As additives to the resin composition for water-based paints of the present invention, if necessary, pigments usually used in paints (white pigments such as titanium dioxide, calcium carbonate, barium carbonate, kaolin, carbon, red iron, cyanine blue, etc.) Colored pigments), plasticizers, solvents, dispersants, thickeners, defoamers, preservatives, anti-settling agents, leveling agents, UV absorbers, and other additives used as ordinary paint components. You may mix and use. When titanium dioxide is added to the resin composition for water-based paints, the use of titanium dioxide having an isoelectric point of 7 or more improves the gloss and weather resistance of the resulting coating film. Specific examples of titanium dioxide having an isoelectric point of 7 or more include, for example, JR805, JR901, JR603,
R602 (all manufactured by Teica Corporation) and the like.

The aqueous coating composition of the present invention can be applied to various substrates by a usual coating method by appropriately blending the above-mentioned additives. Examples of the coating method include a brush coating method, a spray coating method, and a roller method. In addition, the substrate is not particularly limited, for example, concrete, wood,
Metal (iron, stainless steel, aluminum, etc.),
Plastics and other paint films.

By drying and curing at room temperature to 120 ° C. after coating, a cured coating film having good balance of non-staining adhesion, strength, gloss and weather resistance can be obtained.

The resin composition for a water-based paint of the present invention can be used as a paint composition for various uses. In particular, a weather-resistant paint, a low-contamination paint, and a heavy-duty anticorrosion paint used for articles and buildings used outdoors. It is suitable for, for example.

[0043]

EXAMPLES The present invention will now be described specifically with reference to Preparation Examples, Examples and Comparative Examples, but the present invention is not limited to only these Preparation Examples and Examples. In Preparation Examples, Examples and Comparative Examples, “parts” and “%”
Are "parts by weight" and "% by weight", respectively.

Preparation Example 1 (Preparation Example of White Paint) Zaffle SE310 (a composite resin aqueous emulsion of vinylidene fluoride resin / acrylic resin manufactured by Daikin Industries, Ltd. PH = 7, solids concentration 51%) was used as the base emulsion.

Separately, 10.0 parts of water, SN5 as a dispersant
027 (manufactured by Sannobuco) 5.3 parts, FS as antifoaming agent
013B (manufactured by Dow Corning) 0.3 parts, ethylene glycol 4.0 parts, 28% ammonia water 0.1 part, Typek CR97 as titanium oxide (manufactured by Ishihara Sangyo Co., Ltd.)
70.0 parts were dispersed in water by a sand mill to prepare a pigment paste.

Next, 68.
0.6 parts of 28% ammonia water is added to 2 parts, and then
44.1 parts of the pigment paste, diethyl adipate5.
1 part, 0.1 part of FS013B (manufactured by Dow Corning) as an antifoaming agent, and ADECANOL UH420 as a thickener
1.9 parts of a 10% aqueous solution (manufactured by Asahi Denka Kogyo KK) was added and stirred at 400 rpm for 1 hour to obtain a white paint.

Preparation Example 2 (Preparation of Emulsion of Silane Compound (B)) 5 parts of methyl silicate 51 (tetramethyl silicate partially hydrolyzed condensate manufactured by Colcoat) and ethyl silicate 40 (tetraethyl silicate partially hydrolyzed by Colcoat) HLB is 16.
4 parts of polyoxyethylene sorbitan laurate were mixed and stirred at a high speed of 1000 rpm or more, and 76 parts of deionized water was slowly added thereto to prepare an emulsion (S1) of the silane compound (B).

Examples 1 to 4 and Comparative Examples 1 to 3 100 parts (solid resin content) of the white paint obtained in Preparation Example 1 were mixed with the emulsions (S1) and (S1) of the silane compound (B) prepared in Preparation Example 2. C) The amount of the component shown in Table 1 (parts by weight of solid content) was added,
After sufficiently stirring and mixing for 15 minutes, a resin composition for water-based paint was obtained. The pot life of this was examined. Table 1 shows the results.

Pot life: left indoors at 25 ° C.
Evaluate at the time when gelation started. The test is terminated at 24 hours.

In Table 1, the amount of the silane compound (B) in the emulsion is the weight of the silane compound (B) per 100 parts by weight of the resin solid content in the white paint.

The abbreviations in Table 1 indicate the following.

Et40: Partial hydrolyzate of tetraethyl silicate manufactured by Colcoat (about 40% in terms of SiO ₂ )

Et48: Tetraethyl silicate partial hydrolyzate manufactured by Colcoat (about 48% in terms of SiO ₂ )

PVP: polyvinylpyrrolidone manufactured by Aldrich (average molecular weight: about 10,000) and JIS H
The obtained coating composition was applied on an AM712 chemical conversion-treated aluminum plate defined by 4000 with a 10 mil doctor blade, and dried at room temperature for 3 days to prepare a test coated plate. The following items were measured for this test coated plate. Table 1 shows the results.

Gloss: The gloss of the coating film is measured using a gloss meter (manufactured by Suga Test Instruments Co., Ltd.).

Pencil hardness: After the test coated plate is left for one week, it is measured according to JIS K5400.

Contact angle with water after actual exposure:
On the roof of the research building (3rd floor) of the Daikin Industries, Ltd., Settsu-shi, Osaka, on the third floor, actual exposure was performed for one month at a 30 ° inclination on the south side, the painted plate was washed with running water, and the static contact angle of water Is measured with a contact angle meter (manufactured by Kyowa Science Co., Ltd.).

Actual exposure dirt: The color (L value) of the test coated plate is measured by DP300 manufactured by Minolta Co., Ltd., and is set as an initial value. Then, apply the test coated plate to Daikin Industries, Ltd. in Settsu, Osaka.
On the roof of the research building (3rd floor) in the Yodogawa Works, the actual exposure was continued for 6 months at a 30 ° inclination on the south side, and then the L value was measured again.

The evaluation is made by classifying the stain resistance after 6 months as follows. A: ΔL ≦ 3 (almost dirty) B: 3 ≦ ΔL ≦ 5 (somewhat dirty) C: 5 ≦ ΔL ≦ 10 (dirty) D: 10 ≦ ΔL (very dirty) )

Accelerated weather resistance gloss retention:
After the accelerated weathering test was continued for 1000 hours using an I-Super UV tester manufactured by Iwasaki Electric Co., Ltd., the gloss was measured.
The gloss retention GR with respect to the initial gloss is determined by the following equation. GR (%) = (gloss after 2000 hours / initial gloss) ×
100

The results are classified and evaluated as follows. ：: GR ≧ 80% Δ: 80%> GR ≧ 50% ×: 50%> GR

Accelerated weathering appearance: The coated plate subjected to the accelerated weathering resistance test is visually and comprehensively evaluated for cracks in the coating film, the occurrence of blisters, the degree of dirt, and the like.

[0063]

[Table 1]

[0064]

According to the present invention, the pot life is long,
It is possible to provide a resin composition for water-based paint that is excellent in non-staining adhesion and weather resistance in a well-balanced manner and that can form a coating film with high gloss and high hardness.

Continued on the front page (72) Inventor Hiroo Mitsumata 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Manufacturing Co., Ltd. (72) Inventor Tsunehiko Fuwa 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Inside Yodogawa Works (72) Inventor Haruhiko Mohri 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd.Yokogawa Works F-term (reference) 4J038 CA021 CA081 CB011 CB081 CC021 CC071 CC081 CC091 CC101 CD021 CD081 CD101 CD111 CD121 CE022 CE022 CG031 CG071 CG081 CG141 CG161 CG171 CG172 CH031 CH041 CH071 CH081 CH121 CH171 CH201 CH251 CR071 CR072 DB221 DF022 DG002 DH002 DJ022 DL022 DL032 GA03 GA06 GA09 GA13 GA14 GA15 MA08 MA10 NA01 NA05 NA11 PC26 PC06 PC04

Claims (6)

[Claims] (1) 100 parts by weight of a synthetic resin emulsion (A) (parts by weight of solid content of the emulsion), formula (I): (R ¹ O) _4-a SiR ² _a (I) (wherein R ¹ is Same or different, having 1 to 20 carbon atoms
R ² is the same or different and has 1 to 2 carbon atoms
An organic group of 0; a is an integer of 0 or 1) and / or a partial hydrolysis condensate thereof (B) 1
To 50 parts by weight and a group represented by the formula (II): -N (-R) -C (= O)-(II) (wherein R is a hydrogen atom or an organic group having 1 to 20 carbon atoms). A resin composition for an aqueous coating composition comprising 0.1 to 50 parts by weight of a polymer and / or oligomer (C) having the following. 2. The resin composition according to claim 1, wherein the component (C) is water-soluble or water-dispersible. 3. The aqueous paint according to claim 1, wherein the component (C) is at least one selected from the group consisting of polyvinylpyrrolidone, polyoxazoline, polyamide, polypeptide, polyurethane, polyimide and polyacrylamide. Resin composition. 4. The synthetic resin emulsion (A) comprises (1)
The resin composition for a water-based paint according to any one of claims 1 to 3, which is an emulsion of a fluororesin or an emulsion of (2) an acrylic resin. 5. The synthetic resin emulsion (A) is an emulsion of a fluororesin, wherein the fluororesin is a copolymer of (1a) a homopolymer of fluoroolefin or a copolymer of fluoroolefins, or (1b) a fluoroolefin. The resin composition for an aqueous paint according to any one of claims 1 to 4, which is a copolymer with a fluorine-based monomer. 6. The silane compound and / or a partially hydrolyzed condensate thereof in the component (B) is tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-silane.
The resin composition for an aqueous paint according to any one of claims 1 to 5, which is n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, and / or a partially hydrolyzed condensate thereof.