JPS59164376A - Water-based coating composition - Google Patents

Abstract

PURPOSE:To provide a water-based coating composition excellent in drying property, gloss and film properties, prepared by mixing a specified aqueous emulsion of oxidation-polymerized copolymer with an aqueous solution or dispersion of an oxidation-polymerized resin. CONSTITUTION:The water-based coating composition is prepared by mixing an aqueous emulsion of an oxidation-polymerized copolymer with an aqueous solution or dispersion of an oxidation-polymerized resin. The oxidation-polymerized copolymer is prepared by emulsion polymerization of 2-60pts.wt. monomer having an air-drying double bond selected from among unsaturated polyester compds. obtained by reacting alpha,beta-ethylenically unsaturated dicarboxylic acid (anhydride) with a reaction product of (semi) drying oil fatty acid and alpha,beta- ethylenically unsaturated aziridinyl alkyl ester and a reaction product of (semi) drying oil and polyhydric alcohol, and 98-40pts.wt. copolymerizable alpha,beta-ethylenically unsaturated monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides aqueous li1! An aqueous coating consisting of a covering silk composition and an acid, more specifically an aqueous solution or aqueous dispersion of an oxidatively polymerized polymer emulsion and an oxidatively uncontainable resin, which has high drying properties, is glossy, and has good coating film properties. The present invention relates to a composition for use.

Aqueous coating compositions using a polymer emulsion obtained by emulsion polymerization as a color vehicle generally have different drying properties, water resistance, alkali resistance, etc., but there are problems with water resistance and solvent resistance in the early stage of drying. However, emulsions are known to have poor corrosion resistance, weather resistance, salt water resistance, and gloss.Therefore, research has continued to maintain the advantages of emulsions while overcoming their disadvantages, and one noteworthy solution has been developed. As such, a technology was proposed in which an aqueous solution or dispersion of a fatty acid-modified acrylic resin is blended into an emulsion polymer emulsion.
No. 34, No. 50-126724). The acrylic resin with a fatty acid content of 11 is an unsaturated fatty acid (drying oil fatty acid or semi-drying oil fatty acid) that has a non-covalent double bond, for example, as described in JP-A No. 5'1-80334. α, β
-Aqueous solution of fatty acid-modified monomer obtained by reacting ethylenic saturated acid lycidyl ester with copolymerizable bacterial cells is compatible with emulsion and emulsion. By blending with emulsion, the advantages of the emulsion are not lost but are improved, and the glossiness and
It is said that "C" significantly improves weather resistance.

However, it has been found that even with the improvements previously proposed for 4T, the physical properties of the coating film are still insufficient, particularly in terms of water resistance, corrosion resistance, solvent resistance, chemical resistance, hardness, etc. According to research conducted by the present inventors, this is because although the blended fatty acid-modified acrylic resin is three-dimensional, the emulsion, which accounts for more than half of the substance that forms the coating, is fused.
This is because there is a limit to the physical properties of the paint film because it does not form a three-dimensional structure through fusion alone.If emulsions could also be made three-dimensional, the physical properties of the paint film could be significantly improved.What is the conclusion? Obtained. The present invention has been made from this viewpoint.

According to the present invention, 4J (△) drying oil fatty acid d3 and/or semi-drying ↑1 oil fatty acid and α,β-edylenic saturated acid aziridinyl alkyl ester reaction product, and <8> drying oil and/or or a monomer having an air-drying double bond selected from the reaction products obtained by reacting α, β, β-ethylene saturated dicarboxylic acid or the anhydride with the reaction product of semi-drying oil and polyhydric alcohol. ~60 parts by weight of α, β-J square polymer-free suspension body 9
ε 3 to 40 parts by weight of an aqueous emulsion of an oxidative polymerizable copolymer obtained by emulsification C1, an aqueous solution of d3 and an oxidative polymerizable resin, Ig, and an aqueous dispersion. When the acid is introduced +tt, it is expelled.

The aqueous emulsion of the oxidatively polymerized copolymer used in the present invention C is (△) drying oil fatty acid and/or semi-drying oil fatty acid (for example, tung oil, 1 ita water castor oil, linseed oil, safflower music, melodic music). , sesame oil, poppy oil, tall oil, rice bran oil,
1, fatty acids such as helium oil, horseradish oil, etc.) and α,β-J dylenically unsaturated acids, aziridinyl alkyl esters (e.g., aziridinyl methyl acrylate, aziridinyl edyl acrylate, aziridinyl acrylate, aziridinyl acrylate, reaction products of lysinylpropyl acrylate, aziridinyl dityl acrylate and the corresponding methacrylate-1 to J-3 [3] Drying and/or semi-drying oils (e.g. tung oil, dehydrated castor oil, linseed oil) oil, υ flower oil, soybean oil, sesame oil, poppy seed oil, 1 hel oil, bran oil, spruce oil, sunflower oil, etc.) and polyhydric alcohols (e.g., nitylene glycol, propylene glycol, glycerin, pentaerythritol) 2 to 60 parts by weight of a monomer having an air-drying double bond selected from the reaction product obtained by reacting maleic anhydride, maleic acid, fumaric acid, itaconic acid, etc. Polymerizable α, β−
Saturated monomers for ethylenically unsaturated properties include acrylic acid, methacrylic acid and unsaturated amide compounds such as hydroxyalkylnisal, alkylnisder, acrylamide and methacrylamide, sutyrene, vinyl l-luene, Styrene-based styrenes such as α-methylstyrene,
Emulsion polymerization of 98 to 40 parts by weight of unsaturated nitriles such as acrylic nitrile, methacrylonitrile, vinyl acetate, etc.) to the bottom right of the surfactant and 7. It is manufactured by soaking.

The above emulsion is also used as a copolymerizable α,β-ethylenically unsaturated saturated monomer part in Japanese Patent Publication No. 55-41684.
Formula % () (wherein Rs is hydrogen, lower alkyl, halogen or phenyl group: R2, is ethylene or propylene group)
is hydrogen or a lower alkyl group, and n is a positive number from 4 to 25)
2 to 20 parts by weight of a nonionic polymerizable monomer compound represented by, preferably α, β, β-ethylene saturated monomer,
Alternatively, an anionic polymerizable monomer compound having an α, β-1 dylenically unsaturated group and a sulfonic acid or sulfone-1 group, for example, the formula 0 formula % described in Japanese Patent Publication No. 16291 (In the formula, R1 is hydrogen or a methyl group; R2 is a saturated or unsaturated hydrocarbon group or a substituted hydrocarbon group or an organic group containing an oxyalkylene group; A is an alkylene having 2 to 4 carbon atoms or a substituted alkylene IBM is hydrogen, alkali metal, alkaline earth metal, ammonium or organic amine: m is the valence or ionic valence of M; n is O or a positive number), preferably in an α, β, β-edylene saturated monomer. 0.5-10 heavy center, or the formula R2 described in U.S. Pat.
is a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms or a substituted hydrocarbon group, and B is a saturated hydrocarbon group having 1 to 2 carbon atoms, preferably an α,β-ethylenically unsaturated monomer. Emulsion polymerization in the absence of a surfactant and/or a polymeric protective colloid 1- using a monomer that itself functions as an emulsifier, such as 0.5 to 10 parts by weight in the φ-form. It is also manufactured on a 27-day basis.

This emulsion has a drying oil fatty acid J5 and/or a semi-drying oil fatty acid part involved in oxidative polymerization incorporated into the polymer molecule, so it can be processed by natural oxidation after coating or by the oxidation promoting effect of a metal dryer that is preferably added. It has the property of being three-dimensionally cross-linked and cured to form a strong/V-resistant coating.

In the present invention, an aqueous solution or dispersion of an oxidative polymerizable resin is blended with the emulsion. Various types of oxidation-polymerized resins are known, such as maleated oil, fumarated oil, maleated isozolene, and maleated polybutadiene. However, in the present defense, there are special characteristics in terms of compatibility with the above-mentioned upper emulsion.
Or semi-dry oil fat 1'! ! Modified ↑ acrylic covalent resins, vinyl-modified alkyd resins, or alkyd resins are particularly recommended.

Aqueous solutions or dispersions of drying oil fatty acids and/or semi-drying oil fatty acid-modified acrylic copolymers are known per se and can be produced, for example, as follows.

That is, (1) first, the drying oil fatty acid J3 and 7/or semi-drying oil fatty acid is reacted with the glycidyl ester or aziridinyl alkyl ester of α,β-ethylenically unsaturated f41 M'U to form the drying oil fatty acid and /Or make a semi-drying oil fatty acid modified monomer. Next, this modified monomer and α, β
- Saturated acid for ethylenic inertness, other Jj - heavy content 1!1
A fn (* is synthesized by a known solution polymerization method. It is particularly preferable that the solvent be one that can be used as it is when preparing an aqueous coating composition, but of course any other solvent can also be used. .

In this case, it is desirable to reduce the amount of organic solvent by removing the solvent by FC under reduced pressure. An example of a preferred solvent is methyl cellosolve, ]]
Nityl lorosolve butyl cellosolve, ethylene glycol-
There are various types of carbitol, methyl carbitol, ethyl carbitol, butylcarpitol glycol, etc. The copolymerization reaction is usually carried out using 2 to 60 tons of fatty acid-modified single φ body, α,β-1 dilenically unsaturated acid/
Preferred monomer proportions are 4-40, 5-10, and 91-50, respectively, although 1 to 20 doublet parts and 94 to 20 doublet parts of other co-incompatible monomers are used. This is a heavy lifting section. A copolymer having an acid filfi of 20 to 350, preferably 50 to 150 is thus obtained, which is then neutralized in a conventional manner using, for example, an amine, ammonia or an alkali metal hydroxide to make the resin water-soluble or It performs water dispersion.

The above resin can also be obtained by (2) first producing a fat RTQ-modified monomer, then synthesizing this and other oxidants using a known polymerization method, and finally adding 17-leic acid or anhydride. Reacting maleic acid81. ! It is also possible to make it by doing things. However, when using maleic anhydride, it is necessary to open the ring of the acid anhydride later with water, alcohol, ammonia, amine, etc., and then the resin is water-solubilized or water-dispersed.

(3) The aqueous solution or aqueous dispersion of the vinyl-modified alkyd resin can be produced by first using a drying oil, semi-drying oil,
After synthesizing an alkyd resin containing a drying oil fatty acid or a semi-drying oil fatty acid and diluting it with a solvent if desired, α, Add a mixture of β-edylene saturated acid and other copolymerizable monomers (-polymerize,
The saturated acid for the α,β-ethylenically unsaturated resin is adjusted so that the acid value of the resin is 30 to 200, preferably 40 to 150. Finally, it may be water-solubilized or water-dispersed by neutralization using a conventional method. Furthermore, the small fraction of drying oil, semi-drying oil, drying oil fatty acid, or semi-drying oil fatty acid in the solid content is 2 to 40.
% is preferably 5 to 30%, and if this amount is small, it will be difficult to paint.
The acid-1 polymerization of the composition after step i will not proceed, and if the amount is too large, the curing will be too rapid and the coating will shrink, both of which are undesirable.

Although it is not necessarily an essential requirement in the present invention, the solid content ratio of the oxidation polymerization type polymer emulsion and the oxidation polymerization type resin is 95:5 to 5/95, most preferably 90/10 to 5/95.
It is best to use a ratio of 20/80. This is because if there is too much emulsion, the gloss will be low, and if there is too little emulsion, the drying properties will be poor and it will easily sag.

In the aqueous coating composition of the present invention, both the emulsion resin and the resin dissolved or dispersed in water have oxidative polymerization type C, and their compatibility is extremely good. It creates a film and provides a three-dimensional, strong/υ coating film through oxidative polymerization. Although the oxidative polymerization proceeds even when left at room temperature, it is further accelerated by the addition of ordinary metal dry V-. Thus, gloss, water resistance, solvent resistance, mulberry resistance, corrosion resistance, hardness, etc. are 1, dry f1
, a coating composition with excellent adhesion to metals has been developed, and combined with the fact that it is water-based, it is possible to provide a coating composition that is extremely useful in the coating N'1 field and has a wide range of applications. It's 1c.

The present invention will be explained below with reference to Synthesis Examples and Examples. In the example sentence, 1 part 1 means "1 part 1".

Synthesis example 1 (air-drying monomer with double bond No, 1
Synthesis) 237 parts of castor oil fatty acid, 130 parts of aziridinylethyl methacrylate, and 14 parts of hydroxylone were placed in a reaction vessel, and a reaction was carried out at a temperature of 110 to 120°C with stirring. The addition reaction between aziridinyl group and carboxyl group is
The amount of remaining carboxyl groups was tracked while being measured. The reaction took approximately 3 hours to complete.

Synthesis Example 2 (Synthesis of monomer No. 2 with air-drying double bond) Safflower song 350 parts trimethylolpropane 109 parts dizodyltin A oxide
One part was placed in 1 liter of alcohol and heated to 200° C. with stirring to carry out a transesterification reaction.

The reaction was monitored with methanol] and took approximately 1 hour to complete. After cooling this to 120°C, 118 parts of phthalic anhydride was added and the reaction was stirred at 150°C. The reaction was followed by infrared spectroscopy, and observed by the decrease in the absorption spectrum of the acid anhydride. It took about 1 hour to complete the reaction.

Synthesis Example 3 (Aqueous emulsion of oxidative polymerization type copolymer N0
Synthesis of 01) Into 1 to 1 to 100 ml of a stirrer, a cold 1.11 vessel, a temperature control device, and 39 nitrogen tubes, 60 parts of deionized water, 1 to 1 lauryl sulfate, and lithium (manufactured by Kao Soap Co., Ltd.; Emar O
) and 14 parts of polyoxyethylene nonyl phenyl ether (manufactured by Kao Soap Co., Ltd.: Emulgun 935) were added, and the temperature was brought to 80° C. with stirring. Prepared separately, 1.4 parts of potassium persulfate was dissolved in 60 parts of deionized water, and 20 parts of it was added to 1 liter Herkolben.
After 0 minutes, the FP polymer compound obtained in Synthesis Example 1 52.5
Part Z A mixture of 56 parts of styrene, 128 parts of methyl methacrylate, 109 parts of 1)-pudyl acrylic acid, and 4.5 parts of acrylic acid was added dropwise over a period of 3 hours. The reaction was carried out while maintaining the temperature at 80'C under nitrogen flow. The remaining potassium cum persulfate was added dropwise at the same time as the monomer mixture so that the addition was completed in 3 hours and 30 minutes. After dropping the monomer mixture F, the liquid temperature is increased to 8
The temperature was maintained at 0°C for 2 hours, and the temperature was set to ik 7. By this method, an emulsion with a nonvolatile content of 43.5% and a viscosity of 350 cp was obtained. The number average molecular weight of the resin is approximately 150.000
Met.

Synthesis Example 4 (Aqueous emulsion of oxidative polymerization type copolymer N0
Synthesis of Synthesis Example 92) An oxidative polymerization type emulsion was obtained in the same manner as in Synthesis Example 3, except that the monomer obtained in Synthesis Example 2 was used instead of the monomer obtained in Synthesis Example 1. This emulsion has a nonvolatile content of 45.4%.
, a viscosity of 350 cp, and a number average molecular weight of 120,000.

Synthesis Example 5] (Synthesis of aqueous L-mulsion N013 of oxidative polymerization type copolymer) A stirrer, a cold filter, a temperature control device, and a nitrogen inlet tube (diluted 1 liter, 1 liter: 1 lupen) were prepared. 2 ion water 4.0
0 parts, 3 parts of the dosage compound of Synthesis Example 1, methoxypolyethylene glycol monomethacrylate-1.H3 (CHz-CCOO(CI-12Cl-120> z
3 Cl-13NK Nisdel M 23G manufactured by Shinnakaiki Chemical Co., Ltd. (5 parts, 15 parts of styrene, 1 part of ethyl methacrylate)
8 parts of 2-I derhexyl acrylate, 1.2 parts of acrylic acid, and 0.6 parts of ammonium perlfate were added, and the temperature was raised to 80°C under a nitrogen stream. After raising the temperature, a solution prepared by dissolving 9 parts of anhydrous persulfate in 50 parts of deionized water, and 12 parts of the ii tfI compound of IC Synthesis Example 1, meth-hexyl, and polyethylene glycol were added. 24 parts to monomethacrylate 1, 60 parts styrene, 72 parts ethyl methacrylate, 6 parts acrylic 1S92-ethylhexyl,
A mixture of 2 parts of acrylic acid and 4.8 parts of acrylic acid was separately added dropwise over 3 hours. The reaction temperature was kept at 80°C. After the dropwise addition was completed, the reaction was completed by maintaining the temperature at 80° for another 2 hours. By this method, the non-volatile content was 39.5% and the viscosity was 150 cp.
-I got a Marchon. , the number average molecular weight of the resin is approximately 140
,000 IC.

Synthesis Example 6 (Aqueous emulsion of oxidative polymerization type copolymer>NO
, lI synthesis) Equipped with a stirrer, cooler, temperature control device, and nitrogen introduction tube! (
1 liter of colchen, 400 parts of deionized water, Synthesis Example 1
3 parts of 0 homoisomer compound, ■Reminol JS-2 (manufactured by Sanyo Chemical Industries, Ltd.): CI□-〇〇OR C)l-C○QCH2C1-1=cHzS03 Na
R=C121-125 and Ct31-
18.8 parts including bynofl (7.5 parts of active ingredient), 15 parts of styrene, 18 parts of methacrylic NS Idel, 16.8 parts of 2-ethylhexyl acrylate, 1.2 parts of acrylic acid,
Add 0.6 part of ammonium persulfate and heat to 80% under nitrogen stream.
The temperature was raised to 0°C. After raising the temperature, a solution prepared by dissolving 19 parts of ammonium persulfate O in 50 parts of deionized water, 12 parts of the dose compound of Synthesis Example 1 prepared separately, 60 parts of styrene, 72 parts of ethyl methacrylate, and 67 parts of acrylic M2-J thylhexyl were added. A mixture of 2 parts of acrylic liquor and 4.8 parts of acrylic liquor was separately added dropwise over a period of 3 hours. The reaction temperature was kept at 80°C. After the completion of the dropwise addition, the B O'C1 was maintained for approximately 2 hours to complete the reaction.

By this method, a J-mulsion with a non-volatile light content of 37.2% and a viscosity of 140 Cρ was obtained. Number average molecular weight of resin [J approx. 150, (
,)00'? 'there were.

Synthesis Example 7 (Synthesis of oxidative polymerization type resin aqueous solution No. 1 - Manufacturing method <1)) Stirrer, cold 1. (1 vessel,) Equipped with a crystal control device and a nitrogen inlet tube to add 1 to 2 liters of rubene to 1 tirze [1 liter] 1
00 parts and heated to 120°C. Next, drip the mixture in the proportions shown below over a period of 3 hours.

The reaction was carried out under a nitrogen stream.

Intermediate of Synthesis Example 1 125 parts acrylic acid
38,5 parts methyl methacrylate
[-
Add 5 parts of butylperoxy 2-1 dihexyl (I) to the reaction solution and maintain the temperature for another 2 parts at 120'C to complete the reaction.After cooling to 80°C, dimethylethanolamine 23.8 After stirring for about 10 minutes, 730 parts of deionized water was added to Z) and the aqueous dispersion of fatty acid-modified acrylic copolymer was added to the mixture. The nonvolatile content of this aqueous dispersion is 36.9
%, resin solid content and acid value were 60.

Synthesis Example 8 Synthesis of oxidative polymerization type aqueous solution NO12 - Manufacturing method ('
;' ) ) Flax (sesame oil fatty acid 236 parts glycidyl methacrylate 131 parts high 1 ~ roquinone
0.4 parts of tetraethylammonium bromide, 0.2 parts of ethyl cellosolve, and 89 parts of the mixture were placed in a reaction vessel, stirred, and reacted at a temperature of 4K to 130-14.0°C. The f=J addition reaction between an epoxy group and a carboxyl group was followed from A1 by measuring fH of the remaining carboxyl group. It took approximately 4 hours for the reaction to complete. 120 of this thing
The IBJ solvent was heated under reduced pressure with stirring.

1. Pour xylene 300871 into a 3 liter kolben equipped with a bone stirrer, cooler and temperature control device and heat it to 120 liters.
It was set to ℃. Next, a mixture of the following proportions was added dropwise over a period of 3 hours. The reaction was carried out under a nitrogen stream.

Addition reaction product of L 300 parts 11-butyl methacrylate 200 parts azobisinfidyloni-15 parts
After adding ~5 parts to the reaction solution and maintaining the temperature at roughly 120'C, 160 parts of maleic anhydride was added and reacted at 220-230C for about 4 hours. After repulsion, the ring was opened with condensate from which the solvent and unreacted maleic anhydride were removed by distillation under reduced pressure, and 180 parts of butyl cellosolve was added. The mixture was further neutralized with heliodylamine (while stirring at 80° C.) and further added with aqueous solution to obtain a partially maleated aqueous solution of a fatty acid-modified acrylic copolymer having a non-volatile content of 33%.

Synthesis Example 9 (Synthesis of oxidative polymerization type resin aqueous solution N0.3 - Manufacturing method (3)) 2 liters equipped with a stirrer, cold 1ill vessel, and temperature control device
- Le ■ 1 Luhen (150 parts of butyl cellosolve is added, the solid content of linseed oil modified alkyd resin with oil length of 60% is 12
0 parts was dissolved in this. Styrene 100 prepared separately
Part, Medyl methacrylate 260゜1) part, Acrylic M5
To a mixed solution of 1.4 parts of acrylic Wan-butyl and 87.7 parts of acrylic Wan-butyl were added 20 parts of C[-butyl peroxide] and lauryl mercaptan, and the -C1 reaction temperature was raised to 130"G.
It took a while to drip. After the dripping is complete, continue at the same temperature for 3F.
A vinyl-modified alkyd resin varnish was obtained.

This was cooled to 40'C, and the degree of neutralization was reduced to 1.1 times with 25% ammonia aqueous solution while stirring, and then l1fl ion water was gradually added to make a vinyl-modified alkyd resin with a non-volatile content of 36.5%. I made an aqueous solution.

Example 1 Face U 119 base 4 using SG mill with the following formulation
I made it. .

water 2
, 53 parts 25% ammonia water 08 parts Water-dispersible resin varnish of Synthesis Example 7 15.0 parts Ethylene glycol 1.0 part Titanium oxide
20.0 parts silicone oil
0.1 part (SI-1-193 manufactured by i-Heele Silicone)
To 39.43 parts of this pigment paste h was added 60.17 parts of 1 malsion obtained in Synthesis Example 3C', 1.5 parts of butyl cellosolve, and 1 part of water while stirring in a Lab Star Sea, and stirring was continued for about 10 minutes. and made paint. The performance of this paint is shown in Table 1.

Example 4 A coating composition was obtained in the same manner as in Example 1, except that 57.65 parts of the 1q emulsion in Synthesis Example 4 was used instead of the emulsion in Synthesis Example 3. The performance of this product is shown in Table '1.

Example 3 h) In the same manner as in Monthly Example 1, 66.26 parts of the emulsion of Synthesis Example 5 was used instead of the 2-flusion of Synthesis Example 3; A product was obtained.The performance of this product is shown in Table 1.

Example PA4 1 q of paint A11 was prepared in the same manner as in Example 1, except that 70.36 parts of the emulsion obtained in Synthesis Example 6 was used instead of the emulsion in Synthesis Example 3. The performance of this product is shown in Table 1.

Example 5 Pigment dispersion paste i~ was prepared using an SG mill with the following formulation.

water 2
, 36 parts 25% ammonia water 0.8 parts Water-dispersible resin varnish of Synthesis Example 9 15.2 parts Ethylene glycol 1.0 part Titanium oxide
20.0 parts Sirinin Ail
0.1 part (1--Resilicon Co., Ltd. JSH-193) 1-39.4 parts of this face 11 dispersion paste was mixed with 60.1 parts of the emulsion obtained in Synthesis Example 3 while stirring with a lab star and a lar.
Add 7 parts, 1.5 parts of butyl rerosolve and 1 part of water to make approx.
Stirring was continued for 0 minutes to form an aqueous coating composition. The performance of this product is shown in Table 1.

Example 6 In the same manner as in Example 5, 1 [! Emulsion obtained in Synthesis Example 4 instead of emulsion obtained in Synthesis Example 3 57.65
Aqueous coating compositions were prepared using the following.

The performance of this system is shown in Table 1.

Example 7 A pigment dispersion base l- was prepared in the same manner as in Example 1 except that 16.8 parts of the partially maleated aqueous solution obtained in Synthesis Example 8 was used instead of the water-dispersible resin varnish of Synthesis Example 7. While stirring 1-41.2 parts of this pigment paste with a lab stirrer, add 60.17 parts of the 1-mulsion obtained in Synthesis Example 3, 1.5 parts of butyl cellosolve, and 1 part of water, and continue stirring for about 10 minutes. A coating composition was prepared whose performance is shown in Table 1.

J5, for comparison purposes, the color 1'1 below is 1'1.

Comparative Example 1 While stirring Face 11 Dispersion Base 1-39.43 parts prepared in Example 1 with a lab stirrer, Acrycera 1-236
A paint was prepared by adding 52.3 parts of F (styrene-acrylic emulsion manufactured by Ell De Arrow Chemical Co., Ltd.), 1.5 parts of butyl cellosolve, and 1 part of water, and stirring continuously for about 10 minutes. It is shown in Table 1.

Comparative Example 2 While stirring 39.4 parts of the pigment dispersion paste prepared in Example 5 using a Lab Stirrer-C11, 52.5 parts of Acryset 236E was added. 3 parts of butyl, 1 part of Rosolve and 1 part of water were added and stirred for about 10 minutes to make paint C. The performance of this paint is shown in Table 1.

Apply the L-registered paint using a conventional method and check its performance.
The results listed in the table were obtained.

(Note 1) Abnormalities occurring in the coating film were observed after immersion in 40°C warm water for 2 weeks.

No Tatsumi ◎There are some small blister ○The blister is moderate or glossy
'T-I have △Many blisters
× (Note 2) Abnormal state of rust after spraying 5% salt water at 40°C for 120 hours ◎ Slight spots occur ○ Moderate rust
△ Excessive rust, peeling of the paint film × Note 3) Using a Mitsubishi Uni Pencil with a hardness code of 6B-91-1,
Hardness code one step below the hardness produced by scratching and kissing the paint film (Note 4) Wet a cloth with xylene and rub the paint film with your fingertips. Number of times of rubbing when the paint film begins to melt (Note 5) Ad After drying for 3 hours at 20°C and relative humidity of 75% using a Hydration Tester (manufactured by Elcometer), place one drop of water on one side of the paint film and the paint film will repel water. I saw it.

Water repellent and no abnormalities ○ A little cloudy △ Cloudy × -583-

Claims (9)

[Claims] (1) (△) Drying oil fatty acid and/or semi-drying oil fatty acid and α
, β-ethylenically unsaturated acid aziridinyl alkyl ester reaction product, and (B) the reaction product of drying oil and/or semi-drying oil with polyhydric alcohol, α, β, β-ethylene saturated dicarboxylic acid or An α, β-ethylenically unsaturated monomer copolymerizable with 2 to 60 parts (the same applies below parts by weight) of an air-drying double bond-containing monomer selected from unsaturated polyester compounds obtained by reacting the anhydride. The special feature is that it contains an aqueous emulsion of an oxidation-polymerizable copolymer obtained by emulsion polymerization of 98 to 40 parts, and an aqueous solution or dispersion of an oxidation-polymerization resin! l:
An aqueous coating composition. τ
Formula, 1 is also CHz=CCO(RzO)n R3(I)1 (in the formula, R1 is hydrogen, lower alkyl, H1) or phenyl group, R2 is ethylene or propylene group, R
Emulsion polymerization is carried out in the absence of a surfactant and/or a polymeric protective colloid using a nonionic polymerizable single compound represented by 3 is hydrogen or a lower alkyl group, and n is a positive number from 4 to 25. The composition according to claim 1, which is an emulsion obtained by. (3) The composition according to claim 2, wherein the compound represented by the general formula (I) occupies 2 to 20 parts of the copolymerizable α,β-edylenically unsaturated monomer. (4) The aqueous emulsion of the oxidation-polymerizable copolymer contains α,β-ethylenically unsaturated and sulfonic acid or sulfonate groups as part of the copolymerizable α,β-ethylenically unsaturated monomer. The surfactant and imma Iζ are 1''''lugin obtained by carrying out emulsion polymerization using an anionic polymerizable monomer compound in the absence of a polymeric protective colloid. Composition according to item 1. (5) An anionic polymerizable monomer compound, or a compound represented by any of the above (1) 0OR2 or 2 (wherein R1 is hydrogen or a methyl group; R2 is a saturated or (,
l, unsaturated hydrocarbon or substituted hydrocarbon group, or organic group containing oxyalkylene group; A is alkylene or substituted alkylene group having 2 to 4 carbon atoms; M is hydrogen, alkali metal, alkaline earth metal, ammonium or organic amine; valence or ionic valence in ml, tM; n is O or a positive number; Δ' is carbon @1 to . 5. The composition according to claim 4, wherein the composition is a saturated or unsaturated hydrocarbon group of 20 or 20 (g (hydrocarbon group; B is a saturated hydrocarbon group having 1 to 6 carbon atoms). (6) Claim 4 or 5, wherein the anionic polymerizable monomer compound accounts for 0.5 to 10 parts of the copolymerizable α,β-unsaturated monomer. Composition. (7) The composition according to any one of claims 1 to 6, wherein the oxidatively polymerized resin is a drying oil fatty acid and/or a semi-drying oil fatty acid modified acrylic covalent polymer. (8) The composition according to any one of claims 1 to 6, wherein the oxidative polymerizable resin is a vinyl-modified alkyd resin. (9) The composition according to any one of claims 1 to 6, wherein the oxidatively polymerized resin is a medium oil or long oil alkyd resin.