JPS5911376A - Water-based coating composition - Google Patents

Abstract

PURPOSE:To provide the titled composition consisting of an emulsion of an oxidation-polymerization polymer and an aqueous solution (or an aqueous dispersion) of an oxidation-polymerization resin, which has an excellent quick drying property and forms a coating film with high luster and good physical properties. CONSTITUTION:An emulsion of an oxidation-polymerization polymer is prepared by emulsion polymerization of (a) 2-60pts.wt. fatty acid-modified monomer obtained by interaction of drying oil fatty acid (and/or semi-drying oil fatty acid), alpha, beta-ethylenically unsaturated acid and glycidyl ester and (b) 98-40pts.wt. copolymerizable monomer other than above (e.g. acrylic acid) in the presence of surfactant, etc. The above emulsion (A) is mixed with (B) an aqueous solution (or aqueous dispersion) of an oxidation polymerization resin, such as drying oil fatty acid-modified acrylic copolymer, or vinyl-modified alkyd resin, in the blend ratio of about 95:5-5:95 by solid.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aqueous coating composition, and more particularly to an aqueous coating composition comprising an oxidatively polymerizable polymer emulsion and an aqueous solution or dispersion of an oxidatively polymerizable resin, which has excellent drying properties and is glossy. The present invention also relates to an aqueous coating composition with good coating film properties.

Aqueous coating compositions using a polymer emulsion obtained by emulsion polymerization as a color vehicle generally have excellent drying properties, water resistance, alkali resistance, etc., but there are problems with water resistance and solvent resistance in the early stage of drying. It is 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 proposed: a technique of blending an aqueous solution or dispersion of a fatty acid-modified acrylic resin into an emulsion polymer emulsion. Ta.

(Japanese Patent Application Laid-Open Nos. 51-80334 and 50-126724). The fatty acid-modified acrylic resin is disclosed in, for example, JP-A-51-8
Fatty acid modification obtained by reacting an unsaturated fatty acid (drying oil fatty acid or semi-drying oil fatty acid) having a non-conjugated double bond with glycidyl ester of α, β-ethylenically unsaturated acid as described in No. 0334. It is a copolymer of a monomer and a copolymerizable monomer, and its aqueous solution is compatible with emulsions, and by blending with emulsions, it does not lose the advantages of emulsions, but rather improves them, and also has glossiness, It is said to significantly improve weather resistance.

However, it has been found that even with such improvements proposed in the past, the physical properties of the coating film are still insufficient, particularly in terms of water resistance, corrosion resistance, solvent resistance, chemical resistance, hardness, and the like. According to the research of 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 ink coating, fuses and forms a three-dimensional structure only by fusing. It was concluded that this is due to the fact that there is a limit to the physical properties of the coating film because the emulsion does not have to be removed, and that if both the emulsion and the emulsion could be made three-dimensional, the physical properties of the coating film could be significantly improved. The present invention has been made from this viewpoint.

According to the present invention, (A) fatty acid-modified monomers 2 to 60 obtained by reacting drying oil fatty acids and/or semi-drying oil fatty acids with glycidyl esters of α,β-ethylenically unsaturated acids;
part by weight and 40 to 98 parts by weight of another copolymerizable monomer, and an aqueous solution or dispersion of (B) an oxidative polymerizable resin. A coating composition is provided.

The oxidative polymerization type polymer emulsion used in the present invention is disclosed in a patent application filed on July 5, 1982 by the present inventors (No.
) and (2), that is, fatty acid-modified monomers 2 to 60 obtained by reacting drying oil fatty acids and/or semi-drying oil fatty acids with glycidyl esters of α,β-ethylenically unsaturated acids. parts by weight and 98 to 40 parts by weight of other copolymerizable monomers are emulsion polymerized in the presence of a surfactant and/or a polymer protective colloid, or alternatively, the other copolymerizable monomers are emulsion-polymerized. as part of the formula % formula %) (wherein R1 is hydrogen, lower alkyl or halogen; R2
An emulsion obtained by emulsion polymerization using 2 to 20 parts by weight of a compound represented by hydrogen or lower alkyl; n is an integer of 4 to 25 in the absence of a surfactant and/or a polymeric protective colloid. be. Examples of drying oil fatty acids or semi-drying oil fatty acids include tung oil, dehydrated castor oil, linseed oil, safflower oil, soybean oil, sesame oil,
Fatty acids such as poppy oil, tall oil, rice bran oil, corn oil, and sunflower oil; glycidyl esters of α,β-ethylenically unsaturated acids include glycidyl acrylate and glycidyl methacrylate; and other copolymerizable monomers. Acrylic acid, methacrylic acid and their hydroxyalkyl esters and alkyl esters; unsaturated amide compounds such as acrylamide and methacrylamide; styrenic monomers such as styrene, vinyltoluene and α-methylstyrene; acrylonitrile and methacrylonitrile. Unsaturated nitrile such as; vinyl acetate etc. are used.

This emulsion has drying oil fatty acid and/or semi-drying oil fatty acid 4-acid moieties involved in oxidative polymerization incorporated into the polymer molecule, so it is naturally oxidized after painting.
Alternatively, it has the property of being three-dimensionally cross-linked and cured under the oxidation promoting action of a metal dryer, which is preferably added, to form a tough coating film.

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 isoprene, and maleated polybutadiene, and any resin can be used as long as it is appropriately water-solubilized and has some degree of compatibility with the above emulsion. It can be. However, in the present invention, drying oil fatty acids and/or oils having particularly good compatibility with the emulsion are used.
Alternatively, semi-drying oil-fatty acid-modified acrylic copolymers or vinyl-modified 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, first, drying oil fatty acids and/or semi-drying oil fatty acids are reacted with glycidyl esters of α,β-ethylenically unsaturated acids to produce drying oil fatty acids and/or semi-drying oil fatty acid modified monomers. Next, this strange sewing ll4s barre ~ ρ
Other copolymerizable monomers are synthesized by a known solution polymerization method.As a solvent, it can be used as is when preparing an aqueous coating composition. Of course, any other solvent can also be used.

Examples of preferred solvents are methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethylene glycol, methyl carpitol butyl carpitol, diethylene glycol and the like.

The copolymerization reaction is usually carried out using 2 to 60 parts by weight of a fatty acid modified monomer, α
, β-ethylenically unsaturated acid and 94 to 20 parts by weight of other copolymerizable monomers. Preferred proportions of the monomers are 4 to 40, 5 to 10, respectively. and 91 to 50 parts by weight. Thus, the acid value is 20-35
A copolymer having a molecular weight of 0, preferably 50 to 150 is obtained, and the resin is made water-solubilized or water-dispersed by neutralizing the carboxyl in a conventional manner using, for example, an amine, ammonia or an alkali metal hydroxide.

1.Resin 1 can also be prepared by first preparing a fatty acid-modified monomer, then synthesizing this with other copolymerizable monomers using a known polymerization method, and finally reacting with maleic acid or maleic anhydride. It can also be made by

However, when maleic anhydride is used, 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.

To produce an aqueous solution or dispersion of a vinyl-modified alkyd resin, first, an alkyd resin containing a drying oil fatty acid or a semi-drying oil fatty acid is synthesized by a known method, diluted with a solvent if desired, and then diluted with stirring, for example. Using a hydrogen-absorbing polymerization initiator such as -t-butyl peroxide, a mixture of α,β-ethylenically unsaturated acid and other copolymerizable monomers is added to carry out graft polymerization, and the α,β-ethylene The amount of unsaturated acid is adjusted so that the acid value of the resin is 30-200, preferably 40-150. Finally, it may be water-solubilized or water-dispersed by neutralization using a conventional method.

The weight fraction of the total solids semi-drying oil fatty acid and/or semi-drying oil fatty acid is 2 to 40%, preferably 5 to 30%; if this amount is small, oxidative polymerization of the composition after application will not proceed; On the other hand, if the amount is too large, the curing will be too fast and shrinkage of the coating will occur, which is 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 95.
Preferably, it is used in a ratio of 20/80°.

This is because if there is too much emulsion, the gloss will be low, and if it is too little, the drying properties will be poor and the emulsion will tend to sag.

In the aqueous coating composition of the present invention, both the emulsion resin and the resin dissolved or dispersed in water are of the oxidative polymerization type, and their compatibility is extremely good, so that after application, they work together to form a naturally oxidizing coating film. It produces a three-dimensional, tough coating film through oxidative polymerization. Although the oxidative polymerization proceeds even when left at room temperature, it is further accelerated by the addition of an ordinary metal dryer. Thus, gloss, water resistance, solvent resistance,
A coating composition with excellent chemical resistance, corrosion resistance, hardness, etc., excellent drying properties and adhesion to metals can be obtained, and the fact that it is water-based makes it extremely useful in the paint field and has a wide range of applications. It became possible to provide goods.

The present invention will be explained below with reference to Examples.

In the example sentence, "1 part" means "parts by weight."

Example 1 1- (a) Linseed oil fatty acid 237 parts Glycidyl methacrylate 119 parts -8 = Hydroquinone 0.4 parts Tetraethylammonium bromide 0.2 parts were placed in a reaction vessel and heated at a temperature of 170 to 180°C with stirring. The reaction was carried out. The addition reaction between epoxy groups and carboxyl groups was monitored while measuring the amount of remaining carboxyl groups. The reaction took approximately 3 hours to complete.

1-(b) I equipped with a stirrer, cooler, temperature control device and nitrogen inlet pipe
In Q Kolben, 370 parts of deionized water, 4 or 2 parts of sodium lauryl sulfate (manufactured by Kao Soap Co., Ltd.: Emar 0), and polyoxyethylene nonylphenyl ether (manufactured by Kao Soap Co., Ltd.).
Add 14 parts of Emulgen 935) and reduce the temperature to 8.
The temperature was raised to 0°C, and 20 parts of a solution of 1.4 parts of potassium persulfate prepared separately dissolved in 60 parts of deionized water was charged into an IQ Kolben, and after about 10 minutes, the addition reaction product of 1-(a) was added. A mixture of 52.5 parts of styrene, 56 parts of styrene, 128 parts of methyl methacrylate, 109 parts of n-butyl acrylate, 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 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 the dropwise addition of the monomer mixture was completed, the liquid temperature was maintained at 80° C. and the addition was completed after 2 hours had passed. By this method, an emulsion with a nonvolatile content of 44.8%, a viscosity of 400 cp, and a number average molecular weight of about 150,000 was obtained.

1- (c) 2 equipped with a stirrer, cooler, temperature control device and nitrogen inlet tube
100 parts of ethyl cellosolve was placed in a Q-Kolben and heated to 120°C. Next, a mixture in the proportions shown below was added dropwise over a period of 3 hours. The reaction was carried out under a nitrogen stream.

1- Adduct of (a) 125 parts acrylic acid 38.5 parts methyl methacrylate 140 parts styrene
50 parts n-butyl acrylate 146.5
parts azobisisobutyronitrile 20 parts 11 parts
- One hour after the completion of the dropwise addition, 5 parts of t-butylperoxy 2-ethylhexanate was added to the reaction solution, and the mixture was stirred for an additional 2 hours.
The reaction was completed by keeping the temperature at 20°C. After cooling to 80°C, 23.8 parts of dimethylethanolamine was added, and after stirring for about 10 minutes, 730 parts of deionized water was gradually added to obtain an aqueous dispersion of a fatty acid-modified acrylic copolymer. The nonvolatile content of this aqueous dispersion was 36.9%, and the resin solid content acid value was about 60.

1-(d) A pigment dispersion paste was made using an SG mill with the following formulation.

Wednesday 2.53
part 25% ammonia water 0.8 part 1- (
c) Water-dispersible resin varnish 15.0 parts ethylene glycol 1.0 part titanium oxide
20.0 parts silicone oil 0
．． 1 part (5H493 manufactured by Toray Silicone Co., Ltd.) While stirring 39.43 parts of this pigment paste with a lab stirrer, 58.42 parts of the emulsion obtained in i-(b), 1.5 parts of butyl cellosolve, and 1 part of water were added to approx. The paint was prepared by continuing stirring for 10 minutes. The performance of this paint is the first
Shown in the table.

Example 2 In an IQ Nikolon equipped with a stirrer, condenser, and temperature control, 400 parts of deionized water, 1-(a) addition reactant 12
parts, polyethylene glycol monomethacrylate Bremmer PE-350 (manufactured by NOF Corporation) 3 parts, styrene 9.6 parts, methyl methacrylate 18 parts, acrylic acid n
-15 parts of butyl, 2.4 parts of acrylic acid, 0.3 parts of potassium persulfate, and 1.5 parts of sodium bisulfite were charged, and the temperature was raised to 60°C under a nitrogen stream. After raising the temperature, a solution prepared by dissolving 1.2 parts of potassium persulfate in 50 parts of deionized water, 48 parts of the addition reaction product of 1-(a) prepared separately, 12 parts of polyethylene glycol monomethacrylate, and 38.4 parts of styrene were added. , 72 parts of methyl methacrylate, 6 parts of n-butyl acrylate
0 parts of acrylic acid and 9.6 parts of acrylic acid were separately added dropwise over 2 hours and 30 minutes. The reaction temperature was kept at 60°C. After the dropwise addition was completed, the temperature was maintained at 60° C. for another 2 hours. With this method, the non-volatile content is 39.4% and the viscosity is 200.
An emulsion of CP was obtained.

2-(d) A paint was prepared in the same manner as in Example 1 except for the following formulation. The performance of this paint is shown in Table 1.

Pigment dispersion paste of Example 1 39.43 parts 2- (b
) 66.4 parts butyl cellosolve
1.5 parts water
1 part Example 3 3- (a) Safflower oil fatty acid 236 parts Glycidyl methacrylate 131 parts Hydroquinone
0.4 parts Tetraethylammonium bromide 0.2 parts Ethyl cellosolve 8
9 parts were placed in a reaction vessel and the reaction was carried out at a temperature of 130 to 140°C with stirring. The addition reaction between epoxy groups and carboxyl groups was monitored while measuring the amount of remaining carboxyl groups. The reaction took approximately 4 hours to complete. This product was kept at 120° C. and the solvent was removed under reduced pressure while stirring.

3- (b) In an IQ Nikolon equipped with a stirrer, a cooler, and a temperature control device, 220 parts of deionized water, sulfur and lithium dodecylbenzenesulfonate (manufactured by Kao Soap Co., Ltd.: Neoperex No. 6)
1.0 parts of polyoxyethylene sorbitan monolaurate (Nidoween 20, manufactured by Kao Soap Co., Ltd.) and 2.7 parts of the mixture were added, and the temperature was raised to 50°C while stirring. Separately, 1.75 parts of ammonium persulfate was dissolved in 80 parts of deionized water, and 1.75 parts of sodium bisulfite was dissolved in 80 parts of deionized water.
A solution was prepared by dissolving the liquid in a portion. On the other hand, deionized water 140
Addition reaction product of 3-(a) was added to a solution of 2.5 parts of the above surfactant, ie, sulium dodecylbenzenesulfonate, and 10.6 parts of polyoxyethylene sorbitan monolaurate in 1 part of the mixture with stirring. 140 parts, 28 parts of styrene, 87.5 parts of ethyl methacrylate, 70 parts of 2-ethylhexyl methacrylate, and 21 parts of hydroxyethyl methacrylate.

Slowly add 3.5 parts of acrylic acid mixture to approx.
After a few minutes, a pre-emulsion of the reacted monomers was obtained. After confirming that the aqueous emulsifier solution in IQ and Kolben was at 50'C, the previously prepared aqueous solution of ammonium persulfate and aqueous solution of sodium bisulfite were separately added dropwise so as to complete the addition in 3 hours and 30 minutes. After about 15 minutes, the previously prepared pre-emulsion was added dropwise under a nitrogen stream over a period of 3 hours. After dropping the aqueous solution of the reaction initiator, the temperature was maintained at 60° C. for 1 hour to complete the reaction. By this method, the non-volatile content was 40.4
%, viscosity 200 cp, number average molecular weight 12 o, ooo emulsion was obtained.

3-(c) A 3Q colhenium equipped with a stirrer, a cooler, and a temperature control device was charged with 300 parts of xylene and heated to 120°C. Next, a mixture in the proportions shown below was added dropwise over a period of 3 hours.

The reaction was carried out under a nitrogen stream. Addition reaction product of 615-3- (a) 300 parts n-butyl methacrylate 200 parts azobisisobutyronitrile 15 parts One hour after completion of the dropwise addition, t-butyl peroxy 2- After adding 5 parts of ethylhexanate to the reaction solution and keeping it at 120°C, 310 parts of maleic anhydride was added to the reaction solution.
1 part and reacted at 220 to 230°C for about 4 hours. After the reaction, the solvent and unreacted maleic anhydride were removed by distillation under reduced pressure, water was removed, the ring was opened, and 180 parts of butyl cellosolve was added.

Furthermore, while keeping the temperature at 80℃, add 1 with triethylamine while stirring.
．． Neutralize 0 equivalents and add deionized water to reduce the non-volatile content to 33
% of a fatty acid-modified acrylic copolymer was obtained.

3-(d) A pigment dispersion paste was made using an SG mill with the following formulation.

3- (c) Water-soluble resin varnish 28.0 parts 25
%Ammonia water 0.9 parts Ethylene glycol 1.5 parts Titanium oxide
20.0 parts 16- 0.2 parts of gyricon oil (5H-193 manufactured by Toray Silicone Co., Ltd.) 50.6 parts of this pigment paste were stirred with a lab stirrer, and 3- 54.5 parts of the emulsion obtained in (b) and butyl cellosolve were added. 1 part and 1 part water were added, and stirring was continued for about 10 minutes to form a paint.

The performance of this paint is shown in Table 1.

Example 4 4- (a) Tall oil fatty acid 235 parts Glycidyl methacrylate 119 parts Hydroquinone
0.4 parts 0.2 parts of tetraethylammonium bromide was placed in a reaction vessel and heated to 140~ while stirring.
The reaction was carried out at a temperature of 150°C. The addition reaction between epoxy groups and carboxyl groups was monitored while measuring the amount of remaining carboxyl groups. The reaction took approximately 4.5 hours to complete.

4- (b) Put 100 parts of ethyl cellosolve into a reaction container and heat it to 1
The temperature was set to 20°C. Next, a mixture in the proportions shown below was added dropwise to this solution over a period of 2 hours. The reaction was carried out under a nitrogen stream.

4- Addition reaction product of (a) 60 parts n-butyl methacrylate 12 parts styrene
15 parts acrylic acid
13 parts azobisisobutyronitrile
One hour after the completion of the dropwise addition of 4 parts, 1 part of azobisisobutyronitrile was added to the reaction solution, and the temperature was maintained at 120'C for an additional 2 hours to complete the reaction. The solvent was removed under reduced pressure at 120° C. to obtain a tall oil fatty acid-modified acrylic polymer with a nonvolatile content of 96% and an acid value of 95.

4-(c) In an IQ Nikolon equipped with a stirrer, a cooler, and a temperature control device, add 78 parts of the tall oil fatty acid-modified acrylic polymer obtained in 4-(b), 10 parts of butyl cellosolve, and 40 parts of deionized water.
0 parts of dimethylethanolamine and 12 parts of dimethylethanolamine were added, stirred to completely dissolve the tall oil fatty acid-modified acrylic polymer in water, and the temperature was raised to 80°C. Next, azobisdiadovaleric acid 5
55 parts of deionized water and 4.0 parts of dimethylethanolamine.
7 parts. 80% of this was charged into a reaction vessel and after 1°, a mixture of 25 parts of the adduct of 4-(a), 107.5 parts of methyl methacrylate, 35 parts of styrene, and 82.5 parts of n-butyl acrylate was added for 2 hours. It dripped. After finishing the dropping, add the rest of the azobiscyanovaleric acid aqueous solution to 80 ml.
The reaction was completed by keeping at ℃ for 2 hours. The emulsion had a nonvolatile content of 40.2% and a viscosity of 1100CP.

4-(d) A paint was prepared in the same manner as in Example 1 except for the following formulation. The performance of this paint is shown in Table 1.

Pigment dispersion paste of Example 1 39.43 parts 4- (
Emulsion obtained in c) 62.3 parts butyl cellosolve 1.5 parts water
1 part Example 5 5- (a) Put 150 parts of butyl cellosolve into a 2Q colben equipped with a stirrer, a cooler, and a temperature control device, and add 120 parts of solid content of soybean oil-modified alkyd resin with an oil length of 60% to this. Dissolved. Separately prepared 100 parts of styrene, 260.9 parts of methyl methacrylate, 51.4 parts of acrylic acid, acrylic acid n
Di-t-butylperoxide and 20 parts of lauryl mercaptan were added to a mixed solution of 87.7 parts of -butyl, the reaction temperature was set to 130°C, and the mixture was added dropwise over 3 hours. After the dropwise addition was completed, the mixture was kept at the same temperature for an additional 3 hours to obtain a vinyl-modified alkyd resin varnish. After cooling this to 40° C. and adjusting the degree of neutralization to 1.1 equivalent with a 25% ammonia aqueous solution while stirring, deionized water was gradually added to prepare a vinyl-modified alkyd resin aqueous solution with a non-volatile content of 36.5%. .

5-(b) A pigment dispersion paste was made using a lab stirrer using glass peas with the following formulation.

water 2
．． 5 parts 25% ammonia water 0.8 parts 5
- Water-soluble resin varnish of (a) 32 parts 20 parts - Ethylene glycol 2 parts Titanium oxide 19.6 parts Silicone oil
0.1 part (5H manufactured by Toray Silicon Co., Ltd.
-193) Stir 57.0 parts of this pigment paste with a lab stirrer, then add 4 parts of the 45° emulsion obtained in 3-(b), 1 part of butyl cellosolve, and 1 part of water, and continue stirring for about 10 minutes to form a paint. I made it. The performance of this paint is shown in Table 1.

Comparative Example 1 While stirring 39.43 parts of the pigment dispersion paste prepared in Example 1 with a lab stirrer, 52.3 parts of Acryset 236E (manufactured by Eclipse Arrow Chemical Co., Ltd.: styrene-acrylic emulsion) and 1.5 parts of butyl cellosolve were added. One part of water was added and stirring continued for about 10 minutes to form a paint. The performance of this paint is shown in Table 1.

Comparative Example 2 While stirring 57.0 parts of the pigment dispersion paste prepared in Example 5 with a lab stirrer, 36% of Acryset 236E was added.
．． 7 parts of butyl cellosolve and 1 part of water were added and stirring was continued for about 10 minutes to prepare a paint. The performance of this paint is shown in Table 1.

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

No abnormality 0 Some small blister present 0 Moderate blister or lackluster Δ Lots of blister × (Note 2) 5%
No abnormal state of rust after spraying salt water at 40°C for 120 hours 0 Point Rust slightly O Rust is moderate △ Excessive rust, paint film peeling × (Note 3) Mitsubishi with 6B to 9H hardness code Using Uni Pencil,
Hardness code one step below the hardness at which scratches occur when the paint film is scratched (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) Using an adhesion tester (manufactured by Elcometer) (Note 6) After drying for 3 hours at 20°C and a relative humidity of 75%, rub the paint onto the paint film. A drop of water was added and the paint film repelled water.

Water repellent and no abnormalities O Slightly cloudy
Δ becomes cloudy
X Procedural Amendment Letter February 16, 1983 3. Relationship with the person making the amendment Name of patent applicant No. 2 = lEi' Kure Paint Co., Ltd. Representative Masao Suzuki 4, Agent address: 3 Kyobashi, Higashi-ku, Osaka-shi, Osaka Prefecture No. 57-6, subject of amendment Item 7 of [Claims] and “Detailed Description of the Invention” of the specification, Contents of amendment As shown in Attachment 1, the scope of claims of the specification is corrected as follows. .

In(1) (A) 2 to 60 parts by weight of a fatty acid-modified monomer obtained by reacting a drying oil fatty acid and/or a semi-drying oil fatty acid with a glycidyl ester of an α,β-ethylenically unsaturated acid, and other An aqueous coating characterized by containing an oxidatively polymerizable polymer emulsion obtained by emulsion polymerization with 40 to 98 parts by weight of a copolymerizable monomer, and (B) an aqueous solution or aqueous dispersion of an oxidatively polymerizable resin. Composition for use.

(2) Claim 1, wherein the oxidative polymerization type polymer emulsion (A) is obtained by emulsion polymerization of the monomer in the presence of a surfactant and/or a polymeric protective colloid. Compositions as described.

(3) The oxidation-polymerizable polymer emulsion of (A) contains the formula (wherein 81 is hydrogen, lower alkyl, halogen or phenyl group; R2 is ethylene or propylene group) as part of other copolymerizable monomers; R3 is hydrogen or a lower alkyl group; n is an integer of 4 to 25) obtained by emulsion polymerization of the monomer in the absence of a surfactant and/or a polymeric protective colloid. A composition according to claim 1, which is a composition.

(4) The composition according to claim 3, wherein the compound represented by the formula accounts for 2 to 20 parts by weight of the other copolymerizable monomers.

(5) The oxidation-polymerizable polymer emulsion of (A) contains anionic monomers having α, β-ethylenically unsaturated groups and sulfonic acid or sulfonate groups as part of other copolymerizable monomers. 2. The composition according to claim 1, which is obtained by emulsion polymerization of the monomer in the absence of a surfactant and/or a polymeric protective colloid.

(6) A patent claim in which the anionic monomer having an α,β-ethylenically unsaturated group and a sulfonic acid or sulfonate group accounts for 0.5 to IO parts by weight of the other copolymerizable monomers. A composition according to scope item 5.

(7) Claim 5 or Composition according to item 6.

2 (wherein 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 group having 2 to 4 carbon atoms or a substituted alkylene group; M is Hydrogen, alkali metal, alkaline earth metal, ammonium or organic amine; m is the valence or ionic valence of M; n is 0 or a positive number; A'
is a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms or a substituted hydrogen group; B is a saturated hydrocarbon group having 1 to 6 carbon atoms)
8) The oxidative polymerization type resin of (B) is a drying oil fatty acid and/or
The composition according to any one of claims 1 to 7, which is a semi-drying oil-fatty acid modified acrylic copolymer.

(9) The composition according to any one of claims 1 to 7, wherein the oxidatively polymerized resin (B) is a vinyl-modified alkyd resin. J2. Delete the entire text from line 1 to line 7 on page 5 of the specification and insert the following.

[j CH2=C-Coo(R20)n R
31 (wherein R1 is hydrogen, lower alkyl, halogen or phenyl group; R2 is ethylene or propylene group; R3 is hydrogen or lower alkyl group; n is an integer from 4 to 25) (Japanese Patent Publication No. 55-41684) Reference) 2 to 20
Parts by weight may be used, or an anionic monomer having an α,β-ethylenically unsaturated group and a sulfonic acid or sulfonate group, such as a compound 2 represented by any of the following formulas (wherein R1 is hydrogen or 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 group having 2 to 4 carbon atoms or a substituted alkylene group; M is hydrogen, an alkali metal, or an alkaline earth metal , ammonium or organic amine; m is the valence or ionic valence of M; n is 0 or a positive number; A'
is a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms or a substituted hydrocarbon group; B is a saturated hydrocarbon group having 1 to 6 carbon atoms)
Special Publication No. 49-46291, U.S. Patent No. 4,049.60
(see No. 8) is an emulsion obtained by emulsion polymerization using 0.5 to 10 parts by weight. All of the above compounds are polymerizable monomers that themselves have an emulsifier function, so as long as they are used in the above-mentioned preferred amounts during emulsion polymerization, no other surfactants or polymeric protective colloids are required, and these are preferred. However, if desired, a conventional surfactant and/or a polymeric protective colloid may be used in combination (in a smaller amount than the usual amount). J3, 2nd
Insert the following between page 2, line 9 and line 1O.

“Example 6 1 equipped with a stirrer, cooler, temperature control device, and nitrogen inlet pipe”
In a small bottle, add 400 parts of deionized water, 1-(a
), 12 parts of Eleminol JS-2 (manufactured by Sanyo Chemical Industries, Ltd., a mixture of R=C12H2s and Cl3H27), 22.5 parts (9 parts of effective 5-component), 9.6 parts of styrene, methyl methacrylate. 1
8 parts, n-butyl acrylate 15 parts, methacrylic acid 2.
4 parts of potassium persulfate, 0.3 parts of potassium persulfate, and 1.5 parts of sodium bisulfite were added, and the temperature was raised to 60°C under a nitrogen stream. After raising the temperature, a solution prepared by dissolving 1.2 parts of potassium persulfate in 50 parts of deionized water and a separately prepared addition reaction product 48 of 1-(a) were added.
parts, 38.4 parts of styrene, 72 parts of methyl methacrylate,
A mixture of 60 parts of n-butyl acrylate and 6.2 parts of methacrylic acid was separately added dropwise over 2 hours and 30 minutes.

The reaction temperature was kept at 60°C. After the completion of dripping, another 2 hours6
The temperature was maintained at 0°C and the process was completed. With this method, the non-volatile content is 38.3%,
An emulsion with a viscosity of 100 cp was obtained.

A pigment dispersion paste was made using an SG mill with the following formulation.

water 2.5
3 parts 25% ammonia water 0.8 parts 1-
(c) Water-dispersible resin varnish 15.0 parts Ethylene glycol 1.0 parts Titanium oxide
20.0 parts silicone oil
While stirring 39.43 parts of this pigment paste with a lab stirrer, add 67.6 parts of the emulsion obtained in 6-(b), 1.5 parts of butyl cellosolve, and 1 part of water. A paint was prepared by adding 50% of the mixture and stirring continuously for about 10 minutes.

The performance of this paint is shown in Table 1. J 4, page 24, Table 1, the following data of Example 6 is inserted between Example 5 and Comparative Example 1.

"Example 6 5 50〈 3Kg 12' 0　　　　　　　” 5, Table 1, page 24, Example 1, pencil hardness item 18= It says "IF", “I corrected it as “FIt”.

that's all −9=

Claims (6)

[Claims] (1) (A) Fatty acid modified monomers 2 to 60 obtained by reacting drying oil fatty acids and/or semi-drying oil fatty acids with glycidyl esters of α, β-ethylenically unsaturated acids.
and (B) an aqueous solution or dispersion of an oxidative polymerizable resin. An aqueous coating composition characterized by: (2) Claim 1, wherein the oxidative polymerization type polymer emulsion (A) is obtained by emulsion polymerization of the monomer in the presence of a surfactant and/or a polymeric protective colloid. Compositions as described. (3) The oxidatively polymerizable polymer emulsion of (A) is used as a part of other copolymerizable monomers (formula %) (in the formula, R1 is hydrogen, lower alkyl, or halogen; R2
is hydrogen or lower alkyl; n is an integer of 4 to 25), and is obtained by emulsion polymerization of the monomer in the absence of a surfactant and/or a polymeric protective colloid. A composition according to claim 1. (4) The composition according to claim 3, wherein the compound represented by the general formula accounts for 2 to 20 parts by weight of the other copolymerizable monomers. (5) The composition according to any one of claims 1 to 4, wherein the oxidatively polymerized resin (B) is a drying oil fatty acid and/or a semi-drying oil fatty acid modified acrylic copolymer. (6) The composition according to any one of claims 1 to 4, wherein the oxidatively polymerized resin (B) is a vinyl-modified alkyd resin.