JPS62201972A - Water paint composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which has excellent storage stability and gives a coating film having excellent corrosion resistance and curability, by mixing a specified reaction product with a reaction product between a compd. having a glycidyl group and an unsaturated fatty acid, etc., and a condensation product, etc., and dispersing the mixture in an aq. medium in the presence of a base. CONSTITUTION:100pts.wt. reaction product (A) obtd. by reacting a reaction product (a) of a conjugated diene (co)polymer having a number-average MW of 500-5,000 and an iodine value of 100-500 and/or a (semi)drying oil having an iodine value of not lower than 100 with an alpha,beta-unsaturated carboxylic acid anhydride of formula I (wherein R1 is R2 or halogen) with water and/or a primary alcohol, etc. (h) and a polyhydric alcohol (c) is mixed with 10-200pts.wt. reaction product (B) of a compd. having a glycidyl group and a number-average MW of 300-4,000 with an alpha,beta-unsaturated carboxylic acid of formula II (wherein R2 and R3 are each N or CH3), etc., 10-100pts.wt. condensation product (C) between an etherified HCHO and aminotriazine and 10-100pts.wt. reaction product (D) of a condensed HCHO with phenol. The mixture is dispersed in an aq. medium in the presence of a base such as diethylamine, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aqueous coating composition that can be applied by common coating techniques such as dipping or spraying, and can also be used as an anodic electrodeposition coating.

BACKGROUND ART AND PROBLEM Maleated polybutadiene, maleated drying oils, halfesters and half amides thereof are among the most commonly used resin components, especially in the field of electrocoat coatings, primarily due to their excellent bath stability. However, the corrosion resistance of the steel surface is poor,
It had drawbacks such as a relatively high baking temperature.

In order to improve this drawback, for example, if a water-soluble resin represented by a fatty acid ester of Evogin resin is used in combination, the corrosion resistance of the iron surface is generally improved, but the stability of the bath liquid is reduced.

Until now, many proposals have been made for the combined use of various water-soluble resins in order to compensate for the shortcomings of maleated polybutadiene, maleated moieties, half-esters and half-amides thereof (for example, Japanese Patent Publication No. 47-2169
No. 1, Special Publication No. 4L-47594, Japanese Patent Publication No. 48-257
No. 32 and Japanese Patent Publication No. 49-4058), low temperature curing,
None of the paints were satisfactory in terms of slather resistance and paint storage stability.

Therefore, it is an object of the present invention to provide aqueous coating compositions based on maleated diene polymers and maleated oils, particularly anodic electrodeposition coating compositions, which are superior in these properties.

Solution (A) Number average molecular weight 500-5000 and iodine value 1
00 to 500 conjugated diene polymer, a copolymer, and/or a semi-drying oil having an iodine value of 100 or more, and α of the general formula (wherein R3 is a hydrogen atom, halogen or methyl group). , β-unsaturated dicarboxylic anhydride, 100 g of Moesha
To the product obtained by reacting the latter at a ratio of 100 to 300 mmol per 100 to 300 mmol of the latter, (a) not more than 0.9 mol of water per 19 liters of the α,β-unsaturated dicarboxylic anhydride is added.
obtained by reacting a polyhydric alcohol and/or a primary monoalcohol and/or a dialkylamine, and (b) a polyhydric alcohol in an amount of 0.1 mole per 19 liters of the α,β-unsaturated dicarboxylic acid anhydride. Reaction product 10f) 1 m part of ff, (BXi) a compound having a number average molecular weight of 300 to 4000 and having at least one glycidyl group in the molecule, and a grindyl group I of the compound
0.8 to 1.1 mol of the general formula, R, I? per H1?
, 0 (wherein R3 and R are hydrogen atoms or methyl groups), α, β-unsaturated carboxylic acid and/or molecule m I
00 to 350 and a reaction product with an unsaturated fatty acid having an iodine value of 100 or more, Mano; (ii) Number average molecular engineering 300
~4000 and having at least one phenolic hydroxyl group in the molecule and at least 08 moles per mole of the compound of the general formula R4H2C-C11-CH, -0-C-C=CIt (wherein,
R4 is a hydrogen atom or a methyl group) reaction product with α,β-unsaturated carboxylic acid monoglycidyl ester, or a mixture of (i) and (ii) above 10 to 200 parts by weight, (C) one or more 10 to 100 parts by weight of a condensation product of the above optionally etherified formaldehyde and aminotriazine, and (D) 10 to 100 parts of a reaction product of one or more optionally condensed formaldehydes and phenol. An aqueous coating composition containing part M dispersed in an aqueous medium with a base is provided.

The water-based paint composition of the present invention contains cobalt, manganese, iron, lead, calcium-like percussion salt of silconium cum, manganese dioxide, or a mixture thereof as a component (7). 0.005 to 1.0 parts by weight may be included.

The water-based coating composition of the present invention is composed of a water-soluble component (A) which has excellent bath stability but poor corrosion resistance, and a component (B) which has excellent corrosion resistance but is not water-soluble. Dissolved in water as the core component of the emulsion, and further (C
By using a melamine resin as the component () and a phenol resin as the component (D), the curability and corrosion resistance of the coating film can be further improved without impairing the stability of the coating.

Component A Number average molecule ff1500-5000 and iodine value ioo~
A typical example of a copolymer such as 500 conjugated diene polymers is liquid polybutadiene. Copolymers of butadiene and other conjugated diene compounds, such as methylbutadiene, dimethylbutadiene, chlorobrene, or these conjugated diene monomers with small proportions of other vinyl monomers, such as styrene, vinyl acetate, (meth)acrylic acid esters ,
Copolymers with acrylonitrile and the like may also be used. Liquid polybutadiene is particularly preferred because it is readily available on the market.

Examples of the drying oil or semi-drying oil include natural drying oils or semi-drying oils such as tung oil, linseed oil, safflower oil, and soybean oil, and synthetic drying oils such as dehydrated castor oil.

Examples of the α,β-unsaturated dicarboxylic acid anhydride of the general formula (wherein Ro is the same as above) include maleic anhydride, citraconic anhydride, and chloromaleic anhydride.

α to conjugated diene polymer and drying oil to semi-drying oil,
Addition reactions of β-unsaturated dicarboxylic acid anhydrides are well known. Component (A) of the present invention can be prepared according to these known methods. However, the amount of unsaturated dicarboxylic acid anhydride to be added should range from 100 to 300 mmol per 100 g of conjugated diene polymer, semi-drying oil such as drying oil, or a mixture thereof. If the amount of acid anhydride added is insufficient, the water solubility of the reaction product will be insufficient,
Moreover, if it is in excess, the viscosity of the reaction product increases, leading to problems such as gelation of the product and loss of smoothness of the coating film.

The addition product is then reacted with (a) water, a primary monoalcohol and/or a dialkylamine, and (b) a polyhydric alcohol. These reactions themselves are known as cleavage reactions of acid anhydride structures.

The reaction between (a) and (b) with the addition product may be carried out first. For example, the acid anhydride structure of the addition product is first cleaved into a dicarboxylic acid in water, a halfester with a monoalcohol, and a monoamide with a dialkylamine, and then the reaction with a polyhydric alcohol is performed. Alternatively, the reaction with the polyhydric alcohol may be carried out first, and then the reaction with water, monoalcohol or dialkylamine may be carried out.

The amount of water, monoalcohol or dialkylamine should be less than 0.9 mole per mole of added unsaturated carboxylic acid anhydride. If it exceeds 0.9 mol, the reaction amount of polyhydric alcohol will decrease, resulting in insufficient coating film curing properties.
It has drawbacks such as poor spray resistance. The reaction amount of polyhydric alcohol is preferably 1 to 0.1 mol. 0
．． If it is less than 1 mol, the coating film curability will be poor. 1
If the amount exceeds the molar amount, a portion of the polyhydric alcohol remains as an unreacted product, resulting in poor shaving resistance. However, if the reaction order is to react the polyhydric alcohol first, the polyhydric alcohol will be 1.0 to 0.7 mol per mol of saturated carboxylic acid is preferred.

If the amount is less than 0.7 mol, the reaction product will gel.

As primary monoalcohols that can be used in the cleavage reaction, in addition to lower alcohols such as methanol and ethanol, ethylene glycol monoalkyl ethers such as edyl cellosolve can be used. The primary monoalcohol or sialgylamine can be used in excess and can also serve as a component of the aqueous dispersion medium for the resin component. Examples of the dialkylamine include dimedylamine, diethylamine, and the like.

From the viewpoint of reaction control, it is preferable that at least one of the alcoholic hydroxyl groups of the polyhydric alcohol is secondary to trivalent.

Examples of polyhydric alcohols that can be used include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, toluethylene glycol, neopendel glycol, 3-butylene glycol, and 2.2.4-hrimedyl. -1,3-pentadiol, glycerin, pentaerythritol, sorbitol, inositol, trimethylolethane, trimethylolpropane, mannitol, dipentaerythritol, polyethylene glycol, polypropylene glycol, and the like. These can be used in excess of the added acid anhydride structure and can also serve as a component of the aqueous medium of the resin component.

Component B (i) The compound having a number average molecular weight of m300 to 4000 and at least 61 glycidyl groups in the molecule is typically a variety of epoxy resins, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and novolak. It is a phenol epoxy resin.

Typical examples of α,β-unsaturated carboxylic acids of the general formula, 1-IC= C-C-01-1 1]ll R2R30 (wherein R2 and R1 are the same as above) are acrylic acid and methacrylic acid. be.

Examples of unsaturated fatty acids with molecules m100 to 350 and an iodine value of 00 or higher are linoleic acid, lilunic acid, eleostearic acid, linseed oil 1 fatty acid, tall Ml + fatty acid, dehydrated castor Al + fatty acid, and synthetic unsaturated fatty acids. (For example, the product names are Hygiene and Hygiene 100).

The phenol resin and the glycidyl ester are mixed at least 0.0% per molecule of the phenolic resin in order to ensure practical curability of the coating film due to the carbon-carbon bond in the reaction product (ii), which is the curing point. Eight molecules of the glycidyl ester compound should be reacted. Component B can be a mixture of (i) and (ii).

Component C Condensation products of one or more optionally etherified formaldehydes with aminotriazine rings include formaldehyde adducts of melamine, benzoguanamine, acetoguanamine or mixtures thereof and part or all of the total bound formaldehyde. is methanol,
It is better if it is etherified with propatool or butanol.

In this case, if the total amount of formaldehyde bound is less than 1 mol per 71 mol of aminotriazine, the curability of the coating film decreases, which is not preferable.

The reaction products of phenol and formaldehyde condensed to one or more compounds are phenol, p-cresol, p-tert-butylphenol, aluminumphenol, p-phenylphenol, hisphenol A.
A resol type phenol resin having at least 61 or more methylol groups and 1 to 6 phenol nuclei in one molecule obtained by reacting phenols such as and formaldehyde, preferably in the presence of an alkali catalyst, If the number of phenol nuclei is 6 or more, the number average molecular weight will be more than 000, which is undesirable because the anticorrosion property will be lowered.

The U-shaped reaction component A (the same applies to the unsaturated fatty acid ester of Evoquin resin among the reaction components B) is cured by an oxidative polymerization reaction of carbon-carbon double bonds.

Component E acts to accelerate this hardening reaction and lower the baking temperature. Metal compounds that can be used for this purpose are base salts of cobalt, iron, lead, calcium, zirconium, and manganese dioxide.

Examples of H organic acids include formic acid, acetic acid, lactic acid, naphthenic acid, and octanoic acid. Mixtures of these metal compounds can also be used.

The water-based coating composition of the present invention contains 100 to 100 parts by weight of component A, 10 to 100 parts by weight of component C to 100 parts by weight of component D, and 10 to 100 parts by weight of component C to 100 parts by weight of component A (all solid content). conversion)
including. If the m content of component B is small, the effect of improving the corrosion resistance of the coating film will be small; on the other hand, if it is too large, the storage stability of the paint will not be sufficient. If the amount of component C is small, the effect of modifying the curability of the coating film will be small; on the other hand, if it is too large, the storage stability of the coating material will not be sufficient. If there are few insects in the D component (J, the effect of improving the corrosion resistance of the paint film will be small; on the other hand, if there is too much, the hardenability of the paint film and the storage stability of the paint will be insufficient. If the component E is included, it will be converted to metal) A component 100iTfj7) Oil power 0.005~
It should be 1.0 part by weight. The lower limit is the practically effective m for lowering the baking temperature of the paint film, and the upper limit depends on the storage stability of the paint.

Component A and Component B are dispersed in an aqueous medium containing a sufficient amount of base to neutralize at least 20% of the carboxyl groups remaining in Component A and Component B. If the amount of base is small, storage stability of the paint becomes a problem.

Examples of the base used for neutralization include ammonia, jetanolamine, triethanolamine, methylethanolamine, diethylamine, morpholine, and potassium hydroxide.

The aqueous medium is water or a mixture of water and a water-miscible organic solvent. If necessary, the aqueous medium may contain a water-immiscible organic solvent. Examples of water-miscible organic solvents include ethyl cellosolve, propyl cellosolve, butyl cellosolve, ethylene glycol, dimedyl ether, diacetone alcohol, 4-methoxy-4-methylpentanone-2, methyl ethyl ketone, and the like. Further, examples of water-immiscible organic solvents include quinolene, toluene, medyl isobutyl ketone, and 2-ethylhexanol.

As mentioned earlier, the monoalkyl ether of ethylene glycol can also serve as an acid (lit yk tank structure 11 cleaving agent) in the +jk component A+.Since component A is water-soluble, dispersion in an aqueous medium is Although it is easy, component B is poorly water-soluble and is uniformly dispersed in the paint as an emulsion core.Therefore, a known emulsifier may be used if necessary.

The coating composition of the present invention can contain pigments.

Examples include coloring pigments such as titanium dioxide, red iron oxide, carbon black, extender pigments such as aluminum silicate, precipitated barium sulfate, and aluminum phosphomolybdate, strontium chromate, basic lead silicate, lead chromate, etc. There are anti-rust pigments.

The coating composition of the present invention can be used as a general water-based coating by general coating techniques such as dipping or spraying, or can be used as an electrodeposition coating for anodic electrodeposition coating, where the object to be coated is an anode. You can do it.

For the song number, adjust the non-volatile content of the paint to 40-60%,
Paint so that the dry film thickness is 15 to 30μ, and
Bake at a temperature of B. In the case of electrodeposition coating, the non-volatile content is 1O~2
0%, and electrodeposited to a dry film thickness of I5 to 30μ, and
~! Baking can be done at 40°C for 20 to 30 minutes.

Production examples, examples and comparative examples of the present invention are shown below. In these examples, parts and percentages are by weight.

Ingredients Production Example 1 0 Stone Polybutadiene B-1500 * 1 000g
Antigen 6C*li 10g Maleic anhydride 250g Deionized water 20g Diethylamine 0.5g Propylene glycol 100g Ethyl cellosolve
340g*I) Japan Mukoku Kagaku Co., Ltd.
Made: Mn 1500, vinyl 65%, transformer 14%
, cis 16% *2) Manufactured by Sumitomo Chemical Co., Ltd.;
-dimethylbutyl), p-phenylenediamine with cooling tube 2! For Kolben, 0 stone polybutadiene B-150010
00g and added 6010g of antikene and 250g of maleic anhydride. While stirring, reduce the inside to 1.9
While maintaining the temperature between 0 and 200°C, the addition reaction of maleic acid to polybutadiene (=J) was carried out. Approximately 5 hours after the temperature was raised, it was confirmed that the reaction was completed by the dimethylaniline color reaction.Then, the internal temperature was lowered to 100°C. Cool to C and add 2 J of deionized water.
and diethylamine 0.5g dropwise over about 30 minutes.
do. Further, after the dropwise addition was completed, stirring was continued for about 1 hour, and the acid value was confirmed to be 140. Thereafter, 100 g of propylene glycol was added and reacted at 110°C for 3 hours, and the total acid value was confirmed to be 125. After that, 340 g of ethyl cellosolve was added and stirred at 80°C for about 1 hour.
Ending synthesis 1. Ta.

Risen carp 1 0 stone polybutadiene B-1000*3) 500g
Flaxseed oil 500g Antigen Ken 10g Maleic anhydride 250g Deionized water
20g diethylamine
0.5g propylene glycol
100g ethyl cellosolve
Mn
1000, vinyl 65%, trans 14%, cis 16% Synthesis was performed in the same manner as in Production Example 1 except that 500 g of O-stone polybutadiene B-1000 and 500 g of linseed oil were used instead of 1000 g of O-stone polybutadiene 13-1500.

Component B Production Example 3 Evotote YD-014*') 950g Ethyl cellosolve 240g Hydroquinone 10g Acrylic acid
65g Dimedimethyndylamine 5g*3) Epoxy resin manufactured by Tobu Kasei Co., Ltd., Ebokino Tohiko 950 Evotote YD-01495 in a 2fl Kolben with cooling tube
0g and 1240g of ethylse [l vine], gradually add 1
Uniformly dissolve YD-014 while stirring up to 20°C. Thereafter, 10 g of hydroquinone is added, followed by 65 g of acrylic acid and 5 g of dimethylbenzylamine. 1
After reacting at 20° C. for 4 hours, the acid value was confirmed to be below Kawabe.

Production example 4 Evototo YD-012*5) 650g ethyl cellosolve 220g hydroquinone 10g hydien
*8) 280g dimethylbenzylamine 5g*') Evoquin resin manufactured by Tobu Kasei Co., Ltd., Evokine equivalent weight 660 *a) Synthetic drying oil manufactured by Soken Chemical Co., Ltd.: acid value 198, iodine value 167 with an iodine value of 100 or more, conjugated diene 52 Evo tote YD-014950g Evo I-1-YD-01
Synthesis was carried out in the same manner as in Production Example 3, except that 65 g of acrylic acid was replaced with 280 g of acrylic acid.

Production example 5 Tamanol T521 *7) 700g
Ethyl cellosolve 185g Hydroquinone IOg Glyglycidyl methacrylate 100g Dimedylmethidylamine 5g *7) Manufactured by Arayo Kagaku Kogyo Co., Ltd.; Tamanol T521700g in a 2℃ Kolben with oil-soluble phenol resin cooling tube,
Charge 185 g of ethyl cellosolve and gradually stir to 120°C to uniformly dissolve T521. Thereafter, IOg of hydroquinone is added, followed by 100g of glycidyl methacrylate and 5g of dimethylbenzylamine. After reacting at 120'C for 3 hours and 30 minutes, the epoxy
It was confirmed that the number was 6000 or more.

Comparative Production Example I Oral Polybutadiene B-1500 1000 g Antigen 6CIQg Maleic Anhydride 250 g Deionized Water 46 g Diethylamine 085 g Ethyl Cellosolve 340 g In a 2L Kolben equipped with a cooling tube, 1000 g Oral Polybutadiene B-1500 was charged, Antigen 6C 1 Og and maleic anhydride 250 g
Add. Stirring 1. Therefore, the internal temperature is 190-200℃
The addition polymerization reaction of maleic acid to polybutadiene is carried out while maintaining the temperature. Approximately 5 hours after the temperature was raised, it was confirmed that the reaction was completed by the dimedylaniline color reaction. Thereafter, the internal temperature was cooled to 100° C., and a mixture of 46 g of deionized water and 0.5 g of diethylamine was added dropwise over about 30 minutes.

After the addition was completed, stirring was continued for about 1 hour until the acid value reached 190.
It was confirmed that Then ethyl cellosolve 340
After stirring at 80° C. for about 1 hour, the synthesis was completed.

Oikagoi L itU 25g of varnish from Preparation Example 1, 75g of varnish from Preparation Example 3, 40g of butylated melamen (non-volatile content 50%),
40 g of resol type phenolic resin (nonvolatile content 50%) was collected, 2 g of nonionic surfactant was added thereto, and the mixture was stirred uniformly. 13 g of triethylamine was added thereto, and then 707 g of deionized water was gradually added while stirring uniformly. A paint bath having a solids concentration of about 20% was prepared.

A dull steel plate treated with zinc phosphate was immersed in a paint bath, and electrodeposition was carried out at 100 V for 3 minutes using the object to be coated as an anode. Thereafter, the surface of the object to be coated was washed with water and baked in a baking oven at 120° C. for 30 minutes to obtain a coated plate with a film thickness of about 20 μm. Table 1 shows the results of testing the performance of the obtained coating film.

Example 2 Ingredients Parts by weight (
g) Varnish of Production Example I 125 Varnish of Production Example 3 75 Butylated melamine (50% non-volatile content) 40 Nonionic surfactant
2 Cobal naphthenate l-3 Triedylamine 13 Deionized water 707 Processed as in Example I except using the above formulation. The coating performance is shown in Table-1.

χYomachi component 1 Jini＜
<Kamey Varnish of Production Example I 125 Varnish of Production Example 3 75 Butylated melamine (50% non-volatile content) 40 Nonionic surfactant 2 Iron naphthenate
3 triethylamine
13 Deionized water 7
07 Processed in the same manner as in Example I except that the above formulation was used. The coating performance is shown in Table-1.

Really drunk! L-'' ■ City α Part (g) Varnish of Production Example I 125 Varnish of Production Example 4 75 Butylated melamine (non-volatile content 50%) 40 Nonionic surfactant
2Cobalt naphthenate3 Triethylamine I3Deionized water 707Processed as in Example I except using the above formulation. The film-receiving performance is shown in Table-1.

g Erosion l Ingredients Parts by weight (g
) Varnish of Production Example 1 125 Varnish of Production Example 5 75 Butylated melamine (50% non-volatile content) 40 Nonionic surfactant
Cobalt 2 naphthenate
3 Triedylamine I
3 Deionized water 707 Processed in the same manner as in Example 1 except that the above formulation was used. The coating film performance is shown in Table-■.

Fruit ■ Masu 1 Ingredients Parts by weight (g
) Varnish of Production Example 2 125 Varnish of Production Example 3 75 Butylated melamine (non-volatile content 50%) 40 Nonionic surfactant
2 Cobalt naphthenate 3 Triethylamine 13 Deionized water 707 The same procedure as in Example 1 was carried out except that the following formulation was used. Table of coating film performance -■
Shown below.

Example 7 Ingredients Parts by weight (g) Varnish of Production Example 125 Varnish of Production Example 3 75 Butylated melamine (
Non-volatile content 50%) 40 Resol type phenolic resin (non-volatile content 50%) 10 Nonionic surfactant 2 Cobalt naphthenate 3 Triethylamine 13 Deionized water
38 A paint bath was prepared in the same manner as in Example 1 except that the above formulation was used, and a dull steel plate treated with zinc phosphate was dip coated. The coating performance is shown in Table-1.

Comparative Example I Ingredients Parts by weight (g)
Varnish of Comparative Production Example 1 125 Production Example 3
Varnish 125 Nonionic surfactant 2 Cobalt naphthenate
3 Triedylamine
Summer 3 deionized water 73
The procedure was the same as in Example I except that the following formulation was used. The coating film performance is shown in Table-■.

Comparative example 2 Ingredients Parts by weight (g
)1↓A/1IIl+1゛lto11:1blind1/rS100--9 Varnish of Production Example 3 100Resol type phenolic resin (non-volatile content 50%)40 Nonionic surfactant 2Cobalt naphthenate 3Triedylamine 13Deionized water
717 Processed in the same manner as in Example 1 except that the above formulation was used. The coating performance is shown in Table-1.

Developability l Ingredients Heavy! n parts (g
) Varnish of Comparative Production Example 1 125 Varnish of Production Example 3 100 Butylated melamine (non-volatile content 50%) 40 Nonionic surfactant
2 Cobal naphthenate l-3 Triethylamine 13 Deionized water 7 Same as Example 1 except that the prescribed recipe was used for 7- (treated as P. The coating film performance is shown in Table 1.
Shown on the river.

Procedural Amendment (Dear Commissioner of the Self-Responsive Patent Office, January 27, 1986 2)
6 Name of the invention Water-based paint composition 3 Relationship with the case of the person making the amendment Address of the patent applicant 4 agent 2-1-61 Mihigashi-ku, Osaka City, Osaka Prefecture 540
No. 7, Contents of amendment (1) On page 16 of the specification, line 8 from the bottom, [toluethylene glycol] is corrected to "triethylene glycol."

(2) Insert the following statement between the second and third lines of page 18.

"The proportion of epoxy resin and unsaturated fatty acid, such as α,β-unsaturated carboxylic acid, is determined per equivalent of glycidyl group of the epoxy resin, so that the reaction product (B-i) has substantially no acid value. For α, β-unsaturated carboxylic acids, the amount of unsaturated fatty acids should be 0.8 to 11 moles.

(ii) A typical example of a compound having a number average molecular weight of 300 to 4,000 and having at least one phenolic hydroxyl group in the molecule is a phenol resin. The phenol resin may be a novolac type or a resol type.

These are obtained by combining phenol and typically formaldehyde in the presence of an alkali or acid catalyst.

The glycidyl ester of the general formula 01N4 (in the formula, R4 is the same as above) is a glycidyl ester of methacrylic acid, which is similar to acrylic acid. ” (3) Page 25, line 4 from the bottom, r*3) Replace “J” with “
Correct it to ``*tsu''.

that's all

Claims (1)

[Claims] 1. (A) number average molecular weight of 500 to 5000 and iodine value of 1;
00 to 500 conjugated diene polymer or copolymer, and/or drying oil or semi-drying oil with an iodine value of 100 or more, general formula, ▲mathematical formula, chemical formula, table, etc.▼ (In the formula, R_1 is a hydrogen atom , halogen or methyl group) at a ratio of 100 to 300 mmol of the latter per 100 g of the former; 0.9 mole or less of water and/or a primary monoalcohol and/or dialkylamine per mole of α,β-unsaturated dicarboxylic anhydride; and (b) 1 mole of said α,β-unsaturated dicarboxylic anhydride. (B) (i) a compound having a number average molecular weight of 300 to 4000 and at least I glycidyl groups in the molecule; , 0.8 to 1.1 mol per equivalent of glycidyl group of the compound, ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_2 and R_3 represent a hydrogen atom or a methyl group.) α of , a reaction product with a β-unsaturated carboxylic acid and/or an unsaturated fatty acid with a molecular weight of 100 to 350 and an iodine value of 100 or more, or (ii) a number average molecular weight of 300 to 4000 and at least one phenolic hydroxyl group in the molecule. There are compounds having the general formula, ▲mathematical formula, chemical formula, table, etc.▼ (in the formula, R_4 is a hydrogen atom or a methyl group) with at least 0.8 mol per mol of the compound α, β-
Reaction products with unsaturated carboxylic acid monoglycidyl esters or mixtures of (i) and (ii) above 10-2
00 parts by weight, (C) condensation product of aminotriazine with one or more optionally etherified formaldehydes 10
~100 parts by weight, and (D) 10 to 100 parts by weight of one or more optionally condensed formaldehyde and phenol reaction products, dispersed in an aqueous medium with a base. . 2. The aqueous coating composition according to item 1, wherein the copolymer is a butadiene homopolymer or copolymer, which is a conjugated diene polymer, and the α,β-unsaturated dicarboxylic acid anhydride is maleic anhydride. 3. The aqueous coating composition according to item 1, wherein the compound having a number average molecular weight of 300 to 4000 and having at least one glycidyl group in the molecule is a polyglycidyl ether of polyphenol. 4. The aqueous coating composition according to item 1, wherein the compound having a number average molecular weight of 300 to 4,000 and having at least one phenolic hydroxyl group in the molecule is a novolac type or resol type phenolic resin. 5. The aqueous coating composition according to item 1, wherein component C is butylated melamine. 6. The aqueous coating composition according to item 1, wherein component D is a resol type phenolic resin. 7. (A) Number average molecular weight 500-5000 and iodine value 1
00 to 500 conjugated diene polymer or copolymer, and/or drying oil or semi-drying oil with an iodine value of 100 or more, general formula, ▲mathematical formula, chemical formula, table, etc.▼ (In the formula, R_1 is a hydrogen atom , halogen or methyl group) at a ratio of 100 to 300 mmol of the latter per 100 g of the former; 0.9 mole or less of water and/or a primary monoalcohol and/or dialkylamine per mole of α,β-unsaturated dicarboxylic anhydride; and (b) 1 mole of said α,β-unsaturated dicarboxylic anhydride. (B) (i) a compound having a number average molecular weight of 300 to 4000 and at least one glycidyl group in the molecule; , 0.8 to 1.1 mol per equivalent of glycidyl group of the compound, ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_2 and R_3 represent a hydrogen atom or a methyl group.) α of , a reaction product with a β-unsaturated carboxylic acid and/or an unsaturated fatty acid with a molecular weight of 100 to 350 and an iodine value of 100 or more, or (ii) a number average molecular weight of 300 to 4000 and at least one phenolic hydroxyl group in the molecule. and α of the general formula, ▲mathematical formula, chemical formula, table, etc.▼ (in the formula, R_4 represents a hydrogen atom or a methyl group) at least 0.8 mol per mol of the compound.
, a reaction product with β-unsaturated carboxylic acid monoglycidyl ester, or a mixture of (i) and (ii) above, 10 to 200 parts by weight, (
C) Condensation products of one or more optionally etherified formaldehydes with aminotriazines 10-
100 parts by weight, (D) 10 to 100 parts by weight of one or more optionally condensed reaction products of formaldehyde and phenol, and (E) radicals of cobalt, manganese, iron, lead, calcium or zirconium. An aqueous coating composition containing 0.005 to 1.0 parts by weight of an acid salt, manganese dioxide, or a mixture thereof in terms of metal, and dispersed in an aqueous medium with a base. 8. The conjugated diene polymer or copolymer is a butadiene homopolymer or copolymer, and the α, β
- The aqueous coating composition according to item 5, wherein the unsaturated dicarboxylic anhydride is maleic anhydride. 9. The aqueous coating composition according to item 5, wherein the compound having a number average molecular weight of 300 to 4,000 and having at least one glycidyl group in the molecule is a polyglycidyl ether of polyphenol. 10. Fifth, the compound having a number average molecular weight of 300 to 4000 and having at least one phenolic hydroxyl group in the molecule is a novolac type or resol type phenolic resin.
The water-based paint composition described in . 11. The aqueous coating composition according to item 7, wherein component C is butylated melamine. 12. The aqueous coating composition according to item 7, wherein component D is a resol type phenolic resin.