JPS5830344B2 - Water-dispersed thermosetting coating composition - Google Patents

Description

[Detailed description of the invention] The present invention relates to water-dispersed thermosetting coating compositions.

More specifically, the present invention relates to a water-dispersible thermosetting coating composition that forms a coating film with high performance, particularly excellent cold and heat cycle resistance, chemical resistance, and weather resistance.

BACKGROUND ART In recent years, efforts have been made to make paints and coatings pollution-free and resource-saving, and powder coatings and water-based coatings are increasingly being used as coatings suitable for this purpose.

However, such powder coatings require special coating equipment, are not easy to apply like conventional solvent-based coatings, and have excellent coating film smoothness and finished appearance (and 50%
There were problems in use, such as difficulty in coating thin films with a thickness of less than .mu.m.

Furthermore, among water-based paints, water-soluble paints have a low solid content concentration during painting, so it is difficult to apply a thick film at once. The problem was that the durability could not be achieved.

On the other hand, emulsion paints have had the problem of poor water resistance, chemical resistance, etc. of the paint film because they use a large amount of surfactant.

As a method to solve these problems, a slurry paint (water-dispersed paint) has been proposed in which resin powder is suspended in water and applied like a water-based paint.

In general, acrylic resins, unsaturated polyesters, epoxy resins, alkyd resins, etc. are known as resins used in such slurry paints. Acrylic resins and unsaturated polyesters are preferred from the viewpoint of appearance.

In addition, epoxy resin or the like may be used in combination to further enhance anti-corrosion properties.

However, if an epoxy resin is used in combination, the weather resistance will be impaired, so it is not preferable to use it as a component of the top coat resin.

By the way, when melamine resin is used as a cross-linking agent, if a thick film is applied, baking will occur, especially foaming (wax).
It had a drawback in terms of painting workability, and it was necessary to paint it several times to get a thick film.

The present invention aims to solve these problems.

In other words, it is a water-dispersed thermosetting coating composition that has excellent coating performance such as gloss, smoothness, cold and heat cycle resistance, chemical resistance, and weather resistance. It is something that provides something.

That is, the present invention provides (A) (:) 1 to 10% by weight of α/β-unsaturated dicarboxylic acid as one of the constituent components, an acid value of 50 or less, and a hydroxyl value of 5.
0-250, weight average molecular weight 2000-120000 unsaturated polyester
......2 to 40% by weight and (1
1) (a) Hydroxyalkyl ester of α/β-monoethylenically unsaturated carboxylic acid 1 to 30% by weight, (b) α/β-monoethylenically unsaturated carboxylic acid amide N-alkoxymethylated monomer of......5
~30% by weight (・) A monomer mixture consisting of 60 to 90% by weight of α/β-monoethylenically unsaturated monomers other than the above (a) and (b). ...98 to 60% by weight, obtained by graft polymerization with a hydroxyl value of 10 to 180
, acid value 3-40, weight average molecular weight 40000-2000
0.00 polyester-modified vinyl resin, and (B) a flocked incyanate compound.
．． A water-dispersible thermosetting coating composition comprising 0% by weight of surfactant and/or thickener and the required amount of water.

The polyester-modified vinyl resin used in the present invention is obtained by graft polymerizing an α/β-monoethylenically unsaturated monomer mixture (former GilffA) (ii)) to an unsaturated polyester, and is It is characterized by imparting to vinyl resin the flexibility, pigment dispersibility, and superior coating appearance of saturated polyester.

Therefore, it is necessary to use an .alpha..beta.-unsaturated dicarboxylic acid as a raw material for the unsaturated polyester used in the present invention.

The components are reacted in an amount of 1 to 10% by weight, preferably 3 to 7% by weight, in the unsaturated polyester.

That is, if the amount of this component is 1% by weight or less, the amount is not sufficient for the α/β-monoethylenically unsaturated monomer when producing the polyester-modified vinyl resin, and therefore the polyester modification is insufficient and its The resulting product has a composition in which an unsaturated polyester and a polymer of α/β-monoethylenically unsaturated monomer are blended, and the coating film may become white.

Further, due to the difference in reactivity between the crosslinking monomer and the blocked isocyanate compound, coating film performance, particularly adhesion, tends to deteriorate, which is not preferable.

On the other hand, if the content of this component is 10% by weight or more, gelation occurs during the reaction with the α/β-monoethylenically unsaturated monomer, which is not preferable.

Specific examples of the α/β-unsaturated dicarboxylic acid component include:
Examples include fumaric acid, maleic acid (anhydride), itaconic acid, glutaconic acid, and citraconic acid (anhydrous), and these may be used alone or in a mixture of two or more.

In the synthesis of the unsaturated polyester used in the present invention, the carboxylic acid component other than the above acid is preferably 29 to 69
% by weight.

Specific examples of the components include phthalic anhydride, inophthalic acid, trimellitic anhydride, pyromellitic acid anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyltetrahydro phthalic anhydride. phthalic acid,
Methylhexahydrophthalic anhydride, imitsic anhydride, co-phosphoric acid, adipic acid, sebacic acid,
Examples include benzoic acid and para-butylbenzoic acid, and one type or a mixture of two or more of these may be used.

In the synthesis of the unsaturated polyester used in the present invention, the polyhydric alcohol component is preferably reacted in a proportion of 30 to 70% by weight.

Specific examples of the ingredients include ethylene glycol, diethylene glycol, glopylene glycol, neohentyl glycol, dipropylene glycol, chrycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, butanediol, and bentanediol. , hexanediol, ■・4-
Examples include cyclohexane dimetatool, (hydrogenated) bisphenol A, and the like.

These may be used alone or in combination with a mixture of two or more thereof, and if necessary, a glycidyl ester of tertiary synthetic saturated fatty acid (manufactured by Cardulor E Nigel Chemical Co., Ltd., trade name).

In addition, animal and vegetable oils and their fatty acids, petroleum resins,
Rosin, phenolic resin, epoxy resin, etc. can also be used.

The unsaturated polyester in the present invention is produced by a single-stage reaction or a multi-stage reaction by a known method, and there are no restrictions on the reaction method.

Further, a polymerization solvent described below can be used as a diluent if necessary.

The acid value of the unsaturated polyester of the present invention is 50 or less (resin solid content: hereinafter, all indications of the acid value of the present invention are the same),
The hydroxyl value is 50 to 250 (resin solid content is 2 or less and all hydroxyl values in the present invention are expressed in the same way), and the molecular weight is 2,000 to 120,000 in terms of weight average molecular weight.

The weight average molecular weight was measured by gel permeation chromatography (Model A301 manufactured by Toyo Soda).

Hereinafter, the weight average molecular weight in the present invention was measured in the same manner.

In the present invention, the unsaturated polyester has an acid value of 50
If it is more than that, the alkali resistance etc. in the final coating film performance after graft polymerization of the α/β-monoethylenically unsaturated monomer mixture will decrease.

In addition, if the hydroxyl value is lower than 50, the crosslinkability between the polyester-modified vinyl resin obtained by graft polymerization of the α/β-monoethylenically unsaturated monomer mixture and the block isocyanate compound described below is likely to be insufficient; If it is high, the water resistance of the resulting coating film tends to decrease due to an increase in the number of polar groups, which is not preferable.

In addition, if the weight average molecular weight is lower than 2000, the properties of unsaturated polyester cannot be fully exhibited;
If it exceeds 0,000, the molecular weight of the unsaturated polyester is too high, and when modified with an α/β-monoethylenically unsaturated monomer mixture, the viscosity becomes too high, which impairs workability, which is not preferable.

The polyester-modified vinyl resin of the present invention includes the unsaturated polyester, (a) hydroxyalkyl ester of α/β-monoethylenically unsaturated carboxylic acid, and (b)
α°β-N- of monoethylenically unsaturated carboxylic acid amide
It is obtained by graft polymerization of a monomer mixture consisting of an alkoxymethylated monomer and an α/β-monoethylenically unsaturated monomer other than (a) and (b) above.

The hydroxyalkyl ester monomer of the α/β-monoethylenically unsaturated carboxylic acid has α/β-monoethylenically unsaturated carboxylic acid so that the hydroxyl value of the polyester-modified vinyl resin is 10-180.
- monoethylenically unsaturated monomer mixture [pre=aH(1i
) component] is used in an amount of 1 to 30% by weight, particularly preferably 2 to 20% by weight.

If the monomer is used in an amount exceeding 30% by weight, the polyester-modified vinyl resin will have a high viscosity, and the crosslinking density after the thermosetting reaction with the blocked isocyanate compound will be high (too much, resulting in poor coating film quality). This is not preferable because flexibility, water resistance, etc. tend to decrease.

Specific examples of the monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate.
- Hydroquine butyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyakyl (meth)acrylate, neopentyl glycol mono(meth)acrylate, 3-butoxy- 2=Hydroxypropyl (meth)acrylate, 2hydroxy-1-phenylethyl (meth)acrylate, polypropylene glycol mono(meth)acrylate, glycerin mono(meth)acrylate
There are acrylates and the like, and these may be used alone or as a mixture of two or more.

In addition, the N-alkoxymethylated monomer component of the α/β-monoethylenically unsaturated carboxylic acid amide used for graft polymerization with the unsaturated polyester is the hydroxyl of the α/β-monoethylenically unsaturated carboxylic acid. Necessary for crosslinking reactions with alkyl ester components and unsaturated polyester components.

This component is graft-polymerized in a proportion of 5 to 30% by weight, preferably 10 to 20% by weight, in the α/β-monoethylenically unsaturated monomer mixture.

If the content of this component is 5% by weight or less, the crosslinking reaction of the polyester-modified vinyl resin will be insufficient, resulting in a decrease in the solvent resistance of the coating film.

Moreover, if it exceeds 30% by weight, gelation occurs during the graft polymerization reaction, which is not preferable.

Specific examples of this component include N-methoxymethyl (meth)
Acrylamide, N-ethoxymethyl (meth)acrylamide, N-n-propoxymethyl (meth)acrylamide, N-isopropoxymethyl (meth)acrylamide, N-5ee-butoxymethyl (meth)acrylamide, N-t-butoxymethyl ( meth)acrylamide,
α of N-inbutoxymethyl (meth)acrylamide etc.
- N-alkoxymethylated products of β-monoethylenically unsaturated carboxylic acid amide; or N-methylolated products thereof, and the like, and these may be used alone or as a mixture of two or more kinds.

In the present invention, the hydroxyalkyl ester monomer of the α/β-monoethylenically unsaturated carboxylic acid and α
- Monomers other than the N-alkoxymethylated monomer of β-monoethylenically unsaturated carboxylic acid amide are used in combination.

The monomer is used in an amount of 60 to 90% by weight in the monomer mixture.

Specific examples of the monomer include α/β-monoethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (
meth)acrylate, inopropyl(meth)acrylate, n-butyl(meth)acrylate, 5ee-butyl(meth)acrylate, t-butyl(meth)acrylate, isobutyl(meth)acrylate, n-hexyl(
meth)acrylate, 2-ethylhexyl(meth)acrylate, n-octyl(meth)acrylate, Rau・
Alkyl esters of acrylic acid or methacrylic acid such as lyl (meth)acrylate, tridecyl (meth)acrylate, and stearyl (meth)acrylate; other N-
N'-dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)1 acrylate, phenyl methacrylate, benzyl methacrylate, dialkyl esters of fumaric acid such as di-butyl fumarate, styrene, vinyltoluene,
Examples include monomers such as α-methylstyrene, (meth)acrylonitrile, and vinyl acetate.

The above-mentioned monomers can be used singly or in an appropriate combination of two or more depending on the purpose and use of the coating composition.

The polyester-modified vinyl resin contains 2 to 40% by weight of the unsaturated phase polyester and 60 to 40% by weight of the monomer mixture.
98% by weight of a graft polymerization reaction product.

The amount of modification of the unsaturated polyester is 2 to 40% by weight, preferably 3 to 30% by weight.

If it is less than 2% by weight, the excellent flexibility, pigment dispersibility, and coating film appearance of unsaturated polyester cannot be fully demonstrated, and if it is more than 40% by weight, the characteristics of vinyl resin may not be fully exhibited. Hardness, stain resistance, etc. will be impaired.

The polyester modified vinyl resin i used in the present invention is
Manufactured by conventional solution polymerization.

For example, a method in which the remaining monomer (mixture) and a polymerization initiator are dropped into a mixture of unsaturated polyester, part of the monomer (mixture), and a polymerization solvent, and polymerization is performed; There is a method in which polyester, a monomer (mixture), and a polymerization initiator are dropped and polymerized, but there is no particular restriction on the solution polymerization method.

Generally, the polymerization temperature range is about 50 to 150°C, and the polymerization reaction time is about 4 to 12 hours, depending on the temperature.

As the polymerization solvent used in the solution polymerization method, water-soluble or water-miscible solvents are used, such as methyl alcohol, ethyl alcohol, isoflobil alcohol, n-
7'□ Alcohols such as pyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol derivatives such as acetate, diethylene glycol monomethyl ether, ethylene glycol mono Diethylene glycol derivatives such as ethyl ether and diethylene glycol monobutyl ether; esters such as methyl acetate, ethyl acetate, and butyl acetate; ketones such as methyl ethyl ketone and methyl imbutyl ketone; and the like.

These polymerization solvents may be used alone or in an appropriate combination of two or more.

In particular, those having a solubility in water of about 10 to 30% by weight at 20°C are preferred.

The amount of the polymerization solvent used is such that the non-volatile content during production of the polyester modified vinyl resin is 10 to 80% by weight, preferably 20 to 80% by weight.
It is preferable to use it within a range of 70% by weight.

In addition, examples of the polymerization initiator used include pensoyl peroxide, t-butyl perbenzoate, t-
Examples include organic peroxides such as butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, and t-butyl peroctoate, and azo compounds such as azobisisobutyronitrile and azodiynebutyronitrile.

These polymerization initiators may be used alone or in a mixture of two or more thereof.

The polymerization initiator is used in an amount of about 0.1 to 15% by weight based on the nonvolatile content during production of the polyester-modified vinyl resin.

If necessary, chain transfer agents such as dodecyl mercaptan, 2-ethylhexyl thioglycolate, carbon tetrachloride, etc. may be used to adjust the molecular weight.

The chain transfer agent is preferably used in an amount of about 0 to 5% by weight based on the nonvolatile content during production of the polyester-modified vinyl resin.

The hydroxyl value of the polyester-modified vinyl resin of the present invention is 0.
-180, preferably 30-120, and the acid value is 3-40. Preferably it is in the range of 5-30.

When the acid value is less than 3, thermosetting properties are insufficient, resulting in poor coating film hardness, water resistance, corrosion resistance, durability, etc. On the other hand, when the acid value is greater than 40, coating film performance and storage stability are also reduced. .

Moreover, when the hydroxyl value is 10 or less, the crosslinking density decreases and the solvent resistance decreases.

On the other hand, if it is larger than 180, the flexibility will be reduced and the water resistance of the coating will be reduced.

The weight average molecular weight of the polyester modified vinyl resin of the present invention is 40,000 to 200,000. Preferably from 50,000
It is within the range of 150,000.

If the weight average molecular weight is 40,000 or less, the coating performance will be insufficient, while if the weight average molecular weight is 200,000 or more, the smoothness of the coating will be impaired, which is not preferable.

Next, the blocked isocyanate compound used in the present invention is an incyanate compound having two or more isocyanate groups in one molecule, and all of the isocyanate groups are masked with a blocking agent.

The blocked isocyanate compound is necessary for the crosslinking reaction with the polyester-modified vinyl resin, and is characterized by providing the excellent weather resistance and chemical resistance of urethane resins.

The blocked isocyanate compound is a polyisocyanate compound having two or more isocyanate groups in one molecule, such as ethylene diinocyanate, propylene cynonanate, tetramethylene diisocyanate, hexamethylene diisonanate, decamethylene diisocyanate, m -phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1.
5-Naphthylene diisocyanate, 4,4',411
) Riphenylmethane triisocyanate, 4.
4'-diphenylmethane-diisocyanate, 3.3'
- polyinsyanates such as dimethyl-4,4'-diphenylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, inphorone diinocyanate, lysine inocyanate, and excess of the above isocyanate compounds, such as ethylene glycol, propylene Glycol, 1,3-butylene glycol, neopentyl glycol, 2,2,4-trimethylto-3-bentanediol, hexamethylene glycol,
Difunctional or higher functional polyisocyanates obtained by addition reaction with low-molecular polyols such as cyclohexane dimetatool, trimethylolpropane, hexanetriol, glycerin, and pentaerythritol, polyisocyanates with biuret structures, polyisocyanates with allophanate bonds, etc. is an incyanate compound blocked with a blocking agent.

The blocking agents include phenols such as phenol and cresol, alcohols such as methanol, benzyl alcohol, and ethylene glycol monoethyl ether, active methylenes such as methyl acetoacetate and dimethyl malonate, and acid amides such as acetanilide and acetamide. Other imide-based, amine-based, imidazole-based, urea-based, carbamate-based, imine-based, oxime-based, mercaptan-based,
There are sulfite-based, lactam-based, etc.

The crosslinking reaction in the composition of the present invention is carried out by the hydroxyl group in the polyester-modified vinyl resin, the N-alkoxymethyl group in the polyester-modified vinyl resin, and the isocyanate group of the blocked isocyanate compound.

The ratio of the polyester-modified vinyl resin to the flocked isocyanate compound is such that (hydroxyl group in the polyester-modified vinyl resin)/(isocyanate group in the flocked isocyanate compound) -110.1 to 1/1.2 (equivalent ratio). range.

The equivalent ratio is approximately the following weight ratio.

That is, the solid content weight ratio of the polyester modified vinyl resin and the blocked isocyanate compound is approximately 30/70 to
The ratio is 99.510.5.

However, in the present invention, although the N-alkoxymethyl group in the polyester-modified vinyl resin performs a self-crosslinking reaction, it also reacts with a hydroxyl group, so preferably (hydroxyl group in the polyester-modified vinyl resin)/(blocked isocyanate compound) inocyanate group)-110,2-I1
It is preferable to use it within the range of 0.8 (equivalent ratio).

If the amount of the flocked isocyanate compound used is significantly small, the effect of improving the chemical resistance, weather resistance, etc. of the coating film, which is a feature of the present invention, will be poor.

On the other hand, if it becomes significantly large, coating film performance such as water resistance will deteriorate due to unreacted isocyanate groups.

The softening temperature of the mixed resin particles of polyester-modified vinyl resin and blocked inocyanate compound used in the present invention is preferably 30 to 100°C.

More preferably, the temperature is 40 to 80°C. Softening temperature is 30℃
If it is lower than 100°C, the storage stability of the paint tends to deteriorate, and if it is higher than 100°C, the smoothness of the coating film will be insufficient, which is not preferable.

In addition, in the present invention, if necessary, known acid catalysts and dissociation catalysts for promoting the crosslinking reaction between the polyester-modified vinyl resin and the blocked isocyanate compound, as well as epoxy resins, cellulose resins, amino resins, unsaturated polyesters, etc. It is also possible to use one type or two or more types of coating film-forming resins in combination.

Next, a method for producing the water-dispersed thermosetting coating composition of the present invention will be explained.

As a manufacturing method, the usual mechanical pulverization method used in the production of conventional powder paints and slurry paints can also be applied, but if the softening point is low, the stickiness of the resin particles is too high and the resin particles become powdered. This becomes difficult.

Therefore, the water-dispersed thermosetting coating composition of the present invention can be advantageously produced by a special method as described below.

First, a predetermined amount of the mixed resin composition of the polyester-modified vinyl resin and the blocked isocyanate compound, and if necessary, a curing catalyst, a dissociation catalyst, other coating film-forming resins, etc. are dissolved in the water-soluble or water-miscible solvent. A resin solution is obtained, and if necessary, a pigment is added and kneaded and dispersed to obtain a pigment dispersion.

The solvent used in this case is the same as the polymerization solvent used in the solution polymerization method.

The amount used is such that the nonvolatile content of the resin solution or pigment dispersion is in the range of 30 to 80% by weight.

Next, this resin solution or pigment dispersion is emulsified into fine particles in water in an amount such that all of the water-soluble or water-miscible solvent contained therein is dissolved.

The amount of water used at this time is at least 6 times the amount (weight) of the resin solution or pigment dispersion, and is preferably about 40 times the amount (weight) or less in consideration of the mouth-passing process after emulsification. .

The resin solution or pigment dispersion can be emulsified by dropping, pouring, or spraying the solution or dispersion into water under vigorous stirring, or by mixing water and the solution or dispersion using a line mixer. It can be used, but at this time, the temperature of the mixed liquid increases due to stirring, and in order to prevent the resin particles from coalescing or becoming integrated due to the softening of the resin, the mixed liquid must be cooled to a temperature below 30°C. It is preferable to keep it.

The above stirring or mixing using a line mixer+'3 is carried out until the solvent in the emulsion fine particles is transferred into water and resin particles are formed.

In this way, the solvent in the emulsion fine particles is extracted into water, and resin particles are obtained.

The resin particles are separated from the water-solvent mixture by filtration or centrifugation, and if necessary, water washing and separation are repeated a necessary number of times to obtain resin particles in the form of a slurry or a water-containing cake.

In this way, preferably an average particle size of about 1 to 200
Resin particles between μ are obtained.

Furthermore, after adding a surfactant and/or thickener and water to this slurry-like or water-containing cake-like resin particles,
The resin particles are finely pulverized using a dispersing machine normally used for manufacturing paints, such as a sand mill, a ball mill, a disperser, a Sassmeyer mill, and a Sentry mill, so that the average particle diameter is approximately 1 to 1.
Adjust between 50μ.

The thus obtained resin particles of the present invention contain a polyester-modified vinyl resin and a blocked isocyanate compound in each particle.

That is, each particle necessarily contains groups that react with each other when heated, that is, a hydroxyl group, an N-alkoxymethyl group, and an incyanate group.

Therefore, when the composition of the present invention is heated, a coating film having excellent performance can be obtained through crosslinking within the resin particles and crosslinking reactions between the resin particles.

The water-dispersed thermosetting coating composition of the present invention preferably contains the resin particles dispersed in the form of fine particles having an average particle diameter of 1 to 50 μm.

If the average particle diameter is smaller than 1 μm, the cohesiveness of the particles increases, and properties similar to those of water-soluble paints, such as easy foaming during film formation by heating, are undesirable.

On the other hand, if it is larger than 50μ, the resin particles tend to precipitate and coagulate during storage, making it impossible to obtain a smooth coating surface, which is not preferable.

In particular, resin particles having an average particle diameter of 5 to 30 μm are suitable for the present invention because they form a coating material that has excellent storage stability and provides a smooth coating film without foaming.

The composition of the present invention may also contain, if necessary, a curing catalyst, a dissociation catalyst, organic and inorganic coloring and extender pigments commonly used in paints, a temporary rust preventive agent, a flow aid, an antifoaming agent, and a suspending agent. ,
Additives such as fungicides and preservatives, other water-soluble resins, and film-forming resins such as hydrosils and emulsion resins can be included.

As mentioned above, the softening temperature of the resin particles is preferably 30 to 100°C, so it is preferable that components such as pigments that do not melt at the heating film forming temperature in the paint are added to the resin particles in an amount of 50% by weight or less. .

As the surfactant used in the present invention, known surfactants such as nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be used. For example, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alcohol ether, glycerin fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene human oil derivative, holoxy Ethylene alkyl phenyl ether, alkyl phosphate ester, holoxyethylene phosphate ester; anionic surfactants include alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, alkyl sulfosuccinate, N
-Acyl sarcosine salt; As the cationic surfactant, quaternary ammonium salts, pyridinium salts, etc. can be used.

From the viewpoint of dispersion stability of resin particles and coating film performance, nonionic surfactants are preferred, and those having an HLB of 8 to 18 are particularly preferred.

Further, as the above-mentioned thickener used in place of or in combination with these surfactants, those conventionally used in water-based resin paints can be used.

These include, for example, cellulose water-soluble resins such as methyl cellulose, ethyl cellulose, and hydroxyethyl cellulose; polyvinyl alcohol; polyethylene water-soluble resins such as polyethylene glycol ether and polyethylene oxide; Polymers, maleic anhydride copolymer systems such as styrene maleic anhydride copolymers, water-soluble resins, ammonium, amine salts and sodium salts of nialic acid polymers, bentonite, polyvinylpyrrolidone, alginates, polyacrylamide and their partial hydration Examples include decomposition products, naturally occurring water-soluble resins such as casein and gelatin.

The above-mentioned surfactant and/or thickener is added in an amount of 0.01 to 5.0% by weight based on the fine powder resin particles.

If the amount added is less than 0.01% by weight, storage stability, coating workability, etc. will deteriorate, and if it is more than 5.0% by weight, the smoothness, water resistance, etc. of the coating film will be deteriorated. It becomes unsuitable for invention.

Among the above-mentioned thickeners, amine salts of carboxyl group-containing acrylic copolymers are particularly suitable for the present invention because they do not reduce the water resistance of the coating film due to the insolubility of the heated water-drained coating film due to elimination of amines. .

The mixing ratio of water and fine powder resin particles in the coating composition of the present invention is preferably 90-30/10-70 by weight.

When the composition has fewer resin particles than the above mixing ratio, the solid content concentration of the paint is low and the viscosity is low, so the thickness of the normal coating film at one time, for example, 20 to 8
When applied to a thickness of 0μ, phenomena such as sagging occur in the coating film, and to avoid this, several coats are required, causing problems in painting workability.

On the other hand, if there are more resin particles than the above mixing ratio, it will be difficult to make the paint uniform by stirring, kneading, etc. during paint production, and the viscosity characteristics will deviate from the appropriate characteristics for various painting methods such as spray painting and electrostatic painting. Therefore, painting workability tends to be poor and practicality tends to be lowered, which is not preferable.

The water-dispersed thermosetting coating composition of the present invention may be applied using various well-known coating methods such as brush coating, dip coating, spray coating, electrostatic coating, curtain flow coating, shower coating, and roll coating. I can do it.

The conditions for heat curing after coating the coating composition vary depending on the content of crosslinkable functional groups in the composition, film thickness, etc., but are usually heat treated at a temperature of 120 to 200°C for 10 to 40 minutes. By this, a cured coating film can be obtained.

The cured coating film obtained in this way has the flexibility, pigment dispersibility, and excellent appearance of the unsaturated polyester, the hardness and stain resistance of the vinyl copolymer resin, and the urethane resin. It has the excellent weather resistance and chemical resistance that resins have, and also has excellent coating performance without foaming (flanks) that occurs during high-temperature baking.

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

In addition, "part" or "%" represents "weight part" or "weight %."

[Method for producing unsaturated polyester solution]

(1) Unsaturated polyester AI (hereinafter abbreviated as PE-1) 32.6 parts of isophthalic acid and 18.6 parts of adipic acid were placed in a reaction vessel equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introduction tube.
7 parts, fumaric acid 3.0 parts, neopentyl glycol 2
9.0 parts and 16.7 parts of H#-roll propane were charged and reacted at 225°C for about 8 hours in a nitrogen gas atmosphere to give an acid value of 1. ,,! 5. = 111. A resin having a hydroxyl value of 155 and a weight average molecular weight of 6,700 was obtained.

This was diluted with methyl ethyl ketone to a non-volatile content of 60% to give PE-1.

(2) Unsaturated polyester 2 (hereinafter abbreviated as PE-2) In a reaction vessel similar to that in which PE-1 was synthesized, 32.3 parts of isophthalic acid, 15.1 parts of adipic acid, and 3 parts of fumaric acid were added.
．． 0 parts of neopentyl glycol, 22.9 parts of neopentyl glycol, 17.4 parts of trimethylolpropane, and 9.3 parts of glycidyl ester of tertiary synthetic saturated fatty acid (trade name manufactured by Cardular E Nidiel Chemical) were charged, and the mixture was heated under a nitrogen gas atmosphere. 225
After reacting at ℃ for about 8 hours, the acid value was 16.2 and the hydroxyl value was 16.
6, and a resin having a weight average molecular weight of 4,200 was obtained.

This was diluted with methyl ethyl ketone to a non-volatile content of 60% to give PE-2.

(3) Unsaturated polyester &3 (hereinafter abbreviated as PE-3) The same procedure was used except that 32.6 parts of orno-7-talic anhydride was used instead of 32.6 parts of isophthalic acid in PE-1.
The reaction was carried out at 225° C. for about 6 hours in a nitrogen gas atmosphere to obtain a resin having an acid value of 45, a hydroxyl value of 158, and a weight average molecular weight of 2,450.

This was diluted with methyl ethyl ketone to a non-volatile content of 60% to give PE-3.

(4) Unsaturated polyester &4 (hereinafter abbreviated as PE-4) In a reaction vessel similar to that in which PE-1 was synthesized, 36.0 parts of isonotalic acid, 11.5 parts of adipic acid, and 6 parts of fumaric acid were added.
．． 0 parts, neopentyl glycol 34.0 parts, l・4
- Charge 12.5 parts of cyclohexane dimetatool and react at 225°C for about 8 hours in a nitrogen gas atmosphere to obtain an acid value of 7.5, a hydroxyl value of 94, and a weight average molecular weight of 3950.
of resin was obtained.

This was diluted with methyl ethyl ketone to a non-volatile content of 60% to give PE-4.

(5) Unsaturated polyester &5 (hereinafter abbreviated as PE-5) In a reaction vessel similar to that in which PE-1 was synthesized, 16.0 parts of isophthalic acid and 17 parts of methylhexahydrophthalic anhydride were added.
．． 5 parts, adipic acid 14.5 parts, fumaric acid 4.0 parts,
25.0 parts of neopentyl glycol, 10.0 parts of trimethylolethane, and 13.0 parts of hydrogenated bisphenol A were charged and reacted at 225°C for about 16 hours in a nitrogen gas atmosphere to obtain an acid value of 12.3 and a hydroxyl value of 120. , and a resin having a weight average molecular weight of 9,300 was obtained.

This was diluted with methyl ethyl ketone to a non-volatile content of 60% to give PE-5.

[Method for producing polyester modified vinyl resin solution] (1)
Methyl ethyl ketone 24 was added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube, and a nitrogen gas introduction tube.
After adding 9 parts and raising the temperature to 80° C., the following monomer, unsaturated polyester and initiator mixture was added dropwise over 3 hours.

126.5 parts of methyl methacrylate, 10 parts of 2-ethylhexyl acrylate, 111.5 parts of 2-ethylhexyl methacrylate, 45.5 parts of 2-hydroxyethyl methacrylate, 5 parts of acrylic acid, 75 parts of N-n-butoxymethylacrylamide part, the unsaturated polyester (
PE-1) 126.5 parts, azobisisobutyronitrile 6 parts.

After finishing dropping, add 1 part of azobisisobutyronitrile,
After raising the reaction temperature to 87°C, the reaction was carried out for 4 hours, resulting in an acid value of 10.0, a hydroxyl value of 110, and a weight average molecular weight of 78.
000. A resin solution with a nonvolatile content of 59.8% was obtained, and the softening temperature of the resin was about 70 to 74°C.

This was named PE-NY-1.

(2) Put 315 parts of methyl ethyl ketone into the same reaction vessel as the one used to synthesize PE-NV-1, raise the temperature to 80°C, and then dropwise add the following monomer, unsaturated polyester, and initiator mixture over 3 hours. did.

150 parts of methyl methacrylate, 75 parts of styrene, 165 parts of ethyl acrylate, 25 parts of 2-hydroxyethyl methacrylate, 10 parts of acrylic acid, 50 parts of N-n-butoxymethylacrylamide, 25 parts of the unsaturated polyester (PE-2), azo 6 parts bisisobutyronitrile.

After the dropwise addition, 1 part of azobisisobutyronitrile was added, the reaction temperature was raised to 87°C, and the reaction was carried out for 4 hours, resulting in an acid value of 14.4, a hydroxyl value of 41, and a weight average molecular weight of 104.
000 and a resin solution with a nonvolatile content of 59.6% was obtained,
The softening temperature of the resin was about 70-72°C.

This was named PE-NV-2.

(3) Put 315 parts of methyl ethyl ketone into a reaction vessel similar to that in which PE-NV-1 was synthesized, raise the temperature to 80°C, and then add the following monomer, unsaturated polyester, and initiator mixture for 3 hours. dripped.

125 parts of methyl methacrylate, 62.5 parts of styrene,
82.5 parts of ethyl acrylate, 7.5 parts of 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate
) 77.5 parts, 2-hydroxyethyl methacrylate 3
5 parts, 10 parts of acrylic acid, 75 parts of N-n-butoxymethylacrylamide, the unsaturated polyester (PE-3)
) 25 parts, azobisisobutyronitrile 6 parts.

After the dropwise addition was completed, 1 part of azobisisobutyronitrile was added, the reaction temperature was raised to 87°C, and the reaction was carried out for 4 hours, resulting in an acid value of 14. A resin solution having an O1 hydroxyl value of 44, an O1 weight average molecular weight of 95,500, and a nonvolatile content of 59.5% was obtained.

The softening temperature of the resin was about 74-76°C.

This was named PE-NV-3.

(4) Put 7300 parts of methyl ethyl keto into a reaction vessel similar to that in which PE-NY-1 was synthesized, and adjust the temperature to 80°C.
After raising the temperature to 100 ml, the following monomer, unsaturated polyester and initiator mixture was added dropwise over 3 hours.

75 parts of methyl methacrylate, 140 parts of styrene, 165 parts of ethyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 10 parts of acrylic acid, N
-50 parts of n-butoxymethylacrylamide, 50 parts of the unsaturated polyester (PE-1), and 6 parts of azobisisobutyronitrile.

After finishing dropping, add 1 part of azobisisobutyronitrile,
After raising the reaction temperature to 87°C, the reaction was carried out for 4 hours, and the acid value was 16.2, the hydroxyl value was 40.5, and the weight average molecular weight was 6.
1500 and a non-volatile content of 57.5%, the softening temperature of the resin was approximately 66-68°C.

This was named PE-NV-4.

(5) Into the same reaction vessel as the one in which PE-NY-1 was synthesized, 7300 parts of methyl ethyl keto was raised to 80°C, and then the following monomer, unsaturated polyester, and initiator mixture was added dropwise over 3 hours. did.

60 parts of methyl methacrylate, 145 parts of styrene, 150 parts of ethyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 10 parts of acrylic acid, 75 parts of N-n-butoxymethylacrylamide, the unsaturated polyester (PE-2) 50 parts, 6 parts of azobisisobutyronitrile.

After finishing dropping, add 1 part of azobisisobutyronitrile,
After raising the reaction temperature to 87°C, the reaction was carried out for 4 hours, and the acid value was 16.8, the hydroxyl value was 42.5, and the weight average molecular weight was 7.
A resin solution of 2100 and 57.3% non-volatile content was obtained, and the softening temperature of the resin was about 64-67°C.

This was named PE-NV-5.

(6) Put 260 parts of methyl ethyl ketone into the same reaction vessel as used to synthesize PE-NV-1, raise the temperature to 80°C, and then dropwise add the following monomer, T41 polyester and initiator mixture over 3 hours. did.

105 parts of methyl methacrylate, 70 parts of styrene, 125 parts of ethyl acrylate, 15 parts of ronitrile, 30 parts of 2-hydroxypropyl methacrylate, 5 parts of acrylic acid, 40 parts of N-n-butoxymethylacrylamide, the unsaturated polyester (PE- 1) 110
parts, 7 parts of azobisisobutyronitrile.

After the dropwise addition, 1 part of azobisisobutyronitrile was added, the reaction temperature was raised to 87°C, and the reaction was carried out for 4 hours, resulting in an acid value of 103, a hydroxyl value of 77, and a weight average molecular weight of 875.
00, and a resin solution with a nonvolatile content of 60.0% was obtained.

The softening temperature of the resin was about 70-73°C.

This was named pE-NV-6.

(7) Put 249 parts of methyl ethyl ketone into a reaction vessel similar to that in which PE-NV-1 was synthesized, raise the temperature to 80°C, and then add the following monomer, vesicle-coated polyester, and initiator mixture for 3 hours. dripped over the entire area.

126.5 parts of methyl methacrylate, 10 parts of 2-ethylhexyl acrylate, 111.5 parts of 2-ethylhexyl methacrylate, 45.5 parts of 2-hydro-4xyethyl methacrylate, 5 parts of acrylic acid, N-n-butoxymethyl 75 parts of acrylamide, 126.5 parts of the unsaturated polyester (PE-4), and 6 parts of azobisisobutyronitrile.

After the dropwise addition, 1 part of azobisin butyronitrile was added, the reaction temperature was raised to 87°C, and the reaction was carried out for 4 hours, resulting in an acid value of 9.7, a hydroxyl value of 92, and a weight average molecular weight of 613.
00. A resin solution with a nonvolatile content of 59.2% was obtained.

The softening temperature of the resin was about 67-70°C.

This was designated as PE-NV-7.

(8) Put 294 parts of methyl ethyl ketone into the same reaction vessel as the one used to synthesize PE-NV-1, raise the temperature to 80°C, and then dropwise add the following monomer, unsaturated polyester, and initiator mixture over 3 hours. did.

122.5 parts of methyl methacrylate, 155 parts of styrene, 77.5 parts of n-butyl acrylate, 30 parts of 2-hydroxyethyl acrylate, 5 parts of methacrylic acid, N-t
-50 parts of butoxymethylacrylamide, 60 parts of the unsaturated polyester (PE 1), and 7 parts of azobisisobutyronitrile.

After the dropwise addition, 1 part of azobisinobutyronitrile was added, the reaction temperature was raised to 87°C, and the reaction was carried out for 4 hours, resulting in an acid value of 7.8, a hydroxyl value of 68, and a weight average molecular weight of 804.
00. A resin solution with a nonvolatile content of 59.8% was obtained.

The softening temperature of the resin was about 72-75°C.

This was named PE-NV-8.

(9) Put 7317 parts of methyl ethyl keto into a reaction vessel similar to that in which PE-NY-1 was synthesized, raise the temperature to 80°C, and then dropwise add the following monomer, unsaturated polyester, and initiator mixture over 3 hours. did.

155 parts of isobutyl methacrylate, 104 parts of styrene, 45 parts of n-butyl acrylate, 55 parts of 2-hydroxypropyl methacrylate, 6 parts of methacrylic acid, 35 parts of 2-ethylhexyl methacrylate, 75 parts of N-n-butoxymethylacrylamide, 25 parts of saturated polyester (PE-2), 7. azobisisobutyronitrile.
Part 5.

After the addition, 1.2 parts of azobisisobutyronitrile was added, the reaction temperature was raised to 87°C, and the reaction was carried out for 4 hours, resulting in an acid value of 8.2, a hydroxyl value of 79, and a weight average molecular weight of 6.
5300, and a resin solution with a nonvolatile content of 60.1% was obtained.

The softening temperature of the resin was about 64-67°C.

This was designated as PE-NV-9.

(10) 317 parts of methyl ethyl ketone was placed in a reaction vessel similar to that in which PE-NV-1 was synthesized, and the temperature was lowered to 8.
After raising the temperature to 0° C., the following monomer, unsaturated polyester and initiator mixture was added dropwise over 3 hours.

140 parts of n-butyl methacrylate, 149 parts of styrene, 50 parts of ethyl acrylate, 55 parts of 2-hydroquinepropyl methacrylate, 6 parts of methacrylic acid, 75 parts of N-n-butoxymethylacrylamide, 25 parts of the unsaturated polyester (PE-2) parts, 7.5 parts of azobisisobutyronitrile.

After the dropwise addition, 1.2 parts of azobisisobutyronitrile was added, the reaction temperature was raised to 87°C, and the reaction was carried out for 4 hours, resulting in an acid value of 8.3, a hydroxyl value of 78, and a weight average molecular weight of 6.
1800, and a resin solution with a nonvolatile content of 60.0% was obtained.

The softening temperature of the resin was about 70-73°C.

This is PE-NV-10.

(11) 249 parts of methyl ethyl ketone was placed in a reaction vessel similar to that in which PE-NV-1 was synthesized, and after raising the temperature to 80°C, the following monomer, unsaturated polyester, and initiator mixture were added dropwise over 3 hours. .

126.5 parts of methyl methacrylate, 110 parts of 2-ethylhexyl acrylate, 111.5 parts of 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate
) 45.5 parts, acrylic acid 5 parts, Nt-butoxymethylacrylamide 75 parts, the unsaturated polyester (P
E-5) 126.5 parts, azobisisobutyronitrile 6
Department.

After the dropwise addition was completed, 1 part of azobisisobutyronitrile was added, the reaction temperature was raised to 87°C, and the reaction was carried out for 4 hours until the acid value reached 10. O1 hydroxyl value 98, weight average molecular weight 87
500 and a nonvolatile content of 59.2%.

The softening temperature of the resin was 71-74°C.

This was designated as PE-NV-11.

(12) Put 7307 parts of methyl ethyl keto into a reaction vessel similar to that in which PE-NV-1 was synthesized, and lower the temperature to 8.
After raising the temperature to 0° C., the following monomer, unsaturated polyester and initiator mixture was added dropwise over 3 hours.

135 parts of methyl methacrylate, 25 parts of vinyl acetate, 80 parts of ethyl acrylate, 1 part of n-butyl methacrylate
30 parts, 45 parts of 2-hydroxyethyl methacrylate,
5 parts of methacrylic acid, 40 parts of N-n-butoxymethylacrylamide, 40 parts of the unsaturated polyester (PE-2)
parts, 7 parts of azobisin butyronitrile.

After the dropwise addition, 1.2 parts of azobisisobutyronitrile was added, the reaction temperature was raised to 87°C, and the reaction was carried out for 4 hours, resulting in an acid value of 7.4, a hydroxyl value of 77, and a weight average molecular weight of 6.
2500, and a resin solution with a nonvolatile content of 60.2% was obtained.

The softening temperature of the resin was 69 to 71°C.

This was designated as PE-NY-12.

(13) Put 7287 parts of methyl ethyl keto into a reaction vessel similar to that in which PE-NV-1 was synthesized, and lower the temperature to 8.
After raising the temperature to 0° C., the following monomer, unsaturated polyester and initiator mixture was added dropwise over 3 hours.

75 parts of n-butyl methacrylate, 160 parts of styrene,
85 parts of ethyl acrylate, 35 parts of dibutyl fumarate,
35 parts of 2-hydroquinepropyl methacrylate, 5 parts of acrylic acid, 35 parts of N-butoxymethylacrylamide
parts, 70 parts of the unsaturated polyester (PE-1), and 7 parts of azobisisobutyronitrile.

After the dropwise addition, 1.2 parts of azobisinbutyronitrile was added, the reaction temperature was raised to 87°C, and the reaction was carried out for 4 hours, resulting in an acid value of 9.3, a hydroxyl value of 69, and a weight average molecular weight of 7.
9300, and a resin solution with a nonvolatile content of 59.7% was obtained.

The softening temperature of the resin was 69-72°C.

This is PE-NY-13 to I.

04) 284 parts of methyl ethyl ketone was placed in a reaction vessel similar to that in which PE-NY-1 was synthesized, the temperature was raised to 80°C, and the following monomer, unsaturated polyester, and initiator mixture was added dropwise over 3 hours. .

190 parts of methyl methacrylate, 75 parts of inbutyl methacrylate, 85 parts of ethyl acrylate, 30 parts of 2-ethylhexyl methacrylate, 15 parts of 2-hydroxyethyl acrylate, 5 parts of methacrylic acid, 25 parts of N-n-butoxymethylacrylamide, 75 parts of saturated polyester (pE-2), 6 parts of azobisisobutyronitrile
Department.

After the dropwise addition, 1.2 parts of azobisin butyronitrile was added, the reaction temperature was raised to 87°C, and the reaction was carried out for 4 hours, resulting in an acid value of 8.2, a hydroxyl value of 53, and a weight average molecular weight of 6.
8800, and a resin solution with a nonvolatile content of 59.8% was obtained.

The softening temperature of the resin was 70-72°C.

This was designated as PE-NV-14.

7300 parts of methyl ethyl keto was placed in a reaction vessel similar to that in which PE-NV-1 was synthesized, and after raising the temperature to 80°C, the following monomer, unsaturated polyester, and initiator mixture was added dropwise over 3 hours. .

155 parts of methyl methacrylate, 80 parts of styrene, 40 parts of methyl acrylate, 70 parts of ethyl acrylate, 25 parts of lauryl methacrylate, 25 parts of 2-hydroxypropyl methacrylate, 5 parts of acrylic acid, 50 parts of N-n-butoxymethylacrylamide, the above unsaturated 50 parts of polyester (PE-2), 6 parts of azobisisobutyronitrile.

After the dropwise addition, 1 part of azobisisobutyronitrile was added, the reaction temperature was raised to 87°C, and the reaction was carried out for 4 hours, resulting in an acid value of 8.7, a hydroxyl value of 52, and a weight average molecular weight of 701.
00, and a resin solution with a nonvolatile content of 59.9% was obtained.

The softening temperature of the resin was 71-74°C.

This was designated as PE-NV-15.

[Solvent replacement method for flocked isocyanate compound] When a blocked isocyanate compound containing a hydrophobic solvent is used, the solvent in the emulsion fine particles is not extracted into water and remains in the resin particles in the process of forming resin particles. For,
This is not preferable because the resin particles coalesce or become integrated, which impairs stability.

Therefore, the blocked incyanate compound was subjected to solvent substitution using the method described below, and was used in the present invention.

B-82ONSUC (manufactured by Takeda Pharmaceutical Co., Ltd.) Product name: Effective NCO 4.3%, nonvolatile content 60% (solvent Nis-Persol 1500/butyl acetate)] was placed in a vacuum dryer at 440°C and vacuum dried for 2 days. (Non-volatile content 92
．． 6%) Add methyl ethyl ketone to this to reduce the nonvolatile content to 6%.
It was diluted to 0% and designated as NGO-A.

Example 1 1 part of titanium dioxide was added to 24 parts of resin solution (PE-NV-1).
Add 2 parts and 4 parts of methyl ethyl ketone, and grind with a sand mill.
After kneading and dispersing to 0μ or less (measured with a grind gauge, the same is true for 2 or less), 30 parts of resin solution (PE-NY-1), 26 parts of flocked isocyanate compound (NCO-A), and 0.5 parts of dibutyltin dilaurate (dissociation catalyst). 1 part and 3.5 parts of methyl ethyl ketone were added and mixed with stirring to obtain a uniform pigment dispersion.

This was dropped into 2000 parts of water at a water temperature of 15° C. under high speed stirring to emulsify the pigment dispersion and extract the solvent into the water to form resin particles.

After that, filtration and water washing were repeated, and the average particle size was approximately 10.
A water-containing cake of resin particles with a particle size of 0μ and a water content of about 50% was obtained.

Add 40 parts of nonionic surfactant to 100 parts of this water-containing cake.
% aqueous solution (trade name Emuldan 9301 manufactured by Kao Atlas Co., Ltd., HLB 15.1), 2 parts of a 10% aqueous solution of an alkali salt thickener of acrylic acid copolymer were added, and the mixture was dispersed and kneaded with a sand mill. The resin particles were pulverized to obtain a slurry paint having an average particle diameter of 16 μm and a pH of 7.6.

Example 2 1 part of titanium dioxide was added to 24 parts of resin solution (PE-NV-2).
Add 2 parts and 74 parts of methyl ethyl keto, and grind with a sand mill.
After kneading and dispersing to 0μ or less, resin solution (PE-NV-2)
48.5 parts of blocked isocyanate compound (trade name Kleran U-I6109, manufactured by Bayer AG), 0.5 parts of dibutyltin dilaurate (dissociation catalyst), and 3.5 parts of methyl ethyl ketone were added and mixed with stirring. A uniform pigment dispersion was obtained.

All of the following operations were carried out in the same manner as in Example I to obtain a slurry-like paint having resin particles with an average particle diameter of 17 μm and a pH of 7.5.

Example 3 1 part of titanium dioxide was added to 24 parts of resin solution (PE-NV-3).
Add 2 parts and 74 parts of methyl ethyl keto, and mix with a ball mill.
After kneading and dispersing the resin solution (PE-NV-3)
Add 50 parts of blocked isocyanate compound (trade name: Kleran U-I6109, manufactured by Bayer AG), 0.5 parts of dibutyltin dilaurate (dissociation catalyst), and 3.5 parts of methyl ethyl ketone, and stir and mix to uniformly disperse the pigment. It was made into a liquid.

This was sprayed into 3000 parts of water at a water temperature of 20° C. under high speed stirring to emulsify the pigment dispersion and extract the solvent into the water to form resin particles.

After that, filtration and water washing were repeated, and the average particle size was 150 μm.
A resin particle water-containing cake with a water content of about 50% was obtained.

Add 40 parts of nonionic surfactant to 100 parts of this water-containing cake.
% aqueous solution (trade name: Emulgen 910.1, manufactured by Oh Atlas Co., Ltd., HLB 12.2) and 4 parts of a thickener (5% aqueous solution of hydroxyethyl cellulose) were added, and dispersed and kneaded in a ball mill to form resin particles. was finely pulverized to obtain a slurry paint having an average particle size of 16 μm and a pH of 7.4.

Example 4 1 part of titanium dioxide was added to 24 parts of resin solution (PE-NV-4).
2 parts, flow aid (trade name: Modaflow: manufactured by Monsanto)
After adding 0.5 parts of methyl ethyl ketone and 3.5 parts of methyl ethyl ketone, kneading and dispersing the resin solution (PE-NV
-4) 37 parts, flocked isocyanate compound (NCO
-A) 19 parts, dibutyltin dilaurate (dissociation catalyst)
0.5 parts of methyl ethyl ketone and 3.5 parts of methyl ethyl ketone were added thereto and mixed with stirring to obtain a uniform pigment dispersion.

All of the following operations were carried out in the same manner as in Example 1 to obtain a slurry-like paint having resin particles with an average particle diameter of 15 μPH7.5.

Example 5 1 part of titanium dioxide was added to 24 parts of resin solution (PE-NY-5).
2 parts, flow aid (trade name: Modaflow: manufactured by Monsanto)
After adding 0.5 parts of methyl ethyl ketone and 3.5 parts of methyl ethyl ketone, kneading and dispersing the resin solution (PE-NV
-s), 7.0 parts of a flocked isocyanate compound (trade name Fulleran [J-I6109: manufactured by Bayer AG), 0.5 parts of dibutyltin dilaurate (dissociation catalyst), and 3.5 parts of methyl ethyl ketone were added and mixed with stirring. A uniform pigment dispersion was obtained.

All of the following operations were carried out in the same manner as in Example 1 to obtain a slurry-like paint having resin particles with an average particle diameter of 17 μm and a pH of 7.6.

Example 6 1 part of titanium dioxide was added to 24 parts of resin solution (pg-NV-6).
3 parts, 0.5 parts of flow aid (Modaflow) and 74 parts of methyl ethyl keto were added, and after kneading and dispersing to 10μ or less with a sand mill, 69.5 parts of resin solution (PENV-6), blocked inocyanate compound (trade name) Crelan U-I6
109: Bayer) 10.5 parts, dibutyltin dilaurate (dissociation catalyst) 0.5 parts, methyl ethyl ketone 3
．． 5 parts were added and stirred and mixed to obtain a uniform pigment dispersion.

All of the following operations were carried out in the same manner as in Example 1 to obtain a slurry-like paint having resin particles with an average particle size of 18 μm and a pH of 7.7.

Example 7 1 part of titanium dioxide was added to 24 parts of resin solution (PE-NV-7).
Add 2 parts and 4 parts of methyl ethyl ketone, and grind with a sand mill.
After kneading and dispersing to 0 μ or less, resin solution (PE-NV-7) 3
0 parts, flocked isocyanate compound (the above NGO-A
) 26 parts, dibutyltin dilaurate (dissociation catalyst) 0.
5 parts and 3.5 parts of methyl ethyl ketone were added and mixed with stirring to obtain a uniform pigment dispersion.

All of the following operations were carried out in the same manner as in Example 1 to obtain a slurry-like paint having an average resin particle diameter of 17 μm and a pH of 7.8.

Example 8 1 part of titanium dioxide was added to 24 parts of resin solution (PE-NY-8).
3 parts, 0.5 parts of flow aid (Modaflow) and 4 parts of methyl ethyl ketone were added, and after kneading and dispersing in a sand mill to a size of 10μ or less, 46.5 parts of resin solution (PE-NV-8), 46.5 parts of blocked isocyanate compound (described above) were added. Kurera 7U-I
6109), 0.5 parts of dibutyltin dilaurate (dissociation catalyst), and 3.5 parts of methyl ethyl ketone,
A uniform pigment dispersion was obtained by stirring and mixing.

All of the following operations were carried out in the same manner as in Example 1 to obtain a slurry-like paint having resin particles with an average particle size of 15 μm and a pH of 7.6.

Example 9 1 part of titanium dioxide was added to 24 parts of resin solution (PE-NY-9).
3 parts, 0.5 parts of flow aid (the above-mentioned Modaflow) and 4 parts of methyl ethyl ketone were added, and after kneading and dispersing in a sand mill to a size of 10μ or less, 45.5 parts of the resin solution (PE-NV-9), 45.5 parts of the flocked isocyanate compound (the above-mentioned Kurera 7U-I
6109), 0.5 parts of dibutyltin dilaurate (dissociation catalyst), and 3.5 parts of methyl ethyl ketone were added and mixed with stirring to obtain a uniform pigment dispersion.

All of the following operations were performed in the same manner as in Example 1 to obtain a slurry-like paint having resin particles with an average particle diameter of 17 μm and a pH of 7.7.

Example 10 24 parts of resin solution (P E NV-10), 13 parts of titanium dioxide, 0.5 parts of flow aid (Modaflow) and 4 parts of methyl ethyl ketone were added, and the mixture was mixed with a sand mill to give 1.
After kneading and dispersing to below 0μ, resin solution (PE-NV-10)
47.5 parts, blocked isocyanate compound (the above Fulleran U-46109) 8.7 parts, dibutyltin dilaurate (dissociation catalyst) 0.5 parts, methyl ethyl ketone 3.
5 parts were added and stirred and mixed to obtain a uniform pigment dispersion.

All of the following operations were carried out in the same manner as in Example 1 to obtain a slurry-like paint having resin particles with an average particle size of 16 μm and a pH of 7.5.

Example 11 To 24 parts of resin solution (PE-NV-11), 12 parts of titanium dioxide and 4 parts of methyl ethyl ketone were added, and after kneading and dispersing in a sand mill to a size of 10μ or less, the resin solution (PE-NV-11) was added.
11) Add 30 parts, 26 parts of blocked isocyanate compound (the above NGO-A), 0.5 parts of dibutyltin dilaurate (dissociation catalyst), and 3.5 parts of methyl ethyl ketone,
A uniform pigment dispersion was obtained by stirring and mixing.

All of the following operations were carried out in the same manner as in Example 1 to obtain a slurry-like paint having resin particles with an average particle size of 16 μm and a pH of 7.5.

Example 12 To 24 parts of resin solution (PE-NV-12), 13 parts of titanium dioxide, 0.5 parts of flow aid (Modaflow) and 74 parts of methyl ethyl keto were added, and after kneading and dispersing in a sand mill to a size of 10μ or less, the resin Solution (PE-NV-12) 45
．． 5 parts, blocked inocyanate compound (the above fulleran [J-I6109) 10.5 parts, dibutyltin dilaurate (dissociation catalyst) 0.5 parts, methyl ethyl ketone 3.5 parts
1 part and stirred and mixed to obtain a uniform pigment dispersion.

All of the following operations were carried out in the same manner as in Example 1 to obtain a slender IJ-like paint having an average resin particle diameter of 18 μm and a pH of 7.7.

Example 13 To 24 parts of resin solution (PE-NV-13), 13 parts of titanium dioxide, 0.5 parts of flow aid (Modaflow) and 4 parts of methyl ethyl ketone were added, and the mixture was milled to 10 μm using a sand mill.
After kneading and dispersing the following, resin solution (PE-NY-13)
45.5 parts, 10.5 parts of flocked isocyanate compound (the above Fulleran U-I6109), 0.5 parts of dibutyltin dilaurate (dissociation catalyst), 3.
5 parts were added and stirred and mixed to obtain a uniform pigment dispersion.

All of the following operations were carried out in the same manner as in Example 1 to obtain a streak-like coating material having an average resin particle diameter of 17 μm and a pH of 7.7.

Example 14 To 24 parts of resin solution (PE!-NV-14), 13 parts of titanium dioxide, 0.5 parts of flow aid (Modaflow) and 4 parts of methyl ethyl ketone were added, and after kneading and dispersing in a sand mill to a size of 10μ or less, Resin solution (PE-NV-14) 4
7 parts, blocked isocyanate compound (the above-mentioned Fleran U
-I6109), 0.5 parts of dibutyltin dilaurate (dissociation catalyst), and 3.5 parts of methyl ethyl ketone,
A uniform pigment dispersion was obtained by stirring and mixing.

All of the following operations were carried out in the same manner as in Example 1 to obtain a slurry-like paint having resin particles with an average particle diameter of 15 μm and a pH of 7.5.

Example 15 13 parts of titanium dioxide, 0.5 parts of flow aid (Modaflow) and 74 parts of methyl ethyl keto were added to 24 parts of resin solution (PE-NY-i 5 ), and 1
After kneading and dispersing to 0μ or less, resin solution (PE-NV-1s
), 7.5 parts of a blocked isocyanate compound (the above-mentioned Fulleran U-I6109), 0.5 parts of dibutyltin dilaurate (dissociation catalyst), and 3.5 parts of methyl ethyl ketone were added and stirred and mixed to form a uniform pigment dispersion. And so.

All of the following operations were carried out in the same manner as in Example (2) to obtain a slurry-like paint having an average resin particle diameter of 16 μm and a pH of 7.8.

Comparative Example 1 Polyester modified vinyl resin solution used in Example 1 (
From the composition of PE-NV-1), N-butoxymethylacrylamide and unsaturated polyester for modification (PE-NV-1)
The reaction was carried out in the same manner as in polyester-modified vinyl resin solution production (1) except that the monomer composition except for -1) was changed to 199 parts of methyl ethyl ketone as the polymerization solvent, and the acid value was 10.7, the hydroxyl value was 60, Number average molecular weight 210
A resin solution with a nonvolatile content of 0 and 60.5% was obtained.

To 24 parts of the resin solution, 12 parts of titanium dioxide and 4.5 parts of methyl ethyl ketone were added, and after kneading and dispersing with a sand mill to a size of 10 μm or less, 36 parts of the resin solution and an average degree of condensation of 2.
5. 20 parts of a 60% methyl ethyl ketone solution of a butylated methylol melamine resin with a degree of etherification of 2.5 and a water-soluble component of 1% or less and 3.5 parts of methyl ethyl ketone were added and mixed with stirring to obtain a uniform pigment dispersion.

In the same manner as in Example 1, the average particle size was 14μ,
A slurry paint having a pH of 7.5 was obtained.

Comparative Example 2 Polyester modified vinyl resin solution used in Example 2 (
From the composition of PE-NY-2), N-butoxymethylacrylamide and unsaturated polyester for modification (PE-NY-2)
The reaction was carried out in the same manner as in polyester-modified vinyl resin solution production (2) except that the monomer composition except for -2) and the amount of methyl ethyl ketone as the polymerization solvent was changed to 283.5 parts. A resin solution having a value of 42, a number average molecular weight of 1800, and a nonvolatile content of 59.6% was obtained.

To 24 parts of the resin solution, 12 parts of titanium dioxide and 4.5 parts of methyl ethyl ketone were added, and after kneading and dispersing in a ball mill to a size of 10μ or less, 42 parts of the resin solution and a blocked isocyanate resin (trade name: Kleran U-I6109: Bayer AG) were added. io part), 0.5 part of dibutyltin dilaurate (dissociation catalyst), and 7 parts of methyl ethyl ketone were added and mixed with stirring to obtain a uniform pigment dispersion.

The following steps were carried out in the same manner as in Example 3, with an average particle size of 15μ,
A slurry paint having a pH of 7.5 was obtained.

Comparative Example 3 Polyester modified vinyl resin solution used in Example 1 (
The reaction was carried out in the same manner as in polyester-modified vinyl resin solution production (1), except that the unsaturated polyester for modification (PE-1) was removed from the composition of PE-NV-1), and the acid value was 11.6. A resin solution having a hydroxyl value of 54, a number average molecular weight of 1700, and a nonvolatile content of 60.6% was obtained.

To 24 parts of the resin solution, 12 parts of titanium dioxide and 4.5 parts of methyl ethyl ketone were added, and after kneading and dispersing in a ball mill to a size of 10 μm or less, 56 parts of the resin solution and 3.5 parts of methyl ethyl ketone were added and mixed with stirring to form a uniform mixture. A pigment dispersion was prepared.

The following steps were carried out in the same manner as in Example 1, with an average particle size of 15 μm and P
A slurry paint of H7.4 was obtained.

The slurry paint prepared in each of the above Examples and Comparative Examples was spray-painted onto a polished mild steel plate, preheated at 90°C for 10 minutes, and then heated and dried at each predetermined temperature to form a coating film with a thickness of approximately 35 μm. Formed.

Table 1 shows the heating drying conditions and physical property test results for the coating film.

Visual Judgment 60 Degree Specular Gloss Value Using a Mitsubishi Pencil Uni, apply it to the paint film at a 45° angle, press gently forward, and check the hardness of the pencil so that no traces of the pencil will be left on the paint film.

Double eye tape peeling test.

By Erichsen test machine.

According to JIS-540016, 13, 3B method.

Ethyl acetate rubbing test) 50 times ◎No abnormalities ○There are some scratches and scratches ×Glossy marks represent dogs.

Moisture resistance test (50°C, 97%RH<) After 200 hours, goban tape peeling test ◎ 100/100~90/100 0 89/100~60/100 X 59/100~ O/100 Acid resistance test: 5 % sulfuric acid aqueous solution at 20° C. for 24 hours, the appearance of the coating film and the occurrence of flakes were determined.

Alkali resistance test: After immersing in a 3% caustic soda aqueous solution at 20° C. for 48 hours, the appearance of the coating film and the occurrence of flakes are determined.

Cold and heat cycle test knee After immersing in a dry ice-methanol solution at 40°C for 15 minutes, the test piece is taken out and immediately immersed in warm water at 60°C for 15 minutes.

Thereafter, the test piece is taken out, and after being left at room temperature for 10 minutes, the appearance of the paint film on the test piece (cracks in the paint film) is checked, and if there are no abnormalities, the test is considered to have passed the first cycle.

Regarding the cold/heat resistance cycle test, the slurry paint prepared in each example and comparative example was coated with Emalon (:'El)-70 (trade name of Inu Nippon Toyo Co., Ltd., urethane electrocoating paint) using an air spray coating method. The test was carried out using a coated steel plate that was electrodeposited under the following conditions, heated and dried, coated on a zinc phosphate chemically treated dull steel plate, and baked.

Electrodeposition film thickness 18μ Coating voltage 250V Current application time 2 minutes Baking time ISO℃ x 20 minutes (Note 12) Gloss after accelerated weathering test: JIS-D-0
205, 7, 6, accelerated weathering test (test conditions: Sunshine Carbon Weather Meter) Gloss measurement (60 degree specular gloss value) after 1000 hours (Note 9) 1) (Note 10) (Note 1 (Note 8) ( Note 1) (Note 2) (Note 3) (Note 4) (Note 5) (Note 6) (Note 7) It is clear from the above comparison test result table that the coating film obtained from the coating composition of the present invention was It does not foam when heated and dried, and has excellent impact resistance, chemical resistance, weather resistance, and cold/heat cycle resistance, and other physical and chemical properties are also superior to comparative examples. there were.

Claims (1)

[Scope of Claims] 1 (AXi) An unsaturated compound having an acid value of 50 or less, a hydroxyl value of 50 to 250, and a weight average molecular weight of 2,000 to 120,000, containing 1 to 10% by weight of α/β-unsaturated dicarboxylic acid as one of the constituent components. saturated polyester
......2 to 40% by weight, (*
+ N-alcoquine methylated monomer...5
~30% by weight ←→ A monomer mixture consisting of 60 to 90% by weight of α/β-monoethylenically unsaturated monomers other than the above (a) and (b). ...98 to 60% by weight, obtained by graft polymerization with a hydroxyl value of 10 to 180
, acid value 3-40. Weight average molecular weight 40000-2000
0.00 polyester-modified vinyl resin and (B) a block inocyanate compound.
．． A water-dispersible thermosetting coating composition consisting of 0% by weight of surfactant and/or thickener and the required amount of water. 2 The mixing ratio of the component (4) and the component (B) is [
The water according to claim 1, wherein the ratio is such that [hydroxyl group in component A]/[isocyanate group in component (B)] = 110.1 to 1/1.2 (equivalent ratio). Dispersed thermosetting coating composition.