JPS5846232B2 - 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-dispersed thermosetting coating composition that has excellent storage stability and forms a coating film that has excellent corrosion resistance, impact resistance, corrosion 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 as easy to apply as conventional solvent-based coatings, and have excellent coating film smoothness and a difficult-to-image finished appearance.
There were problems in use, such as difficulty in coating a thin film of 0 μm or less.

Furthermore, among water-based paints, water-lubricant paints have a low solid content concentration during coating, 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 coating film durability, chemical resistance, etc. 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, polyester resins, epoxy resins, alkyd resins, etc. are known as resins used in such slurry paints, but they are especially important for stability during storage, smoothness of the coating film, and finish. Acrylic resin and polyester resin are said to be preferable 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 crosslinking agent, if a thick film is applied, foaming (flanks) may occur during baking, so this has a drawback in terms of painting workability. I needed to.

Additionally, since slurry paints generally use water,
When painted directly onto iron plates such as mild steel plates, similar to conventional water-based paints, there is a problem in that phenomena such as temporary rusting that cannot be seen with solvent-based paints occur.

In order to suppress this phenomenon, temporary rust preventive agents and the like are often used in the same way as with water-based paints, but the use of these agents is not preferable because it has an adverse effect on storage stability.

The present invention aims to solve these problems.

In other words, it has excellent storage stability, a wide working width, no defects such as wrinkles during firing, and coating properties such as gloss, smoothness, temporary rust prevention, corrosion resistance, chemical resistance, weather resistance, and impact resistance. The present invention provides a water-dispersible thermosetting coating composition with excellent film performance.

That is, the present invention provides (A) (i) 1 to IO wt. ,000~120,0
00 unsaturated polyester・・・・・・2～50
(ii) α,β-monoethylenically unsaturated monomer containing acid group...0.01 to 10% by weight, G11) (a) α,β -Hydroxyalkyl ester of monoethylenically unsaturated carboxylic acid...
...1 to 40% by weight (b) α,β-monoethylene other than the N-alkoxymethylated monomer of (ii), (a) and α,β-monoethylenically unsaturated carboxylic acid amide obtained by graft polymerization of a sexually unsaturated monomer......99 to 60% by weight and a monomer mixture......99 to 40% by weight, Hydroxyl value 30-200
．． Acid value 5-30. Weight average molecular weight 10,000-180
,000 polyester modified vinyl resin, and (B)
Fine powder thermosetting resin particles consisting of a blocked isocyanate compound, 0.01 to 5.0% by weight based on the particles
The present invention relates to a water-dispersible thermosetting coating composition having excellent temporary rust prevention properties, which comprises a surfactant and/or thickener, and a necessary amount of water.

The polyester-modified vinyl resin used in the present invention is obtained by graph-1 polymerization of α, β-monoethylenically unsaturated monomers [(A) (ii) and (4) Oii)) into unsaturated polyester. It is characterized by imparting to vinyl resin the flexibility, pigment dispersibility, and excellent coating appearance of unsaturated polyester.

It is necessary to use an α,β-unsaturated dicarboxylic acid as a raw material for the unsaturated polyester used in the present invention.

The component is 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-monoethylenic nonvesicular monomer when producing the polyester-modified vinyl resin, and therefore the polyester modification is insufficient. As a result, the product has a blended composition of unsaturated polyester and a polymer of α,β-monoethylenically unsaturated monomer, resulting in whitening of the coating film.

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

On the other hand, when the component is 10% by weight or more, α.

This is not preferable because gelation occurs during the reaction with the β-monoethylenically unsaturated monomer.

Specific examples of the α,β-unsaturated dicarboxylic acid component include:
Examples include fumaric acid, (anhydrous) maleic acid, icconic acid, glutaconic acid, (anhydrous) citraconic acid, 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 6
The reaction is carried out at a ratio of 9% by weight.

Specific examples of the components include phthalic anhydride, isophthalic acid, trimellitic acid (anhydride), pyromellitic acid (anhydride), tetrahydrophthalic acid (anhydride), hexahydrophthalic acid (anhydride), and methyltetrahydro (anhydrous). phthalic acid,
Examples include methylhexahydrophthalic anhydride, hymic anhydride, succinic acid (anhydride), adipic acid, sebacic acid, benzoic acid, para-tert-butylbenzoic acid, etc., and these can be used singly or as a mixture of two or more. It's okay.

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 components include ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, dipropylene glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, phthanediol, bentanediol, hexanediol. , 1,4-
Examples include cyclohexane dimetatool, (hydrogenated) bisphenol A, and the like.

One type or a mixture of two or more of these resins is used, and if necessary, a glycidyl ester of a tertiary synthetic saturated resin (manufactured by Cardular E Nigel Chemical Co., Ltd., trade name) is used in combination.

If necessary, animal and vegetable oils, their fatty acids, petroleum resin rosins, phenolic resins, epoxy resins, etc. can also be used as modified raw materials for unsaturated polyesters.

The unsaturated polyester in the present invention is produced by a known method by a single-stage reaction and a multi-stage reaction, 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; hereinafter, all hydroxyl values in the present invention will be expressed in the same way), and the molecular weight is 2,000 to 120,000 in weight average molecular weight.

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

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 properties after graft polymerization of the α,β-monoethylenically unsaturated monomer will decrease.

Furthermore, if the hydroxyl value is lower than 50, the crosslinkability between the polyester-modified vinyl resin obtained by graft polymerization of α, β-monoethylenically unsaturated monomer and the blocked isocyanate compound tends to be insufficient, and if the hydroxyl value is higher than 250, This is not preferred because the water resistance of the resulting coating film tends to decrease due to an increase in the number of polar groups.

In addition, if the weight average molecular weight is lower than 2,000, the properties of unsaturated polyester may not be fully exhibited;
If it exceeds 20,000, the molecular weight of the unsaturated polyester is too high, and when it is modified with an α,β-monoethylenically unsaturated monomer, the viscosity becomes too high, which impedes workability, which is not preferable. .

The polyester-modified vinyl resin in the present invention includes the unsaturated polyester, a phosphoric acid group-containing α,β-monoethylenically unsaturated monomer, and one or more other α,
It is obtained by graft polymerization with a β-monoethylenically unsaturated monomer.

Phosphate group-containing α,β- in polyester modified vinyl resin
By introducing the monoethylenically unsaturated monomer (component (A) and (ii)), even when the coating composition is applied directly onto an iron plate, it not only suppresses temporary rusting but also improves the storage stability of the composition. Furthermore, it is possible to obtain a coating film that has even stronger adhesion to metal surfaces and has significantly superior corrosion resistance and water resistance.

The phosphoric acid group-containing α,β-monoethylenically unsaturated monomer is 0.01 to io,o% by weight, preferably 0.5 to 6% by weight.
．． It is used in a range of 0% by weight.

If the monomer is used in an amount less than 0.01% by weight, the temporary rust prevention effect, storage stability, and high corrosion resistance, which are the characteristics of the present invention, cannot be sufficiently exhibited; This is not preferable because it tends to gel during the graft polymerization reaction process.

In addition, sufficient effects can be obtained within 10% by weight, so 1
It is economically undesirable to use more than 0% by weight.

Specific examples of the monomer include acidophosphoxyethyl (meth)acrylate, acidophosphoxypropyl (
Primary phosphoric acid esters of acrylic acid or methacrylic acid containing hydroxyl groups such as meth)acrylate, 3-chloroL7-ate: bis(meth)acryloxyethyl phosphate, acrylic alcohol acid phosphate, vinyl phosphate, mono[2] - hydroxyethyl (meth)acrylate core cytophosphite,
etc., and one or a mixture of two or more of these salts and esters.

Such a monomer is prepared by reacting an α,β-monoethylenically unsaturated monomer having a hydroxyl group with phosphoric anhydride,
It is produced by hydrolyzing products, such as Ikemasa phosphoric acid, metaphosphoric acid, phosphorus oxychloride, phosphorus trichloride,
It can also be produced using phosphorus pentachloride.

The monomer other than the phosphoric acid group-containing α,β-monoethylenically unsaturated monomer [component (4) Gii)] to be graft-polymerized to the unsaturated polyester is (a) α.

A mixture is used consisting of a hydroxyalkyl ester of a .beta.-monoethylenically unsaturated carboxylic acid and (b) an .alpha.,.beta.-monoethylenically unsaturated monomer other than said (a).

The hydroxyalkyl ester monomer of the α,β-monoethylenically unsaturated carboxylic acid is added to the monomer mixture [component (1) Gii)] so that the hydroxyl value of the polyester-modified vinyl resin is 30 to 200. It is used in an amount of 5 to 40% by weight, particularly preferably 5 to 20% by weight.

If the monomer is used in an amount exceeding 40% by weight, the resulting polyester-modified vinyl resin will have a high viscosity and the appearance of the coating will deteriorate, which is not preferable.

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.
-Hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (
meth)acrylate, neopentyl glycol mono(meth)acrylate, 3-butoxy-2-hydroxypropyl(meth)acrylate, 2-hydroxy-1-phenylethyl(meth)acrylate, polypropylene glycol mono(meth)acrylate, glycerin mono(meth)acrylate There are meth)acrylates, etc., and these may be used alone or as a mixture of two or more.

In addition, other than the N-alkoxymethylated monomer of (II+) (b) (ii), (a) and α,β-monoethylenically unsaturated carboxylic acid amide used for graft polymerization with unsaturated polyester The α,β-monoethylenically unsaturated monomer is a monomer mixture [(4) (Ij
i) component] 60 to 99% by weight, particularly preferably 80 to 99% by weight
It is used in a range of 95% by weight.

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, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 5eC-butyl (
meth)acrylate, isobutyl(meth)acrylate, n-hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, n-octyl(meth)acrylate, lauryl(meth)acrylate, tridecyl(meth)acrylate, stearyl(meth)acrylate Alkyl esters of acrylic acid or methacrylic acid such as acrylate; Sonoike N.

N-dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)
Examples include dialkyl esters of fumaric acid such as acrylate, phenyl methacrylate, benzyl methacrylate, and di-butyl fumarate, and monomers such as styrene, vinyltoluene, α-methylstyrene, (meth)acrylonitrile, and vinyl acetate.

The above monomers may be used depending on the purpose and use of the coating composition.
You may use one species or a combination of two or more as appropriate.

The polyester modified vinyl resin contains (1) 2 to 50% by weight of the unsaturated polyester, and (+i) 0,01 to 1% of the phosphoric acid group-containing α,β-monoethylenically unsaturated monomer.
0% by weight and G11) (a) 1 to 40 hydroxyalkyl esters of α,β-monoethylenically unsaturated carboxylic acids
Weight % and (b) above (ii), (a) and α, β
- Monomer mixture 95 to 99% by weight of an α,β-monoethylenically unsaturated monomer other than the hepanoenoethylenically unsaturated carboxylic acid amidurkoxymethylated monomer
It is a graft polymerization reaction product with 40% by weight.

The amount of modification of the unsaturated polyester is 2 to 50% by weight, preferably 4 to 30% by weight.

If it is less than 2% by weight, the excellent flexibility, pigment dispersibility, and coating appearance of unsaturated polyester will not be fully exhibited, and if it is more than 50% by weight, the hardness, which is a characteristic of vinyl resin, will not be fully demonstrated. , stain resistance etc. will be impaired.

The polyester-modified vinyl resin used in the present invention is produced by conventional storage polymerization.

For example, 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 the remaining monomer (mixture) and a polymerization initiator are added dropwise to polymerize the unsaturated polyester. , a method in which a monomer (mixture) and a polymerization initiator are dropped and polymerized, but there is no particular restriction on the acid liquid polymerization method.

Generally, the polymerization temperature range is about 50-150°C;
Although depending on the temperature, the polymerization reaction time ranges from about 4 to 12 hours.

As the polymerization solvent used in the acid liquid polymerization method, water-soluble or water-miscible solvents are used, such as methyl alcohol, ethyl alcohol, isopropyl alcohol,
Alcohols such as n-propyl alcohol, ethylene glycol derivatives such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether acetate; diethylene glycol monomethyl ether, diethylene glycol monoethyl Ethylene glycol derivatives such as ether and diethylene glycol monobutyl ether; esters such as butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone are used.

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 nonvolatile content during production of the polyester modified vinyl resin is 10 to 80% by weight, preferably 20% by weight.
It is preferable to use it in a range of ~70% by weight.

In this case, the nonvolatile content should be lowered as more phosphoric acid group-containing α,β-monoethylenically unsaturated monomer is used.

In addition, examples of the polymerization initiator used include benzyl peroxide, t-butyl perbenzoate, t-
-Organic peroxides such as butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, and t-butyl peroctoate, and ab compounds such as abbisisobutyronitrile and azodiisobutyric acid nitrile. .

These polymerization initiators may be used alone or in combination of two or more.

The mixing 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 30
~2001, preferably in the range of 50 to 150, and the acid value is 5 to 30. Preferably it is in the range of 7-27.

If the acid value is less than 5, the thermosetting properties will be insufficient, resulting in poor coating film hardness, water resistance, corrosion resistance, durability, etc. If the acid value is greater than 30, the coating film performance and storage stability will also decrease. .

Moreover, when the hydroxyl value is 30 or less, the crosslinking density decreases and the solvent resistance decreases.

On the other hand, if it is larger than 200, flexibility and water resistance are reduced.

The weight average molecular weight of the polyester modified vinyl resin of the present invention is 10,000 to 180,000. Preferably 20,0
Within the range of 00 to 150,000.

If the weight average molecular weight is less than io, ooo, the coating film performance will not be sufficient;
In the above cases, the smoothness of the coating film is impaired, which is not preferable.

Since the polyester-modified vinyl resin of the present invention is highly reactive, it tends to increase in viscosity at high temperatures such as in summer.

In such cases, in order to further improve storage stability, a more stable polyester-modified vinyl resin can be made by neutralizing the acid groups introduced into the polyester-modified vinyl resin with a basic compound. .

Examples of the basic compound include inorganic alkalis such as st-IJium hydroxide and potassium hydroxide; ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, 7-n-propylamine, dimethyl-n-
Water-soluble amines such as propylamine; monoethanolamine, jetanolamine, triethanolamine,
One or more water-soluble oxyamines such as N-methylethanolamine, N-aminoethylethanolamine, N-methylgetanolamine, monoisopropanolamine, diisopropanolamine, tripropropanolamine, hydroxylamine, etc. A mixture of two or more types may be mentioned.

When neutralizing with such a compound, it includes neutralizing some or all of the acid groups in the polyester-modified vinyl resin, and furthermore, the stability of the polyester-modified vinyl resin composition is Alternatively, it can be added in an excessive amount in consideration of coating film performance and the like.

Next, the blocked isocyanate compound used in the present invention is a blocked isocyanate compound having two or more inocyanate 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 diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, m-phenylene diisocyanate, P-phenylene. -diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, ■
, 5-naphthylene-cyanocyanate, 4°4', 4
“-Triphenylmethane triisocyanate, 4.4'
-diphenylmethane diisocyanate, 3,3-dimethyl-4,4-sophenylecy diisocyanate, m-
Excess of polyisocyanates such as xylylene diisocyanate, P-xylylene diisocyanate, inphorone diisocyanate, lysine isocyanate and the above incyanate compounds, such as ethylene glycol,
Fukomapyrene glycol, ■, 3-butylene glycol,
Neopentyl glycol, 2,2,4-trimethyl 1,
3-bentanediol, hexamethylene glycol, cyclohexane dimetatool, trimethylolpropane,
Incyanate compounds obtained by blocking polyisocyanates with two or more functionalities obtained by addition reaction with low-molecular polyols such as hexanetriol, glycerin, and pentaerythritol, polyisocyanates with a biuret structure, polyisocyanates with allophanate bonds, etc. with a blocking agent. It is.

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. system, its function imide system, amine system, imizole system, urea system, carbamate system, base, imine system, oxime system, mercaptan system,
There are sulfite-based, lactam-based, etc.

As described above, the crosslinking reaction of the composition of the present invention is carried out by the hydroxyl groups of the polyester-modified vinyl resin and the incyanate groups of the blocked isocyanate compound.

In the present invention, it is preferable to use the hydroxyl group in the polyester modified vinyl resin/the incyanate group in the blocked isocyanate compound in a ratio of -171,3 to -0,3 (equivalent ratio).

The hydroxyl group in the polyester modified vinyl resin/incyanate group in the blocked isocyanate compound is 110.3
When it is larger, crosslinking between each component is not sufficiently performed,
Solvent resistance, chemical resistance, etc. of the coating film tend to decrease.

On the other hand, when the value is less than 1.3, the properties such as water resistance of the coating film decrease due to unreacted incyanate groups, which is also economically unfavorable, and the amount of polyester-modified vinyl resin decreases. The characteristics of the invention, such as the flexibility, pigment dispersibility, and excellent coating film appearance that the polyester resin has, are impaired.

Note that the softening temperature of the resin particles obtained from the mixture of the polyester-modified vinyl resin and the blocked isocyanate compound used in the present invention is preferably 30 to 100°C.

More preferably, the temperature is 40 to 80°C.

If the softening temperature is lower than 30°C, the storage stability of the paint tends to decrease, 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, one type of known dissociation catalyst, such as epoxy resin, cellulose resin, amino resin, unsaturated polyester, etc., is used as necessary to promote the reaction between the polyester-modified vinyl resin and the blocked isocyanate compound. Alternatively, it is also possible to use 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 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 polyester-modified vinyl resin, a basic compound or block isocyanate compound that neutralizes some or all of the acid groups in the polyester-modified vinyl resin, and, if necessary, a dissociation catalyst and a pond, are added. The coating film-forming resin and the like are dissolved in the water-soluble or water-miscible solvent to obtain a resin solution, 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 acid medium 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 considering the p-pass step 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. However, 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 and becoming coarse, the mixed liquid should be cooled to keep the liquid temperature below 30°C. It is preferable to keep it at

The above-mentioned stirring or mixing using a line mixer progresses so that the solvent in the emulsion fine particles migrates 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-containing agent 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 1 to 300
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, a dispersing machine normally used for manufacturing paints is used, such as a sand mill, a ball mill, a Deisharcer, a Sassmeyer mill, and a Sentry mill. etc. to finely crush the resin particles to an average particle size of about 1 to 5.
Adjust between 0μ.

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

That is, each particle necessarily contains groups that react with each other when heated, that is, a hydroxyl 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, it is not preferable because the cohesion of the particles becomes large and the particles tend to foam during heating, resulting in properties similar to those of water-soluble paints.

On the other hand, if it is larger than 50μ, the resin particles tend to precipitate and aggregate 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 dissociation catalysts, organic and inorganic coloring and extender pigments commonly used in paints, temporary rust preventive agents, flow aids, antifoaming agents, anti-settling agents, and anti-mold agents, if necessary. The composition may contain additives such as agents, preservatives, and film-forming resins such as pond water-resistant resins, hydrosils, emulsion resins, and the like.

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

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 cervicune fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alcohol ether, chrycerin fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene castor oil derivative, polyoxy Ethylene alkyl phenyl ether, alkyl phosphate ester, polyoxyethylene phosphate ester, anionic surfactants such as alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, alkyl sulfosuccinate, N
-As the acyl sarcosine salt and cationic surfactant, quaternary ammonium salts, pyridinium salts, etc. can be used.

Nonionic surfactants are preferred from the viewpoint of dispersion stability of resin particles and coating film performance, and those with 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.

For example, cholera is produced by cellulose-based water-soluble resins such as methylcellulose, ethylcellulose, and hydroxyethylcellulose; polyvinyl alcohol; polyethylene-based water-soluble resins such as polyethylene gelcol ether and polyethylene oxide; methylvinyl ether maleic anhydride copolymer, and ethylene maleic anhydride. Water-soluble resins based on maleic anhydride copolymers such as copolymers and styrene-maleic anhydride copolymers; ammonium, amine salts and sodium salts of acrylic acid polymers, bentonite, polyvinylpyrrolidone, alginates, polyacrylamide and their Examples include partially hydrolyzed 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 is achieved.
Paint workability, etc. deteriorate, and if it exceeds 5.0% by weight, the smoothness, water resistance, etc. of the coating film deteriorates, making it unsuitable for the present invention.

Among the above-mentioned thickeners, amine salts of carboxyl group-containing acrylic copolymers are particularly suitable for the present invention because they become insoluble in water formed by heating the coating film due to elimination of amines and do not reduce the water resistance of the coating film. be.

The mixing ratio of water and fine powder resin particles in the coating composition of the present invention is preferably 90 to 30,710 to 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, it is necessary to recoat several times, 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 usually at an appropriate temperature in the range of 120 to 200°C for 10 to 20 minutes.
A cured coating film can be obtained by heat treatment for 40 minutes.

The cured coating film thus obtained suppresses temporary rusting on the steel plate, and has excellent adhesion to metal surfaces, corrosion resistance, and water resistance.

In addition, polyester resin has excellent flexibility, pigment dispersibility, and coating film appearance, vinyl copolymer resin has excellent hardness and stain resistance, and urethane resin has excellent weather resistance and chemical resistance. In addition, it has excellent coating performance with no bubbling 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 1 (hereinafter abbreviated as PE-1) 32.6 parts of isophthalic acid and 18 parts of adipic acid were placed in a reaction vessel equipped with a stirrer, thermometer, cooling tube, and nitrogen gas introduction tube.
7 parts, fumaric acid 3.0 parts, neopentyl glycol 2
9.0 parts of trimethylolpropane and 16.7 parts of trimethylolpropane were charged and reacted at 225°C for about 8 hours in a nitrogen gas atmosphere to produce a resin with an acid value of 15.1, a hydroxyl value of 155, and a weight average molecular weight of 6,700. 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): 32.3 parts of isophthalic acid, 15.1 parts of adipic acid, 3.0 parts of fumar in a reaction vessel similar to that in which PE-1 was synthesized.
1 part, 22.9 parts of neopentyl glycol, 17.4 parts of trimethylolpropane, and 9.3 parts of glycidyl ester of tertiary bottom saturated fatty acid (trade name manufactured by Cardular E Nidiel Chemical) were charged, and the mixture was heated under a nitrogen gas atmosphere. at 225℃
After reacting for about 8 hours, the acid value was 16.2 and the hydroxyl value was 166.
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) A pond using 32.6 parts of ortho-phthalic anhydride instead of 32.6 parts of isophthalic acid in PE-1 was prepared using nitrogen gas in the same manner. The reaction was carried out in an atmosphere at 225°C for about 6 hours, resulting in an acid value of 45, a hydroxyl value of 158, and a weight average molecular weight of 2.45.
0 resin was obtained.

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

(4) In a reaction vessel similar to that in which the unsaturated polyester NtlL4 (hereinafter abbreviated as PE-4) was synthesized, 36.0 parts of isophthalic acid, 11.5 parts of azapic acid, and 6 parts of fumaric acid were added.
．． 0 parts, 340 parts of neopentyglycol, and 125 parts of 1,4-cyclohexane dimetatool were charged, and reacted at 225°C in a nitrogen gas atmosphere for about 8 hours to obtain an acid value of 7.5.
A resin having a hydroxyl value of 94 and a weight average molecular weight of 3,950 was obtained.

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

(5) Unsaturated polyester Nct5 (hereinafter abbreviated as PE-5) In a reaction vessel similar to that in which PE-1 was synthesized, 16.0 parts of isophthalic acid, 14.5 parts of adipic acid, and 4.0 parts of fumaric acid.
0 parts, 25.0 parts of neopentyl glycol, io, o parts of trimethylolethane, 17.5 parts of methylhexahydrophthalic anhydride, and 13.0 parts of hydrogenated bisphenol A. The reaction was carried out for a period of time to obtain a resin having an acid value of 12.3, a hydroxyl value of 120, and a weight average molecular weight of 9,300.

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 25 was added to a reaction vessel equipped with a stirrer, thermometer, dropping funnel, cooling tube and nitrogen gas introduction tube.
After adding 6 parts and raising the temperature to 80℃, the following monomers,
The unsaturated polyester and initiator mixture was added dropwise over a period of 3 hours.

175 parts of methyl methacrylate, 35 parts of styrene, 145 parts of ethyl acrylate, 35 parts of 2-hydroxyethyl methacrylate, 5 parts of acrylic acid, 5 parts of acidophosphoxyethyl methacrylate, 100 parts of the unsaturated polyester (PE-2), Abvis After dropping 6 parts of isobutyronitrile, 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 15.3 and a hydroxyl value of 11.
9, weight average molecular weight 83.000, and non-volatile content 62
．． A 1% resin acid solution was obtained.

The softening temperature of the resin was about 79-81°C.

PE-PV-1 was obtained by adding 2 parts and 3 moles of triethylamine to the acid value of the resin acid solution to neutralize it.

(2) In polyester modified vinyl resin solution production (1), 200 parts of methyl ethyl ketone, 133 parts of methyl methacrylate, 25.5 parts of styrene, 109 parts of ethyl acrylate, 26 parts of 2-hydroxyethyl methacrylate, and acrylic acid were added. 4 parts of acid phosphoxyethyl methacrylate, 2.5 parts of acid phosphoxyethyl methacrylate, and 200 parts of the unsaturated polyester (PF, -2) were all reacted in the same manner, and the acid value was 15.0 and the hydroxyl group was A resin acid liquid having a value of 93, a weight average molecular weight of 70,200, and a nonvolatile content of 61.9% was obtained.

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

This was named PE7PV-2.

(3) Put 430 parts of methyl ethyl ketone into a reaction vessel similar to that in which PE-Pv-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.

157.5 parts of methyl methacrylate, 15 parts of styrene,
2-ethylhexyl acrylate, 12.5 parts, 2-ethylhexyl methacrylate 180 parts, 2-hydroxyethyl methacrylate 45 parts, acrylic acid 5 parts, acidophosphoxyethyl methacrylate 5 parts, 3-chloroni2-acidophos 5 parts of foxypropyl methacrylate,
75 parts of the unsaturated polyester (PE-3) and 6 parts of azobisisobutyronitrile.

After dropping, add 6 parts of azobisisobutyronitrile,
After raising the reaction temperature to 87°C, the reaction was carried out for 4 hours,
Acid value 20.6, hydroxyl value 103, weight average molecular weight 65.
0001 and a resin solution with a nonvolatile content of 50.5% was obtained.

The softening temperature of the resin was about 69-73°C.

PE-PV-3 was obtained by adding 2 parts and 3 moles of triethylamine to the acid value of the resin solution to neutralize it.

(4) Put 250 parts of methyl ethyl ketone into a reaction vessel similar to that in which PE-PV-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.

157 parts of methyl methacrylate, 12.5 parts of 2-ethylhexyl acrylate, 138 parts of 2-ethylhexyl methacrylate, 5 parts of 2-hydroxyethyl methacrylate
6.5 parts of acrylic acid, 5 parts of andphosphoxyethyl methacrylate, the unsaturated polyester (PE-
1) After dropping 125 parts and 7.5 parts of abbisisobutyronitrile, add 1.2 parts of abbisisobutyronitrile, raise the reaction temperature to 87°C, and conduct the reaction for 4 hours. Acid value 17.7, hydroxyl value 115, weight average molecular weight 3
2,100 and a non-volatile content of 61.degree. 5% was obtained.

The softening temperature of the resin was about 67-69°C.

PE-PV-4 was obtained by adding 2 parts and 3 moles of triethylamine to the acid value of the resin solution to neutralize it.

(5) In polyester modified vinyl resin solution production (1), 750 parts of methyl ethyl ketone, 190 parts of methyl methacrylate, 50 parts of styrene, 180 parts of ethyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 5 parts of acrylic acid 25 parts of the unsaturated polyester (PE)
-2) was added to 40 parts, the reaction was carried out in the same manner, and the acid value was 23.1, the hydroxyl value was 35, and the weight average molecular weight was 34.
, 200, and a resin solution with a nonvolatile content of 39.8% was obtained.

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

PE-PV-5 was obtained by neutralizing the oxidation of the resin solution by adding 3 parts and 4 moles of triethylamine.

(6) Put 267 parts of methyl ethyl ketone into a reaction vessel similar to that in which PE-PV-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.

Methyl methacrylate 127.5 parts, styrene 77.5 parts
parts, 15 parts of acrylonitrile, 113 parts of ethyl acrylem
0 parts, 40 parts of 2-hydroxypropyl methacrylate,
5 parts of acrylic acid, 5 parts of acidophosphoxyethyl methacrylate, 100 parts of the unsaturated polyester (PE-1)
parts, 6 parts of abbisisobutyronitrile.

After finishing dropping, add 1 part of azobisisobutyronitrile,
After raising the reaction temperature to 87°C, the reaction was carried out for 4 hours to obtain an acid value of 15.7, a hydroxyl value of 100, a weight average molecular weight of 86,
200, and a resin solution with a nonvolatile content of 60.9% was obtained.

The softening temperature of the resin was about 80-83°C.

This was designated as PE-PV-6. (7) Said PE-PV-
Methyl ethyl ketone 2 was placed in a reaction vessel similar to that in which 1 was synthesized.
After adding 50 parts and raising the temperature to 80°C, the following monomer, unsaturated polyester and initiator mixture was added dropwise over 3 hours.

120 parts of methyl methacrylate, 125 parts of styrene, 70 parts of ethyl acrylate, 10 parts of 2-ethylhexyl methacrylate, 40 parts of 2-hydroxyethyl acrylate
1 part, 6 parts of methacrylic acid, 14 parts of acidophosphoxyethyl acrylate, 1 part of the unsaturated polyester (PE-1)
25 parts, 6 parts of abbisisobutyronitrile.

After finishing dropping, add 1 part of azobisisobutyronitrile,
After raising the reaction temperature to 87°C, the reaction was carried out for 4 hours to obtain an acid value of 15.9, a hydroxyl value of 114, and a weight average molecular weight of 81.5.
00. A resin solution with a nonvolatile content of 61.1% was obtained.

The softening temperature of the resin was about 68-71°C.

This was named PE-PV-7.

(8)-Put 267 parts of methyl ethyl ketone into a reaction vessel similar to that in which PE-PV-1 was synthesized, and adjust the temperature to 80°C.
After raising the temperature to C, the following monomer, unsaturated polyester and initiator mixture was added dropwise over 3 hours.

175 parts of methyl methacrylate, 35 parts of styrene, 145 parts of ethyl acrylate, 35 parts of 2-hydroxyethyl methacrylate, 5 parts of acrylic acid, 5 parts of andphosphoxyethyl methacrylate, the unsaturated polyester (
PE4) 80 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 to obtain an acid value of 15.5, a hydroxyl value of 64, and a weight average molecular weight of 61.1.
00 and a resin solution with a nonvolatile content of 61.1% was obtained.

The softening temperature of the resin was about 73-76°C.

This was named PE-PV-8.

(9) Put 277 parts of methyl ethyl ketone into a reaction vessel similar to that in which PE-PV-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.

150 parts of methyl methacrylate, 96.5 parts of styrene, 60 parts of n-butyl acrylate, 50 parts of 2-ethylhexyl methacrylate, 50 parts of 2-hydroxypropyl methacrylate, 6 parts of acrylic acid, 2.5 parts of acidophosphoxyethyl acrylate. part, the unsaturated polyester (
PE2) 85 parts, abbisisobutyronitrile 6 parts.

After the dropwise addition, 1 part of azobisisobutyronyl-IJ was added, the reaction temperature was raised to 87°C, and the reaction was carried out for 4 hours to give an acid value of 14.2, a hydroxyl value of 107, and a weight average molecular weight of 6.
9,800. A resin solution with a nonvolatile content of 60.5% was obtained.

The softening temperature of the resin was about 77-80°C.

PE-PV-9 was obtained by adding 2 parts and 3 moles of triethylamine to the acid value of the resin solution to neutralize it.

00) 234 parts of methyl ethyl ketone was placed in a reaction vessel similar to that in which PE-PV-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. .

107.5 parts of methyl methacrylate, 75 parts of ethyl acrylate, 90 parts of n-butyl methacrylate, 25 parts of vinyl acetate, 42 parts of 2-hydroxyethyl methacrylate.
5 parts, 5.5 parts of methacrylic acid, 4.5 parts of acidophosphoxyethyl methacrylate, the unsaturated polyester (
PE-1) 150 parts, 6 parts of azobisisobutyronitrile, and after the completion of 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 to determine the acid value. 16.0. Hydroxyl value 1207 Weight average molecular weight 89
．． 5001 and a resin solution with a nonvolatile content of 60.8% was obtained.

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

This was designated as PE-PV-10.

0υ 450 parts of methyl ethyl ketone was placed in a reaction vessel similar to that in which PE-PV-1 was synthesized, the temperature was raised to 80°C, and the following 7-mer monounsaturated polyester and initiator mixture was added dropwise over 3 hours. .

102.5 parts of isobutyl methacrylate, 18 parts of styrene
1.5 parts, n-butyl acrylate 37.5 parts, 2-ethylhexyl methacrylate 80 parts, 2-hydroxypropyl methacrylate 40 parts, acrylic acid 1 part, acidophosphoxyethyl methacrylate 5 parts, 3-chloro −
2-acidophosphoxypropyl methacrylate 2.5
50 parts of the unsaturated polyester (PE-3), 7.5 parts of azobisisobutyronitrile, and after the completion of the dropping, 12 parts of azobisisobutyronitrile were added, and the reaction temperature was raised to 87%.
After raising the temperature to ℃, the reaction was carried out for 4 hours and the acid value was 12.0.
A resin solution with a hydroxyl value of 89, a weight average molecular weight of 61,700, and a nonvolatile content of 51.1% was obtained.

The softening temperature of the resin was about 73-76°C.

PE-PV-11 was obtained by adding 2 parts and 3 moles of triethylamine to the acid value of the resin solution to neutralize it.

02) 284 parts of methyl ethyl ketone was placed in a reaction vessel similar to that in which PE-PV-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. .

n-butyl methacrylate - 180 parts, styrene 200 parts,
75 parts of ethyl acrylate, 15 parts of dibutyl fumarate,
45 parts of 2-hydroxypropyl methacrylate, 4 parts of methacrylic acid, 6 parts of andphosphoxyethyl methacrylate, 75 parts of the unsaturated polyester (P E-2), 6 parts of abbisisobutyronitrile, and 6 parts of abbisisobutyronitrile after the completion of dropping. Add 1 part of butyronitrile and raise the reaction temperature to 87°C.
After raising the temperature to , the reaction was carried out for 4 hours to obtain an acid value of 13.7, a hydroxyl value of 99, and a weight average molecular weight of 79,800. A resin solution with a nonvolatile content of 60.8% was obtained.

The softening temperature of the resin was about 80-82°C.

This was designated as PE-PV-12. 03) Said PE-PV
267 parts of methyl ethyl ketone was placed in a reaction vessel similar to that in which -1 was synthesized, the temperature was raised to 80°C, and then the following monomer, unsaturated polyester and initiator mixture was added dropwise over 3 hours.

175 parts of methyl methacrylate, 35 parts of styrene, 145 parts of ethyl acrylate, 35 parts of 2-hydroxyethyl methacrylate, 5 parts of acrylic acid, 5 parts of andphosphoxyethyl acrylate, the unsaturated polyester (P
E-5) Add 80 parts of azobisisobutyronitrile, 6 parts of azobisisobutyronitrile, and 1 part of azobisisobutyronitrile after the dropwise addition, raise the reaction temperature to 87°C, and carry out the reaction for 4 hours to determine the acid value. 15.6, hydroxyl value 81, weight average molecular weight 76.30
0. A resin solution with a nonvolatile content of 60.9% was obtained.

The softening temperature of the resin was about 75-78°C.

This was designated as PE-PV-13. α(1) Said PE-P
260 parts of methyl ethyl ketone was placed in a reaction vessel similar to that in which V-1 was synthesized, the temperature was raised to 80°C, and then the following monomer, unsaturated polyester and initiator mixture was added dropwise over 3 hours.

196.5 parts of methyl methacrylate, 50 parts of ethyl acrylate, 79 parts of isobutyl methacrylate, 20 parts of 2-ethylhexyl methacrylate, 35 parts of 2-hydroxyethyl acrylate, 4.5 parts of methacrylate, 5 parts of acidophosphoxyethyl methacrylate, the above 110 parts of unsaturated polyester (PE-2), 6 parts of azobisin butyronitrile.

After finishing dropping, add 1 part of azobisisobutyronitrile,
After raising the reaction temperature to 87°C, the reaction was carried out for 4 hours to obtain an acid value of 14.2, a hydroxyl value of 108, a weight average molecular weight of 74,
500 and a nonvolatile content of 61.2%.

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

This was designated as PE-PV-14.

05) Put 267 parts of methyl ethyl ketone into the same reaction vessel as the one used to synthesize PE-PV-1, and raise 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.

145 parts of methyl methacrylate, 50 parts of styrene, 117.5 parts of methyl acrylate, 37.5 parts of lauryl methacrylate, 4 parts of 2-hydroxypropyl methacrylate
0 parts, 2.5 parts of acrylic acid, 7.5 parts of acidophosphoxyethyl methacrylate-F, the unsaturated polyester (P
E-2) 100 parts, azobisisobutyronitrile 7.5
Department.

After the dropping was completed, 1.2 parts of Abbisisobutyronitrile was added, the reaction temperature was raised to 87°C, and the reaction was carried out for 4 hours to obtain an acid value of 14.8, a hydroxyl value of 97, and a weight average molecular weight. 60,300. A resin solution with a nonvolatile content of 60.4% was obtained.

The softening temperature of the resin was about 76-79°C.

This was designated as PEPV-15.

[Method for replacing a block isocyanate compound with a dilution agent] When a block isocyanate compound containing a hydrophobic solvent is used, the acid agent in the emulsion fine particles is not extracted into water and is absorbed into the resin particles in the process of forming resin particles. In order to remain
This is not preferable because the resin particles coalesce or become integrated, which impairs stability.

Therefore, the blocked isocyanate compound was replaced with an acid agent by the method described below and used in the present invention.

Takenate B-82ONSU (manufactured by Takeda Pharmaceutical Co., Ltd., trade name: effective NCO 4.3%, non-volatile content 60%, (@ agent: Super Dull 15.00/butyl acetate)) was placed in a vacuum dryer at 440°C and vacuumed for 2 days. After drying (non-volatile content: 92.6%), methyl ethyl ketone was added to this to dilute the non-volatile content to 60% to obtain NC0-A.

[Example 1] 50 parts of resin solution (PE-PV-1), 38 parts of titanium dioxide [6 Hara Sangyo ■R-930], 1 and 0 parts of flow aid (Monsanto Co., Ltd.: Modaflow), 21 parts of methyl ethyl ketone
．． Add 5 parts of the resin solution (
PE-PV-1) 50 parts, 90 parts of blocked isocyanate compound (NGO-A), 1.0 parts of dibutyltin dilaurate (dissociation catalyst), and 2.5 parts of methyl ethyl ketone were added and mixed with stirring to give hydroxyl group/isocyanate group = 110
．． A uniform pigment dispersion liquid with an equivalent ratio of 7 (equivalent ratio) was obtained.

This was dropped into 5000 parts of water at a water temperature of 15° C. under high speed stirring to emulsify the pigment dispersion and extract the acid agent into the water to form resin particles.

After that, filtration and washing with water are repeated, and the average particle size is approximately 1.
A resin particle water-containing cake with a particle diameter of 0.00μ and a water content of about 50% was obtained.

Add 40 parts of nonionic surfactant to 100 parts of this water-containing cake.
% hydrolysis solution (trade name Emaruan 9301 manufactured by Kao Atlas Co., Ltd., HLB 15.1), 0.5 parts of a 10% aqueous solution of an alkali salt thickener of an acrylic acid copolymer were added, and the mixture was dispersed and kneaded with a sand mill. The resin particles are finely pulverized to an average particle size of 1
A slurry paint having a pH of 7.6 and a pH of 7.6 was obtained.

[Example 2] Add 100 parts tc of resin solution (PE-PV-2), 29 parts of titanium dioxide [the above R-930], 10 parts of flow aid (the above Modaflow), and 10 parts of methyl ethyl ketone, and grind to below 10μ with a sand mill. After kneading and dispersing, 52 parts of a methyl ethyl ketone acid solution (adjusted to a non-volatile content of 50% by weight) of a blocked isocyanate compound (trade name Kleran U-I6109: Bayer AG), 1.0 part of dibutyltin dilaurate, and 20 parts of methyl ethyl ketone were added and stirred. Mix to form hydroxyl group/
A uniform pigment dispersion having an isocyanate group of -110.7 (equivalent ratio) was prepared.

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 16 μm and a pH of 7.7.

[Example 3] Titanium dioxide [
Add 528 parts of the above R-930) and 20 parts of methyl ethyl ketone, and after kneading and dispersing in a hole mill to a size of 10μ or less, 50 parts of the resin solution (PE-PV-3) and a methyl ethyl ketone solution (non-volatile (adjusted to 50% by weight) and 1.0 part of dibutyltin dilaurate were added and mixed with stirring.
A uniform pigment dispersion with a hydroxyl group/isocyanate group ratio of -170.7 (equivalent ratio) was prepared.

This is sprayed into 4000 parts of water at a water temperature of 18° C. under high speed stirring to emulsify the pigment dispersion and extract the acid agent into the water to form resin particles.

After that, filtration and washing with water were repeated, and the average particle size was 150.
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 manufactured by Kao 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. Finely pulverized to an average particle size of 15μ
, a slurry paint having a pH of 7.7 was obtained.

[Example 4] Add 50 parts of resin solution (P E-P V-4), 33 parts of titanium dioxide (the above R-930), 1 and 0 parts of flow aid (the above Modaflow), and 10 parts of methyl ethyl ketone,
After kneading and dispersing in a sand mill to a size of 10μ or less, 50 parts of resin solution (PE-PV-4), 62 parts of blocked isocyanate compound (NCO-A), 1.0 part of dibutyltin dilaurate, and 2 parts of methyl ethyl ketone were added and mixed with stirring. and hydroxyl group/isocyanate group -110.5 (equivalent ratio)
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 15 μm and a pH of 7 and 8.

[Example 5] To 50 parts of resin solution (PE-PV-5), 18 parts of titanium dioxide [the above R-930], 1.0 part of flow aid (the above Modaflow), and 7 parts of methyl ethyl ketone were added, and the mixture was milled to 10 μm using a sand mill. After kneading and dispersing the resin solution (PE-PV
-5) 50 parts, blocked isocyanate compound (NC
O-A) 22 parts, dibutyltin dilaurate 0.5 part,
Add 2.0 parts of methyl ethyl ketone and mix with stirring to obtain a solution of hydroxyl group/isocyanate group -170.9 (equivalent ratio).
It was made into a pigment dispersion liquid.

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 13 μm and a pH of 7.7.

[Example 6] 29 parts of titanium dioxide [R-930 above], 1.0 parts of flow aid (Modaflow above), and 10 parts of methyl ethyl ketone were added to 100 parts of lubricant liquid (PE-PV-6), and the mixture was milled in a sand mill. After kneading and dispersing to 10μ or less, 55 parts of a methyl ethyl ketone solution (adjusted to a non-volatile content of 50% by weight) of a blocked isocyanate compound (the above-mentioned Fulleran U-I6109),
1.0 part of dibutyltin dilaurate and 2.0 parts of methyl ethyl ketone were added and mixed with stirring to obtain a uniform pigment dispersion having a hydroxyl group/isocyanate group -170.7 (equivalent ratio).

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 14 μm and a pH of 7.4.

[Example 7] To 100 parts of resin solution (PE-PV-7), 30.5 parts of titanium dioxide [the above R-930], 1.0 parts of flow aid (the above Modaflow), and 10 parts of methyl ethyl ketone were added,
After kneading and dispersing in a sand mill to a size of 10μ or less, a methyl ethyl ketone solution (adjusted to a non-volatile content of 50% by weight) of a blocked isocyanate compound (the above-mentioned Fulleran U-I6109) 63
1.0 parts of dibutyltin dilaurate and 2.0 parts of methyl ethyl ketone were added thereto and mixed with stirring to obtain a uniform pigment dispersion having a hydroxyl group/isocyanate group ratio of -110.7 (equivalent ratio).

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 7.5.

[Example 8] 50 parts of resin solvent (P E-I) V-8), 130 parts of titanium dioxide [R-930 described above, and flow aids (1.0 parts of Modaflow described above, 21.5 parts of methyl ethyl ketone) were added. After kneading and dispersing to 10μ or less using a ball mill, 48 parts of blocked isocyanate compound (NDO-A) and resin solution (P
E-PV-8) 50 parts, dibutyltin dilaurate 1
．． Add 0 parts of methyl ethyl ketone and 2.5 parts of methyl ethyl ketone, stir and mix to obtain hydroxyl group/isocyanate group -170.7 (equivalent ratio)
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 a flat particle diameter of 18 μm and a pH of 7.9.

[Example 9] To 100 parts of resin solution (PE-PV-9), 30 parts of titanium dioxide [R-930 above], 1.0 parts of flow aid (Modaflow above), and 10 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, 59 parts of a methyl ethyl ketone solution (adjusted to a non-volatile content of 50% by weight) of a blocked isocyanate compound (Fleran U-I6109),
1.0 part of dibutyltin dilaurate and 20 parts of methyl ethyl ketone were added and mixed with stirring to obtain a uniform pigment dispersion having a hydroxyl group/isocyanate group ratio of -110.7 (equivalent ratio).

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 15 μm and a pH of 7.7.

[Example io] To 100 parts of resin solution (PE-PV-10), 31 parts of titanium dioxide [R-930 above], 10 parts of flow aid (Modaflow above), and 10 parts of methyl ethyl ketone were added, and the mixture was milled with a sand mill to a size of 10μ or less. After kneading and dispersing, 66 parts of a methyl ethyl ketone solution (adjusted to a non-volatile content of 50% by weight) of a blocked isocyanate compound (the above-mentioned Fulleran U-16109),
1.0 parts of dibutyltin dilaurate and 2.0 parts of methyl ethyl ketone were added and mixed with stirring to obtain a uniform pigment dispersion having a hydroxyl group/isocyanate group ratio of -110.7 (equivalent ratio).

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 18 μm and a pH of 7.5.

[Example 11] To 100 parts of resin solution (PE-PV-11), 24 parts of titanium dioxide [11(-930), 1.0 part of flow aid (Modaflow), and 10 parts of methyl ethyl ketone were added, and the mixture was mixed with a sand mill. After kneading and dispersing to 10μ or less, a methyl ethyl ketone solution (adjusted to non-volatile content of 50% by weight) of the blocked isocyanate compound (Fleran U-16109) 4
2 parts of dibutyltin dilaurate, 1.0 part of dibutyltin dilaurate, and 2.0 parts of methyl ethyl ketone were added and mixed with stirring to obtain a uniform pigment dispersion having a hydroxyl group/isocyanate group=110.7 (equivalent ratio).

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 -16 μm and a pH of 7.9.

[Example 12] To 100 parts of the resin solution (PE-PV-12), 29 parts of titanium dioxide [the above R-930], parts i and o of the flow aid (the above Modaflow), and 10 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, 55 parts of a methyl ethyl ketone solution (adjusted to non-volatile content of 50% by weight) of a blocked isocyanate compound (the above Fulleran U-16109), 1.0 part of dibutyltin dilaurate, and 2.0 parts of methyl ethyl ketone were added and mixed with stirring. A uniform pigment dispersion having a hydroxyl group/isocyanate group ratio of -110.7 (equivalent ratio) was obtained.

All of the following operations were carried out in the same manner as in Example 1 to obtain a slurry-like paint with resin particles having an average particle size of 18 μm and a PL of 7.6.

[Example 13] To 50 parts of the resin solution (PE-PV-13), 32 parts of titanium dioxide [the above R-930], parts i and o of the flow aid (the above Modaflow), and 21.5 parts of methyl ethyl ketone were added,
After kneading with a ball mill to a size of 10μ or less, 60 parts of blocked isocyanate compound (NCO-A) and resin liquid (PE-
PV-13) 50 parts, dibutyltin dilaurate 1.
0 parts and 2.5 parts of methyl ethyl ketone were added and mixed with stirring to obtain a uniform pigment dispersion having a hydroxyl group/isocyanate group -170.7 (equivalent ratio).

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 16 μm and a pH of 7.4.

[Example 14] To 100 parts of resin solution (PE-PV-14), 30 parts of titanium dioxide [the above R-930], flow aids (1.0 parts of the above Modaflow, 10 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, 60 parts of a methyl ethyl ketone solution (adjusted to a non-volatile content of 50% by weight) of a blocked isocyanate compound (the above Fulleran U-I6109), 1.0 part of dibutyltin dilaurate, 2 parts of methyl ethyl ketone
．． 0 parts were added and mixed with stirring to obtain a uniform pigment dispersion having a hydroxyl group/isocyanate group -170.7 (equivalent ratio).

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 18 μm and a pH of 7.3.

[Example 15] To 100 parts of the resin solution (PE-PV-15), 29 parts of titanium dioxide [the above R-930], parts i and o of the flow aid (the above Modaflow), and 10 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, 53 parts of a methyl ethyl ketone solution (adjusted to non-volatile content of 50% by weight) of a blocked isocyanate compound (the above-mentioned Fulleran U-I6109)9. 1.0 part of dibutyltin dilaurate and 2.0 parts of methyl ethyl ketone were added and mixed with stirring to obtain a uniform pigment dispersion having a hydroxyl group/isocyanate group ratio of -110.7 (equivalent ratio).

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 7.7-.

[Comparative Example 1] Polyester modified vinyl resin solution used in Example 1 (
The monomer composition was the same as PE-PV-1) except for the unsaturated polyester for modification (PE-2) and acidophosphoxyethyl methacrylate, and all the ponds were reacted in the same manner as in the production of polyester-modified vinyl resin solution (1). The acid value was 11.9 and the hydroxyl value was 49 (weight average molecular weight 12).
．． 2.00) and a resin solution with a nonvolatile content of 58.9% was obtained.

To 50 parts of the resin solution were added 24 parts of titanium dioxide, 11.5 parts of methyl ethyl ketone, and 1.0 parts of flow aid (Modaflow).
After kneading and dispersing in a ball mill to a size of 10 μm or less, further add 40 parts of the resin solution and 60% methyl ethyl ether of a butylated methylolmelamine resin with an average degree of condensation of 2.5, etherified cold 25, and a water-soluble component of 1% or less. 30 parts of ethitone solution and 3.5 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 1, with an average particle size of 15 μm and p
A slurry paint of H7.4 was obtained.

[Comparative Example 2] Polyester modified vinyl resin acid i used in Example 3 (
From the composition of PE-PV-3), unsaturated polyester (PE-PV-3)
-3), except for acidophosphoxyethyl methacrylate and 3-chloro-2-acidophosphoxypropyl methacrylate, all monomer compositions were reacted in the same manner as in polyester-modified vinyl resin liquid production (3). A resin solution having an acid value of 11.3, a hydroxyl value of 51 (weight average molecular weight 18.500), and a nonvolatile content of 59.2% was obtained.

Titanium dioxide [the above R-93033] was added to 50 parts of the resin acid solution.
0 parts, 1 part of flow aid (the above-mentioned Modaflow), and 11.5 parts of methyl ethyl ketone were added, and after kneading and dispersing in a ball mill to a size of 10 μm or less, further 50 parts of the resin solution and 48 parts of blocked isocyanate compound (NCO-A) were added. , dibutyltin dilaurate 1.0 parts, methyl ethyl ketone 2.0
of hydroxyl groups/isocyanate groups, stir and mix.
A uniform pigment dispersion with an equivalent ratio of 170.9 was obtained.

The following steps were carried out in the same manner as in Example 3, with an average particle size of 15 μm and p
A slurry paint of H7.4 was obtained.

[Comparative Example 3] Polyester modified vinyl resin solution used in Example 1 (
PE-PV-1) with a monomer composition excluding acidophosphoxyethyl methacrylate, and all ponds were reacted in the same manner as in the production of polyester-modified vinyl resin guide liquid (1), with an acid value of 15°6 hydroxyl value. 121, weight average molecular weight 33,000. A resin solution with a nonvolatile content of 61.1% was obtained.

3 parts of titanium dioxide [R-930 above] was added to 50 parts of the resin solution.
8 parts, 1.0 part of flow aid (the above-mentioned Modaflow), and 21.5 parts of methyl ethyl ketone were added, and after kneading and dispersing in a ball mill to a size of 10 μ or less, 50 parts of the resin solution, 90 parts of blocked isocyanate compound (NCO-A), Dibutyltin dilaurate (dissociation catalyst) 1.0 parts, methyl ethyl ketone 2
．． 5 parts were added and mixed with stirring to obtain a uniform pigment dispersion having a hydroxyl group/isocyanate group -110.7 (equivalent ratio).

Hereinafter, in the same manner as in Example 1, the average molecular diameter was 14μ, and the pH was 7.
, 7 was obtained.

[Comparative Example 4] 12 parts of titanium dioxide was added to 24 parts of a phosphoric acid group-free polyester modified vinyl resin solution prepared as follows.
1 part and 4 parts of methyl ethyl ketone and milled with a sand mill to 10 parts.
After kneading and dispersing to below μ (same as below 2 as measured by grit gauge), 30 parts of the resin solution, 26 parts of blocked isocyanate compound (NCO-A), 0.5 part of dibutyltin dilaurate (dissociation catalyst), 3 parts of methyl ethyl ketone ．．
5 parts were added and stirred and mixed 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 casting agent into the water to form resin particles.

Thereafter, in the same manner as in Example 1, the average particle size was 16μ, the pH was 7,
A slurry paint of No. 6 was obtained.

[Method for producing a polyester-modified vinyl resin conductive liquid containing no phosphoric acid group] 249 parts of methyl ethyl ketone was placed in a reaction vessel similar to that in which PE-PV-1 was synthesized, and after raising the temperature to 80°C, the following monomers were added. , unsaturated polyester and initiator mixture were 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 (P
E-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, and the acid value was 1001, the hydroxyl value was 110, and the weight average molecular weight was 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.

The slurry paint prepared in each of the above Examples and Comparative Examples was sprayed onto a polished mild steel plate, set for 10 minutes, preheated at 90°C for 10 minutes, and then baked and dried at each predetermined temperature to give a film thickness of approx. A coating film of 40μ was formed.

Table 1 shows the baking conditions and test results for the coating film.

Claims (1)

[Claims] 1 (A) (i) 1 to 10% by weight of α, β-
Acid value 50 or less, hydroxyl value 50 to 250, weight average molecular weight 2.000 to 2.000, with unsaturated dicarboxylic acid as the constituent component.
120,000 unsaturated polyester...
・2 to 50% by weight, (ii) IJ acid group-containing α,
β-monoethylenically unsaturated monomer・・・・・・0
．． 01 to 10% by weight, (ui) (a) α, β
- hydroxyalkyl ester of monoethylenically unsaturated carboxylic acid...1 to 40% by weight; (b) the above (ii), (a) and α,β-monoethylenically unsaturated carboxylic acid; A monomer mixture consisting of 99 to 60% by weight of α,β-monoethylenically unsaturated monomers other than N-alkoxymethylated monomers of acid amide. ...Hydroxyl value 30-2 obtained by graft polymerization with 95-40% by weight
001 acid value 5-30, weight average molecular weight 10,000-1
80.000 polyester modified vinyl resin and (B)
fine powder thermosetting resin particles consisting of a blocked isocyanate compound, a surfactant and/or thickener in an amount of 0.01 to 5.0% by weight based on the particles, and a necessary amount of water;
A water-dispersible thermosetting coating composition with excellent temporary rust prevention properties. 2. The mixing ratio of the polyester modified vinyl resin and the blocked isocyanate compound is (hydroxyl group in the polyester modified vinyl resin)/(incyanate group in the blocked isocyanate compound) -1/1.3 to 170.3 (equivalent ratio) A water-dispersed thermosetting coating composition having excellent temporary rust prevention properties as claimed in claim 1, wherein the ratio is such that: