JPS5865769A - Water-dispersed thermosetting coating composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent temporary rust proofness and film performance, consisting of finely divided specified thermosetting resin particles, a surfactant and/or a thickening agent and water. CONSTITUTION:0.01-5.0wt% (based on the amount of resin particle mentioned below) surfactant and/or thickening agent and water are added to finely divided thermosetting resin particles having an average particle size of 1-200mu, consisting of 20-80wt% mixture (A) composed of 15-95wt% polyester resin (i) having a hydroxyl value of 10-300 and 85-5wt% phosphate group-contg. copolymer (ii) having a hydroxyl value of 3-150 derived from 0.01-10wt% alpha,beta-monoethylenically unsaturated monomer contg. a phosphate group and other alpha,beta-monoethylenically unsaturated monomer, and 80-20wt% crosslinkable copolymer resin (B) derived from 0.01-10wt% N-alkoxymethylated monomer of an alpha,beta-monoethylenically unsaturated carboxylic acid amide and other alpha,beta-monoethylenically unsaturated monomer. The mixture is pulverized to give particles having a particle size of 1-50mu.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-dispersed thermosetting coating composition that has excellent temporary rust prevention properties and coating performance, and satisfies resource saving and low pollution properties.

In recent years, in the field of paints and coatings, resource conservation, energy conservation, and environmental issues have been taken up as overlapping themes, and efforts are being made to develop new paints and improve coating methods in these areas. In particular, organic solvents, which are diluents for paints, are emitted into the atmosphere during the drying process of paint films, which poses an extremely serious problem from the standpoint of resource conservation and environmental protection. In order to improve this situation, efforts are being made to reduce the amount of organic solvents in paints.
As a result, a high non-volatile content paint called a high solid, NAD (non-aqueous dispersion) III family, in which high molecular weight IJ, - is dispersed in a non-polar organic solvent (aliphatic hydrocarbon) to a high degree of III; Nine-type paints that use water as a diluent and powder paints that do not use any diluents are already on the market, and are gradually replacing solvent-reduced paints. Among them, water-based paints are attracting attention as the future paint system because they use water as a diluent, so there is no risk of fire or other dangers, conventional painting equipment can be used as is, and the painting environment is comfortable. ing. Such water-based paints can be classified into water-based paints, water-based paints, dispersion paints, water-soluble paints, slurry paints, etc.Water-based paints have the above-mentioned advantages, but on the other hand, they also have drawbacks. The main reason for this is that the coating environment, especially the temperature,
It is difficult to form a film that is easily influenced by the temperature, and it is easy to cause paint film defects such as wrinkles, sagging, and repellency when the film dries. For example, the use of dispersants, surfactants, etc. in combination may reduce the durability of the coating film. The current situation is that current water-based paints use a considerable amount of organic solvent in order to eliminate defects caused by water, and are truly resource-saving.
It is hard to say that it is a paint that prevents separation.

On the other hand, slurry paints have overcome these defects of water-based paints and have become a new type of paint, and have already been used on the Shoda F-32.
T! / issue, special public @SS-da issue 33, etc. To briefly list its characteristics, a slurry paint is a paint in which particulate resin of about q to gθμ is dispersed in water as a medium with a solid content concentration in the range of 70 to 70 weight ff1−. Therefore, it has many advantages, such as using only water as a medium as a volatile component, it can be coated with a high solid content, it can be applied thickly, and it can be used directly with conventional solvent-based paint coating equipment. It is an excellent paint with excellent properties.

In general, acrylic resins, polynisder 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 may be used in combination to provide additional anti-corrosion properties. However, if an epoxy resin is used in combination, the weather resistance will be impaired, so it is not a good idea to use it as a component of a 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, which has the disadvantage of poor paint workability and the film becomes thicker, so K is coated several times. There are 6 things you need to do.

First, slurry paints generally use water, so
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 is a water-dispersed heat treatment that has excellent storage stability, is free from defects such as burning during operation, and has excellent gloss, smoothness, temporary rust prevention, chemical resistance, corrosion resistance, etc., and has cold film performance. A curable coating composition is provided.

The gist of one embodiment of the present invention is to provide a water-dispersed heat-curable coating composition with the excellent roundness properties of polyester resins and acrylic resins. In other words, in addition to Mukuro polyester resin's water-related properties such as water resistance, humidity resistance, and boiling water resistance, corrosion resistance such as salt spray and salt water immersion, weather resistance, and chemical resistance, acrylic resin has excellent properties. It is possible to impart properties such as smoothness, texture, texture, surface smoothness), stain resistance, etc.

19 The gist of another aspect of the present invention is to provide excellent performance as a urethane resin, such as adhesiveness and impact resistance, in addition to the advantages of the above-mentioned polyester resins and acrylic resins.

Furthermore, it was discovered that by crosslinking a polyester resin with an acrylic resin or an acrylic resin and an incyanate compound, it was possible to maintain a suitable balance between hardness and flexibility and obtain a castable film.

In addition to these nine excellent features, the composition of the present invention has the effect of significantly improving the flowability of the coating film during baking and drying and improving the appearance of the coating film.

Furthermore, the polyester resin contained in the composition of the present invention has a higher affinity for rounded water than acrylic resins and the like, and has the effect of improving storage stability in a dispersed state in water.

That is, the present invention provides: (1) (A) (a) Polyester resin having a hydroxyl value of 10 to 300 73 to 95 weight-2 and φl IJ 7 acid group-containing α, β-monoethylenic non-ester resin The hydroxyl value obtained from a monomer mixture consisting of a saturated monomer and (-) an α, β-monoethylenically unsaturated monomer other than the above (1): 3~/! fO phosphate group-containing copolymer resin ・
... a mixture consisting of (El(1) α,β-monoethylenically unsaturated carboxylic acid ado N-alkoxymethylated monomer and (1) the above Fine powder thermosetting resin particles consisting of a crosslinkable copolymer resin obtained from a monomer mixture with an α,β-monoethylenically unsaturated monomer other than (1),
．． A water-dispersed, slightly thermosetting coating composition consisting of a surfactant and/or thickener of 0/-5,0 weight Is and the required amount of water, and (, IJ (A) (a) hydroxyl value lO ~ 300 Polyester resin .../j-9!! Weight - Tsuta and (b) (1) Phosphate group-containing α,/-monoethylenically unsaturated monomer, (1) (1) above Phosphate group-containing copolymer resin with hydroxyl groups @ 3 to ISO obtained from a monomer mixture consisting of α,β-monoethylenically unsaturated monomers other than ......gs-s weight-. (9) (a) (1) an N-alkoxymethylated monomer of α, β-monoethylenically unsaturated carboxylic acid amide; (−) α* / −′ other than the above (1); a crosslinkable copolymer resin obtained from a monomer mixture with an ethylenically unsaturated monomer, and
, oi-s, o by weight of a surfactant and/or thickener, and the required amount of water.

The polyester resin used in the composition of the present invention is obtained by esterifying a polyvalent carboxylic acid, and if necessary, a monovalent carboxylic acid and a polyhydric alcohol. The weight average molecular weight of the resin is 7.000
~100.000, preferably ko, 000~bo,
It's ooo. If the molecular weight is less than this range, it is not only difficult to stably disperse the particles in water at the slurry stage, but also the coating film performance, particularly mechanical performance and chemical performance, deteriorates, which is not preferable. If the molecular weight exceeds this range, not only will it lack compatibility with the acrylic resin or protoxyisocyanate compound used in combination, but it may also cause problems in the appearance of the coating film. The hydroxyl value of polyester resin is 10 to 300
(The number of milligrams (resin solid content) of potassium hydroxide used to neutralize the carboxyl groups corresponding to the hydric groups present in sample II is 2 or less). The range of 30 to -〇〇 is preferable. If the hydroxyl value is less than this range, the degree of crosslinking will be low and the coating film will not be able to exhibit its original performance, but secondary performances such as water resistance, solvent resistance, and weather resistance will deteriorate. If the range is exceeded, the ratio of the curing component of the blocked isocyanate compound to the polyester resin and acrylic resin increases, which not only makes it impossible to exhibit the desired performance inherent to the polyester resin, but also impairs the flexibility and adhesion of the coating film.

Next, the synthesis of polyester resin Kl! The polyhydric alcohols used include ethylene glycol, diethylene glycol, triethylene glycol, polypylene glycol,
Dipropylene glycol, butylene glycol, /, 3
-bentanediol, neoventruda recall, /l
A-hexanediol, 734 bisphenol A, /
, 4(-Cyclohexane dimetatool, pentaerythritol, glycerin, trimethylolpropane, trimethylolethane, etc., as well as higher alcohols such as polypropylene glycol, polyethylene glycol, etc. can also be used. These can be used as Fi/species or a mixture of two or more types. In addition, if necessary, Cardular EC Shell (manufactured by Kekikaru Co., Ltd., trade name) may be used in combination. Polycarboxylic acids and monovalent carboxylic acids include phthalic anhydride, isophthalic acid, terephthalic acid, endomethylenetetrahydrophthalic anhydride, tetrahydroheptalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, Hexahydroheptalic anhydride, trimellitic anhydride, succinic acid, adipic acid, azelaic acid, cepatic acid, citric acid, pericic acid, malic acid, /.

Naphthalic acid etc. can be used. Benzoic acid, pt-butylbenzoic acid, etc. may also be used as a reaction regulator. 711 or a mixture of one or more of these may be used.

Since the performance of the coating film is significantly affected by the combination of these constituent raw materials, it is necessary to consider the composition of the nine raw materials in accordance with the target performance. For example, if water resistance or chemical resistance of the coating film is required, use isophthalic acid, neopentyl glycol, etc. for one coating film, and if crack resistance is required, use adipic acid, sepacic acid, diethylene glycol, etc. It is already well known that 7-talic anhydride, propylene glycol, etc. are used to round resins and the like to improve their compatibility with other resins. Further, it is possible to use, as a raw material, 9-tetrachlorophthalic anhydride, which imparts special properties to the coating film, such as anti-scratch properties.

Manufacturing method of polyester resin This is a common condensation reaction, and there are a melting method and an azeotropic method conveniently using an azeotropic solvent such as Kijirol. What you need to be careful about is removing the by-product combined water from the yarn as quickly as possible, increasing the capacity of the complete esterification equipment to efficiently recover the glycol that comes out as azeotropy, and increasing the capacity of the complete esterification equipment. In order to avoid coloring, inert gas may be introduced. Further, it is desirable that the acid value of the polyester resin be less than or equal to Sθ (number of milligrams of potassium hydroxide required to neutralize resin l-duram: resin solid content).

Next, the phosphoric acid group-containing copolymer resin [above (b) component] used in the present invention has phosphoric acid group-containing α, β
- monoethylenically unsaturated monomer ((bl component)) and α,β-monoethylenically unsaturated monomer other than the above [(b) (I
Component I)]. By introducing the phosphoric acid group-containing α,β-monoethylenically uncelled monomer tube, even when the coating composition of the present invention is applied directly onto an iron plate, it not only temporarily suppresses rusting, but also improves the composition. In addition, highly saturated monomers with improved storage stability (and even stronger adhesion to metal surfaces, corrosion resistance, water resistance, etc.) have O0θ7~io, o in the monomer mixture. Weight-1 is preferably used in the range of 0.5-s, o*. On the other hand, if the weight exceeds 70%, it tends to gel in the copolymerization reaction process, so it is not desirable. It is economically undesirable to use more than 70% by weight, since sufficient effects can be obtained with less than Primary phosphoric acid esters of acrylic acid or methacrylic acid containing hydroxyl groups such as probyl(meth)acrylate, 3-chlorocoacide phosphoxyprobyl methacrylate: bis(meth)acryloxyethyl phosphate, 7/I ) sy alcohol acid phosphate, vinyl phosphate, mono[-monohydroxyethyl (meth)acrylate core acid phosphite, tonato and their salts and esters, etc.0
/11To or a mixture of one or more. Such monomers are produced by reacting an α,β-monoethylenically unsaturated monomer having a droxyl group with anhydrous phosphorus and hydrolyzing the resulting product, but the processed phosphoric acid , metaphosphoric acid, phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, etc.

The α, β-monoethylenically unsaturated monomers other than the phosphoric acid group-containing α,β-monoethylenically unsaturated monomers used as essential components in the phosphoric acid group-containing copolymer resin are as described below. , α, β-monoethyl 17-unsaturated carboxylic acid,
Common α,/-monoethylenically unsaturated monomers such as hydroxyalkyl esters of carboxylic acids, alkyl esters of acrylic acid or methacrylic acid, etc. can be used as a mixture of seven or more types.

In addition, the above-mentioned phosphoric acid group-containing copolymer resin needs to contain a hydroxyl group in the molecule in order to undergo a crosslinking reaction with the crosslinkable copolymer resin and the block isocyanate compound. Therefore, in order to maintain a balance with monovalent hydroxyl in the polyester resin, α is used as a type of α,β-7noemonic unfouled monomer.

It is preferred to use the required amount of hydroxyalkyl ester of β-monoethylenically unsilated carboxylic acid.

1 monomer in the monomer mixture constituting the phosphoric acid group-containing copolymer resin, / ~ 30 weight - 1 preferably λ ~ /,! -Use a range of weight values. If the monomer is used in an amount exceeding 30% by weight, it tends to gel during the copolymerization reaction, and the obtained phosphoric acid group-containing copolymer resin has a high viscosity, and moreover, it has a high viscosity with respect to the polyester resin and crosslinkable copolymer resin. The degree of crosslinking between the mixture of the above and the blocked isocyanate compound becomes too high, which tends to reduce the flexibility, water resistance, etc. of the coating film, which is undesirable.

Specific examples of the monomer include 7-ethyl (meth)acrylate, co-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, -1 and droxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate,
-Hydroxybutyl (meth)acrylate, derhydroxybutyl (meth)acrylate,! - HydrodPV pendel(meth)acrylate, 6-hydrodadihexyl(meth)acrylate, neopentyl glycol mono(
meth)acrylate, 3-ptoxy-1-hydroxyglobil (meth)acrylate, co-hydroxy-7-phenylethyl (meth)acrylate, polypropylene glycol mono(meth)acrylate, glycerin mono(
There are meta)acrylates, and these can be used as one type or Fi
They may be used as a mixture of one or more.

Motoyaaki Kl! As a component of the phosphoric acid group-containing copolymer resin used, 0.
It is preferable to use it in a range of 5 to 10% by weight. The monomer has the effect of improving the compatibility between the phosphoric acid group-containing copolymer resin and the polyester resin and promoting the crosslinking reaction. If θ, 3 weight gIIIK is unsightly, the effect will be weakened, and if it exceeds 70 weight, the curing performance at 1 kHz will be degraded, which is not preferable.

Specific examples of the component include acrylic acid, methacrylic acid,
Examples thereof include chlorinated acid, itaconic acid, maleic acid, fumaric acid, etc., and these may be used as a mixture of 1w or more. As a raw material for the phosphoric acid group-containing copolymer resin used in the present invention, it is preferable to react with α,β-monoethylenically unsaturated monomers other than those mentioned above in a proportion of 70 to 90% by weight. Specific examples of the components include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 5eC
-Butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (methanoacrylate, coethylhexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meta)
Acrylate, stearyl (methanoacrylate and other acrylic acid or methacrylic/I/l12 alkyl esters *: Others N,N'-dimethylaminoethyl (meth)acrylate, glyphudyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl methacrylate, Examples include monomers such as di-alkyl fumarate esters such as bayyl methacrylate and dibutyl fumarate, styrene, vinyltoluene, α-methylstyrene, (meth)acrylonitrile, and vinyl acetate.The above monomers are used in paints. Depending on the purpose and use of the composition, seven types or a combination of two or more types may be used as appropriate.

The phosphoric acid group-containing copolymer resin of the present invention is produced by conventional S liquid polymerization. As the polymerization solvent used in the solution polymerization method, a water-soluble or water-miscible bath is used. For example, alcohols such as methyl alcohol, ether alcohol, inglobil alcohol, n-10 bil alcohol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol motsubutyl ether, ethylene glycol monoethyl x -
f Ethylene glycol derivatives such as A/7 acetate;
Diethylene dalycol derivatives such as diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether;
Esters such as methyl acetate, ethyl acetate, butyl acetate;
Ketones such as methyl ethyl ketone and methyl isobutyl ketone are used. These polymerization solvents may be used in combination of seven or two or more. I# preferably has a solubility in water of 70 to 30 weight-11 at 40°C.

In addition, examples of the polymerization initiator used include benzoyl peroxide, t-butyl perbenzoate, t-
Examples thereof include organic peroxides such as butylhydroperoxide, cumene hydroperoxide, di-t-butylhydroperoxide, and t-butylperoctoate, and azo compounds such as azodiisobutyric acid nitrile and azodiisobutyric acid nitrile. These polymerized Rfllhken oi@ or 扛yu kinds or more may be mixed and used as appropriate. If necessary,
To adjust the molecular weight, chain transfer agents such as dodecyl mercaptan, 1-ethylhexyl thioglycolate,
Carbon tetrachloride or the like may also be used.

The polymerization temperature during production of axillary sulfuric acid group-containing copolymer resin is approximately 3θ~
/Sθ℃, the reaction time is about 4 to 12 hours, and the polymerization solvent used at that time has a nonvolatile content of IO during the resin production.
It is conveniently used in a range such that the amount is preferably 20 to 70% by weight.

In this case, it is better to use a larger amount of the phosphoric acid group-containing α,β-monoethylenically unsaturated monomer and lower the nonvolatile content.

Further, the amount of the polymerization initiator used is approximately 0.0% based on the nonvolatile content during the production of the phosphoric acid group-containing copolymer resin. The chain transfer agent is preferably used at the same time in a range of about 0 to 5 weight.

The weight average molecular weight of the phosphoric acid group-containing copolymer resin of the present invention is g
, ooo~'to, ooo, preferably koo,
It is preferably within the range of ooo to so, ooo. If the weight average molecular weight is less than g, ooo, the coating performance is insufficient, while the weight average molecular weight is less than θ, o
If it exceeds oot-, the smoothness will be impaired.

Moreover, the hydroxyl value Fi3 of the phosphoric acid group-containing copolymer resin of the present invention
It is in the range of ~/Sθ. When the hydroxyl value does not appear to be 3, the crosslinking density becomes low and the abrasion resistance of the coating film decreases. On the other hand, if it exceeds 1 sot, the flexibility and water resistance of the coating film will decrease.

Because the phosphoric acid group-containing copolymer resin of the present invention is highly reactive,
, it tends to thicken under high temperatures such as summer. This^,
In such cases, the storage stability can be further improved by neutralizing the acid groups introduced into the monophosphoric acid group-containing copolymer resin with a basic compound. It can be made of resin.

Inorganic alkalis such as IJum and potassium hydroxide; ammonia, monomethylamine, dimethylamine, trimethylamine, triethylamine, monoethylamine, mono-propylamine, dimethyl-propylapo Water-soluble amines such as monoethanolain, cyethanolaman%)
IJ ethanol, N-methylethanol,
Seven or a mixture of two or more water-soluble oxyamines such as N-aminoethylethanolamine, N-methyljetanolamine, monoisopropanolamine, diisopropanolamine, trypanolamine (ζ), and hydroxylamine are used. Can be mentioned. 117 like this
When neutralizing using a compound, it is necessary to neutralize some or all of the acid groups in the phosphoric acid group-containing copolymer resin. An excessive amount may be added in consideration of the stability of the composition or the performance of the coating film.

Next, α and β constituting the crosslinkable copolymer resin in the present invention
- Monoethylenically unsexed saturated monomer mixture, α, β
- An N-alkoxymethylated monomer of monotyrenically unsaturated carboxylic acid amide is used as an essential component, and this component is necessary for the crosslinking reaction with the polyester resin and the phosphoric acid group-containing copolymer resin. This component is present in the crosslinkable copolymer resin in an amount of 5 to 30% by weight, preferably 10-2! It is preferable to react in a weight ratio of -. If the amount of this component is less than 5% by weight, the crosslinking reaction with the polyester resin and the phosphoric acid group-containing copolymer 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 production of the crosslinkable copolymer resin, which is not preferable. Variants of this component include N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-n-propoxymethyl(meth)acrylamide, N-impoxymethyl(meth)acrylamide,
N-n-butoxymethyl (meth)acrylide, N
-5ec-butoxymethyl(meth)acryland, N
-α, β- of t-butoxymethyl (meth)acrylamide, dimethyl (meth)acrylide in N-isobutylene, etc.
N-alkoxymethylated products of heptano'monolenic unterated carboxylic acid amides; or N-methylolated products thereof, and the like may be used alone or as a mixture of two or more.

In the present invention, α,
It may be used within the range of β-monoethylenically unsaturated carbon@to, 5-io weight. The monomer has the effect of improving the compatibility between the crosslinkable copolymer resin and the polyester resin and promoting the crosslinking reaction. If O, S weight does not appear within the above range, the effect will be weakened,
Moreover, if it exceeds 10% by weight, it is not preferable because the performance of the cured coating film decreases.

Specific examples of ingredients include acrylic acid, methacrylic acid,
Examples include crotonic acid, itaconic acid, maleic acid, fumaric acid, etc., and these may be used alone or as a mixture of more than one type.

As a raw material for the crosslinkable copolymer resin used in the present invention, it is preferable to react copolymerizable α,β-monoethylenically unsaturated monomers other than those mentioned above in a proportion of 60 to 90% by weight. Specific examples of the components include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl' (meth)acrylate, n-butyl (meth)acrylate, 5ec-butyl (
meth)acrylate, t-butyl(meth)acrylate, inbutyl(meth)acrylate, n-hexyl(meth)acrylate, -monoethylhexyl(meth)acrylate, n-octyl(meth)acrylate, lauryl(meth)acrylate, Alkyl varnish fL' of acrylate or methacrylic acid such as tridecyl (meth)acrylate and Skeltonyl (meth)acrylate; 2-ey
Roxyethyl (meth)acrylate, Cohydroxyptevir (methane acrylate, 3-hydroxypropyl (meth)acrylate, -monohydroxybutyl (meth)
Acrylate, 3-Droxybutyl (meth)butarylate, Terhydroxybutyl (meth)acrylate, S
-Hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, neopentyl glycol mono(meth)acrylate, 3-butoxycohydroxyglobil (meth)acrylate, euhydroxy-/-phenylethyl (meth)acrylate , holipropylene glycol mono(meth)acrylate, glycerin mono(meth)acrylate, etc. α,! -Monoethylenic IL! hydroquine alkyl esters of carboxylic acids and other N,N'-dimethylamine ethyl (
meth)acrylate, glycidyl(meth)acrylate, cyclohegycyl(meth)acrylate, phenyl methacrylate, benzyl methacrylate, di-butyl fumarate, etc., styrene, vinyltoluene, α-methylstyrene, (meth) ) Monomers such as acrylonitrile and vinyl acetate may be mentioned.The above monomers may be used alone or in an appropriate combination of more than one type depending on the purpose and use of the coating composition.

The crosslinkable copolymer resin of the present invention is produced by a conventional solution solution. As the polymerization solvent used in the bath liquid polymerization method,
The above-mentioned water-soluble or water-miscible solvents are used.

Also, the polymerization initiator used is the above-mentioned organic peroxide or azo compound. The chain transfer agents mentioned above can also be used to adjust the molecular weight tg*. Polymerization temperature fFi during production of skeleton crosslinkable copolymer resin approximately 5θ~/jθ℃,
The reaction time is about 1 to 1 hours, and the polymerization solvent used is such that the non-volatile content during the resin production is 10 to 75% by weight, preferably 35 to 75% by weight. .

Furthermore, the amount of the polymerization initiator is approximately 0.0% based on the nonvolatile content during production of the crosslinkable copolymer resin. The chain transfer agent is preferably used at the same time in a range of about O-5 by weight. The weight average molecular weight of the crosslinkable copolymer resin of the present invention is 10.000 to ioo, θOθ, preferably coO
It is preferably within the range of 1θOO to to, ooθ. If the weight average molecular weight is not /θ, OθO,
The coating performance was insufficient, and the weight average molecular weight was 100.
If it exceeds 000 t-, the smoothness will be impaired.

Next, the blocked inocyanate compound, which is one component of the crosslinking agent mixture used in the present invention, is an isocyanate compound having two or more inocyanate groups in seven molecules, and all of the isocyanate groups are blocked. It is a nine-block isocyanate compound masked with a masking agent.

The blocked inocyanate compound is necessary for the crosslinking reaction with the polyester resin and the phosphoric acid group-containing copolymer resin, and is characterized by providing the excellent weather resistance and chemical resistance of urethane resins.

The blocked incyanate compound is a polyisocyanate compound having one or more incyanate groups in one molecule, such as ethylene diincyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, m-phenylene diisocyanate, p -phenylene diisocyanate, co-tertarylene diisocyanate, 2. i>-tolylene diinocyanate,
/, ,! i'-naphthylene diisocyanate, ri.

1.44"-triphenylmethane triisocyanate),
44.4'-diphenylmethane-diisocyanate, 3,3'-dimethyl-q, q'-diphenylene-diisocyanate, m-xylylene-diisocyanate, p
- polyinocyanate such as xylylene diisocyanate, inphorone diisocyanate, lysine isocyanate, and an excess of the above-mentioned isocyanate compound, such as ethylene glycol, propylene gellicol, /, 3-butylene glycol, neopentyl glycol, 2.2゜1J- ) Biuret, a co-functional or higher polyisocyanate obtained by addition reaction with a low-molecular polyol such as trimethyl l, 3-bentanediol, hexamethylene glycol, cyclohexane dimetatool, trimethylolpropane, hexanetriol, glycerin, pentaerythritol, etc. Polyincyanate having a structure is an incyanate compound obtained by blocking a polyincyanate etc. with an allophanate bond with a blocking agent.The blocking agent includes phenolics such as phenol and cresol, alcohols such as methanol, benzyl alcohol, and ethylene glycol monoethyl ether. active methylene series such as methyl acetoacetate and dimethyl malonate, acid amide threads such as acetanilide and acetate amide, other ide series, amine series, imidazole series, urea series, carbamate series, imine series, and oxime series. , mercaptan-based, sulfite-based, lactam-based, etc.

In the water-dispersed thermosetting coating composition of the present invention, effective crosslinking occurs when the blocking agent in the blocked isocyanate compound dissociates, so the dissociation temperature change of the blocking agent is preferably 100°C or higher. .

In the present invention, the weight ratio of the polyester resin and the phosphoric acid group-containing copolymer resin is 15/g5~q! ;/3, good tL(
is used at a ratio of 30/θ to 9θ/10.

In the range H, if the polyester resin is less than 1 szy, the seven characteristics of the present invention, such as the polyester resin's greater flexibility, pigment dispersibility, and excellent coating film appearance, are impaired. On the other hand, if the weight of the polyester resin exceeds 95%, the phosphoric acid group-containing copolymer resin will inevitably decrease, and the temporary rust prevention effect and corrosion resistance, which are the characteristics of the present invention, will decrease.

In one embodiment of the present invention, the amount of the mixture consisting of polyester am and phosphoric acid group-containing copolymer resin and the crosslinkable copolymer resin used is 207 x θ to gO/20' (
, weight %). Within this range, if the crosslinkable copolymer resin is less than 20% by weight, the crosslinkability of the coating film will be insufficient and the solvent resistance, chemical resistance, etc. of the coating film will tend to decrease; If the amount of synthetic resin exceeds go weight, the amount of polyester resin will inevitably decrease, and the flexibility, pigment dispersibility, etc., which are the characteristics of the present invention, will be impaired.

In another embodiment of the present invention, the amount of the polyester resin and the phosphoric acid group-containing copolymer resin and the crosslinking agent mixture consisting of the crosslinkable copolymer resin and the block incyanate compound is determined by weight ratio. 20/gO-g! ;//, 5-
(weight -). In this range, the crosslinking agent mixture is
If the weight is more than 0, the amount of the crosslinkable copolymer resin will increase, and the same problems as in the case of 9 will occur.

When a crosslinking agent mixture is used in the present invention, the crosslinking reaction is performed between the hydroxyl groups of the polyester resin and the phosphoric acid group-containing copolymer resin, and the N-alkoxymethyl groups and blocked isocyanate compound of the crosslinkable copolymer resin in the crosslinking agent mixture. This is done through the incyanate group in the.

The proportions of the crosslinkable copolymer resin and blocked isocyanate compound in the crosslinking agent mixture are preferably as follows.

[Amount of crosslinking agent mixture used (parts by weight)] - [Equivalence ratio of incyanate groups to hydroxyl groups is 0. The usage amount (parts by weight) of the blocked isocyanate compound that is /~/, 2
] = [Amount of crosslinkable copolymer resin used (parts by weight)], and approximately blocked isocyanate compound/crosslinkable copolymer resin = 0. / / 99.9~9/, 37za, S(
solid content weight ratio).

If the amount of blocked isocyanate compound used increases significantly, polyester resin and phosphoric acid group i! The reaction between the 1-copolymerized resin and the crosslinkable copolymer resin becomes poor, and the effect of improving the corrosion resistance, water resistance, etc. of the coating film, which is a characteristic of the crosslinkable copolymer resin, becomes poor.

Note that the polyester resin, the phosphoric acid group-containing copolymer resin, and the crosslinkable copolymer resin used in the present invention are made of the polyester resin, the phosphoric acid group-containing copolymer resin, the crosslinkable copolymer resin, and the block incyanate compound. The softening temperature of the fine powder resin particles obtained from the crosslinking agent mixture is 3
Preferably, the temperature is 0 to 100°C. More preferably Da 0~
gθ°C. As a result, the IJ II stability of paints with a softening temperature lower than 30°C tends to decrease.
If the temperature is higher than ℃, the smoothness of the coating film will be insufficient and rounding is undesirable. In the present invention, if necessary, a known acid catalyst for promoting the crosslinking reaction between the polyester resin and the phosphoric acid group-containing copolymer resin and the crosslinkable copolymer resin or the crosslinking agent mixture, as well as an epoxy resin, a cellulose-based It is also possible to use seven or more types of coating film-forming resins such as resins and anno resins.

Next, a method for producing the water-dispersed thermosetting coating composition of the present invention will be explained. The normal mechanical pulverization method used in conventional powder coatings and slurry coating Oa production can also be applied as a lI production method, but if the softening point is low, the stickiness of the resin particles is too high and the resin particles will be 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 f11@ and a phosphoric acid group-containing copolymer resin, and if necessary, a basic compound and a crosslinking agent that partially or completely neutralizes the acid groups in the phosphoric acid group-containing copolymer resin. A mixed resin composition with a polymeric copolymer resin or a crosslinking agent mixture, 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 to form a resin bath solution. Further, if necessary, a pigment is added and kneaded and dispersed to obtain a pigment dispersion.

The m-agent used in this case is the same as the polymerization solvent used in the solution polymerization method. The amount used is such that the non-volatile content of the above tree+11 solution or pigment dispersion is 30-8.
It is used in such a proportion that it is in the range of 0 weight -.

Next, this tree and bath solution or pigment dispersion i is emulsified into fine powder in an amount of water that dissolves all of the water-soluble or water-miscible solvent contained therein.

The amount of water used at this time is at least 6 times the amount (weight) of the resin solution or pigment dispersion, and should not exceed about 40 times the amount (weight) considering the mouth-passing process after emulsification. "preferable.

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 heating water and the solution or dispersion in a line mixer. 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, it is necessary to cool the mixed liquid to lower the liquid temperature. It is preferable to maintain the temperature at 30°C or lower. The above-mentioned stirring or mixing using an L-line mixer is carried out until the solvent in the emulsion fine particles is transferred to 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. These No. 11 fat particles are separated from the water-solvent mixture by passing or centrifuging, and if necessary, water washing and separation are repeated as many times as necessary to obtain resin particles in the form of a slurry-like or water-containing cake. In this way, preferably resin particles with an average particle size of between about 200 microns are obtained. Further, a surfactant and /1! are added to the slurry or water-containing cake-like resin particles. After adding a thickener and water, the resin particles are finely pulverized using a dispersion machine, a sand mill, a ball mill, a disperser, a Sassmeyer mill, or a Sentry mill, which are normally used for manufacturing paints, to obtain an average particle size. The phrase is arranged between approximately l and So-.

The thus obtained resin particles of the present invention contain a polyester resin, a phosphoric acid group-containing copolymer resin, a crosslinkable copolymer resin, or a crosslinkable copolymer resin and a block incyanate compound in -1 particles. In one particle, there are groups that react with each other when heated, that is, hydroxyl groups and N-
It necessarily contains an alkoxymethyl group, 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 adhesive properties can be obtained through crosslinking within each resin particle and crosslinking reaction 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 /~SOμ. If the average particle diameter is smaller than 7 μm, the particles tend to coagulate among themselves, and the particles tend to foam during heating, which is similar to that of water-soluble paints, which is undesirable. In addition, if it is larger than the SOS, the resin particles tend to precipitate and agglomerate during storage, making it impossible to obtain a smooth coating surface, which is undesirable for rounding.Resin particles with an average particle diameter of 32% have excellent storage stability. , a coating that provides a smooth coating film without foaming is formed and is suitable for the present invention. 1. The composition of the present invention may also contain, if necessary, a curing catalyst, organic and organic coloring and extender pigments commonly used in paints, temporary rust preventive agents, flow aids, antifoaming agents, anti-settling agents, Additives such as fungicides and preservatives, other water-soluble resins, and film-forming resins such as hydrosil and lusion resins can be included. 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 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. The ingredients are 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 1 propylene glycol fatty acid ester, polyoxyethylene castor oil derivative, polyoxycheti L /7 Alkyl phenyl ether, alkyl phosphate ester, phoroxyethylene phosphate ester, anionic surfactant:
Alkyl sulfate ester salt Bird polyoxyethylene alkyl ether sulfate ester salt, Alkyl sulfosucci 1lf
As the i, N-acyl sarcosine salt and the cationic surfactant, there may be used ammonium salts, viridinicum salts, and the like.

From the viewpoint of dispersion stability of ll11 particles and coating film performance, nonionic surfactants are preferred, and those having an HLB of g to 7t are preferred. In addition, instead of these surfactants,
Alternatively, as the thickener used in combination, those conventionally used in water-based resin paints can be used.

These are examples of t? , methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, etc. q) *Lulose water-soluble resin; polyvinyl alcohol; polyethylene water-soluble properties such as polyethylene glycol ether, polyethylene oxide, etc.: Mether vinyl ether anhydrous! Water-soluble resins based on maleic anhydride copolymers such as leic acid copolymers, ethylene maleic anhydride copolymers, and ethylene maleic anhydride copolymers; ammonium, amine salts, and sodium salts of acrylic acid polymers, bentonite, polyvinyl Examples include naturally occurring water-soluble resins such as pyrrolidone, alginate, polyacrylamide and its partially hydrolyzed products, casein and latin.

The above-mentioned surfactant and/or thickener is added to the fine powder resin particles by weight of o, oi-s, o. The amount added is 000
If the weight is less than 7.0, storage stability, painting workability, etc. will deteriorate, and if it is more than 5.0, the smoothness, water resistance, etc. of the coating film will deteriorate, making it unsuitable for the present invention. .

Among the above-mentioned thickeners, 72 salt of a carboxyl group-containing acrylic copolymer is particularly suitable for the present invention because it becomes water-insoluble after heating the coating film by eliminating the amine and does not reduce the water resistance of the coating film. suitable.

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

When the composition has fewer resin particles than the above mixing ratio, the solid content concentration of the coating material is low and the viscosity is low, so that the thickness of the normal coating film at one time, such as co-o-g.
When applied to oμ, a phenomenon of sagging occurs 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 will not be suitable for various painting methods such as spray painting and electrostatic painting. This is undesirable because it tends to result in poor AM workability and reduced practicality.

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

The conditions for heat curing after coating the coating composition vary depending on the content of crosslinkable functional group O in the composition, film thickness, etc., but are usually suitable within the temperature range of 1-θ to -0θ°C. Todoro na IIIf
A cured coating film can be obtained by heat treatment for 1o-ao minutes.

The cured coating film thus obtained suppresses temporary rust prevention on the steel plate, and has excellent adhesion to metal surfaces, corrosion resistance, and water resistance. Maku polyester resin has excellent flexibility, raw material dispersibility, and coating appearance, and phosphoric acid group-containing copolymer resin has excellent corrosion resistance, gI degree, and stain resistance, and crosslinking. It has the excellent hardness, stain resistance, and water resistance of polyurethane copolymer resins, and the weather resistance and chemical resistance of urethane resins. ), it has excellent coating performance.

The present invention will be explained below with reference to Examples. Oka, "bu" Mata F
ir(l Fi represents "parts by weight" or "weight-".

[Method for producing polyester resin solution]

(1) Synthesis of polyester 1HWPX-/II A reaction vessel equipped with a seismic intensity meter stirrer, a sparge gas introduction tube, a temperature control device, a partial condenser, etc. was charged with 704 parts of phthalic anhydride, 9 parts of Azivia'tll, and 1 part of propylene glycol. , 67 parts of dipropylene glycol, and trimethylolpropane 67&B were mixed and heated to 0-230°C while flowing nitrogen gas. After heating for S hours, when the acid value reached 20, the system was depressurized. 3 more
As a result of continuing the reaction for hours, acid value g1 hydroxyl value 751 weight average molecular weight 10. ! f: It is difficult to obtain a solid resin of 0θ. Dissolve this in methyl ethyl ketone, and the nonvolatile content t, o's tree Wt
Synthesis of polyester tree @px-1 by the same method as above (c)
Part O, 37 parts of adipic acid, 9 parts of benzoic acid, neopentyl glycol ggg, 61 parts of PAT' astragalus 1]col, and 7103 parts of trimethylolpro/(7103 parts) were combined and reacted in a nitrogen stream for 5 hours. Acid value 12, hydroxyl value ts, weight average molecular weight q, go.

A solid resin was obtained. This was dissolved in methyl ethyl ketone to obtain a resin solution with a nonvolatile content of 60%.

0) Synthesis of polyester resin PX-3 Using the same method as in V) above, 8100 parts of isophthalic acid and 20q of adipic acid were added.
Part, benzoin 1i 2 'I @% neopentyl glycol! fAW6, diglobylene glycol, S-1, 752 parts of trimethylolpro//, 6 hexanediol//1s were mixed and reacted for hours in a V-grade gas to give an acid value/
, S-, hydroxyl value 110s Weight average molecular weight t, 5o
ovviarn*h was obtained. This is methyl ethyl keto/
and a resin solution with a non-volatile content of 60%.

[Method for producing phosphoric acid group-containing copolymer resin solution] (1)
7,340 parts of methyl ethyl keto was placed in a reaction vessel equipped with a stirring t[, IIv meter, dropping funnel, and cooling tube, and after the temperature was lowered to gθ℃, the following compound and initiator mixture was added dropwise over 3 hours. 17. Methyl methacrylate gS part, methyl ref 160 parts Ethyl acrylic I7-t!
fO part, 2-L droxyethyl methacrylate 2! W&
, 22ethylhexyl acrylate), 25 parts 1,2--
f-Tylhexyl methacrylate 1llOW&, acidophosphoxyethyl methacrylate,! Ti! 1, Acrylic@IOm, 70 parts of azobisin butyronitrile.

After the dropwise addition was completed, a portion of azobisisobutyronitrile/, S was added, the reaction temperature was raised to 7°C, and the reaction was carried out for an hour to obtain an acid value/g of 2 and a hydroxyl value of 2 h. , weight average molecular weight 37.1. On and non-volatile content! A resin solution of 9.6- was obtained, and the softening temperature of the resin was about 7-? The temperature was 4°C. This was made into IPV-/3゜＠ The above PV-/ was synthesized, and methyl ethyl ketone 344 (Ha was added to the same reaction vessel as in 9), and the temperature was raised to 1!tgO℃. was added dropwise over 3 hours.Methyl methacrylate/10 parts, styrene l10WA.

Ethyl acrylate toco IO part, -monohydroxyethyl methacrylate SO part, acidophosphoxyethyl methacrylate 3 parts, 3-chlorocoacidophosphoxypropyl methacrylate)! s, acrylic @ 10s, azobisisobutyronitrile 10W 6° After completion of dropwise addition, azobisisobutyronitrile/, 3s was added, the reaction temperature was raised to t°C, the reaction was carried out for 9 fIk 4 hours, and lI! Ryoko O, da, hydroxyl value da S1 weight average molecular weight! f3. ! f00 and non-volatile content! ;9. t-
A resin solution with a softening temperature of approximately 60° C. was obtained. Said fil@fll*.

Neutralize by adding 34 liters of triether to the acid value and set the acid value to Pv-1.

[Method for producing crosslinkable copolymer resin solution]

(1) Synthesis of crosslinkable copolymer resin AX-/3 qO parts of methyl ethyl ketone was placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube, and a nitrogen gas introduction tube, and the temperature was raised to 0°C. , the following monomer and initiator mixture was added dropwise over 3 hours. Methyl methacrylate 50 parts, Ste 2 Fufu 50 parts, ethyl acrylate/6
! part f, N-n-butoxymethylacrylamide 12
Part s, 810 parts of acrylic, 70 parts of azobisisobutyronitrile.

After finishing dropping, add anobisisobutyronitrile/,! Part f was added, the reaction temperature was raised to g7°C, and the reaction was carried out for 4 hours after death, acid value /, 2. θ, weight average molecular weight 3g, 000s
A resin solution with a non-volatile content of Sg and 'l- was obtained, and Ws
The softening temperature of fat is about 73 to 75 degrees Celsius. AX-
/ Closed.

(J Synthesis of crosslinkable copolymer resin AX-co) Into a reaction vessel similar to the one in which the above-mentioned AX-/ was synthesized was heated to 0°C, the following monomer and initiator mixtures were added dropwise over 3 hours. Methyl methacrylate /10 parts, styrene A, Si
'l! 6. Ethyl acrylate/6! f, 100 parts of N-n-butoxymethylacrylamide, 10 parts of acrylic acid, 70 parts of azobisin butyronitrile.

After finishing the dropping, azobisin butycarbonitrile/, jWLe
After increasing the reaction temperature to 7°C, core decoupling was performed for 4 hours to obtain an acid value of 3.9 and a weight average molecular weight of 12.00.
A resin solution with 0 and non-volatile content of 19.0% was obtained.
The softening temperature of tl was 72-5°C. This is t-AX
-I made it.

[Solvent replacement method for blocked isocyanate compound] When using a blocked isocyanate compound containing a hydrophobic solvent, the solvent in the emulsion fine particles is not extracted into water and remains in the resin particles during the process of forming resin particles. In order to
41flff? This is not preferable because the particles coalesce or become integrated, which impairs stability. Therefore, the blocked isocyanate compound was subjected to solvent substitution using the method described below and used in the present invention.

Takenate B-g, 2θN5U (Narita Pharmaceutical Co., Ltd.)
Product name: Contains NCO @ 11.3 yen, non-volatile content t, o
's<solvent varnish-percy kl! ;00/butyl acetate)
) e After vacuum drying for 2 days in a vacuum dryer at 40° C. (non-volatile content: 9Ql*), methyl ethyl ketone was added thereto and diluted to a non-volatile content of bo's to obtain NGO-A.

[Implementation car/]

25 parts of polyester resin solution (PX-/), 33.3 parts of titanium dioxide, 770 parts of methyl ethyl keto, flow aid (
Product name: Moda Flow (manufactured by Monsanto) / Contains i6
Polyester resin solution (PX-/) i7.
2 parts, phosphoric acid group-containing copolymer resin (PV-/) t-, 1,
Part g, and crosslinkable copolymerized tree @CAX-2>'1k10
After mixing and stirring 7 parts, this was made into a uniform coating solution.

This was dropped into 3000 parts of water at a water temperature of 75° C. under high speed stirring to emulsify the pigment dispersion and extract the solvent into the water to form resin particles. Thereafter, filtering and washing with water were repeated to obtain a water-containing cake of resin particles having an average particle diameter of about IQθμ and a water content of about SO. To 100 parts of this water-containing cake was added nonionic surfactant 4IQ-water layer 1 [(1llA4 Engineering 9301 manufactured by Kao Atlas Co., Ltd., HL B/!;
, / ) 0. ! WL, a part of aqueous solution of alkali salt thickener OvI of 7-acrylate copolymer was added, and the resin particles were finely pulverized by dispersion kneading with a sand mill, and the average particle diameter/lμ was obtained.
, -7,9 slurry paint was obtained.

[Example-K]

33.3 parts of titanium monoxide, 770 parts of methyl ethyl ketone, and flow aid (
(Product name: Modaflow Common Sand Co., Ltd.) ls blended and kneaded and dispersed in an am pot mill until it becomes less than IOμ, then added to Ninele Pace and polyester** solution (PX-2')
tJ t,, 3g, IJ/acid fili copolymerized tree *CPV-2) t2 eight part and crosslinkable tree 111r (A
X-/)qIl and JIl were added and mixed to form a uniform coating solution. The water temperature of this tube is 6°C under high stirring.
The pigment dispersion was emulsified by adding the water dropwise into the water, and the Kf# agent was extracted into the water to form resin particles.

After that, filtration and washing with water were repeated, and the average particle size was approximately 1OO.
A water-containing cake of resin particles with a water content of approximately SO- was obtained. Add 100 seconds of this water-containing cake to a 7-ionic surfactant da-θ-aqueous solution (trade name Emuldan 910 HLB manufactured by Kao Atlas Co., Ltd.).
, 2. λ) 0.6 part, a thickener (hydroxyethyl cellulose j17t[[)elm] was added, dispersed and kneaded in a ball mill, and the resin particles were finely pulverized to obtain an average particle diameter of 1μ, pl.
i'7. , t was obtained.

[Actual IIA Example 3] Polyester resin solution CPX-, 3) 2 g parts, titanium diml, 33.3 W&, methyl ethyl ketone 108,
Flow aid (trade name: Modatsuroni manufactured by Monsanto) 1st
Polyester resin 1111t (PX-
3) t/A, 7m, phosphate group-containing copolymerized tree 11 (
t of PV-,2), and parts of crosslinkable copolymer resin (A
After mixing X-'/) with /-0IB and stirring, this was made into a uniform paint S*. A slurry-like paint having resin particles having an average particle diameter of lSμ and pM of 7.3 was obtained by the method described in Example 1.

[Execution 11] Polyester Itllll solution 11 on the mill base of Execution M
Add 23 parts of (PX-1) and a phosphate group-containing copolymer @
(PV-/), 2 t, partially crosslinkable copolymerized tree @(
AX-/)? 0.7 Ill, and further 22 tm of a blocked isocyanate compound (NGO-^) and a dissociation catalyst (>0.3 parts of dibutyltin dilaurate) were added to make a homogeneous coating solution.This was done according to the method of the present study**
Average particle diameter of particles / ! T5Xpi? ,? 9. Obtain a slurry of paint.

[Example S]

Polyester wood (PX-
3)t4c/? il, I) 7 acids & containing 11 synthetic wood l1
16.7 parts of l(PV-co), crosslinkable copolymer resin (^X-
c) 20.0 parts, blocked isocyanate compound (NG
63.7 parts of O-^), and 0. Uniform paint 1111 by adding flB
i [Toshiku. This was carried out according to the method described in fi/, to obtain a slurry-like paint having an average particle diameter of 41 fat particles/6β, -7.9.

[Comparative Example 1] In addition to the integrated and dispersed mill base of Example 1, 100 parts of polyester resin solution (PX-/) and 11 parts of melamine tree were added.
(Average degree of condensation S1 etherification [2, S and water-soluble components/Is or less of butylated methylolmelamine resin 6
Add 7 parts of methyl ethyl ketone solution [3] to make a uniform paint solution. This was slurried by the same method as in Example 11/ to obtain a slurry paint having an average particle size/Sμ of -7.6.

[Comparison 1 pIl] Crosslinkable copolymerization - obtained from the monomer blend of the fat solution (AX-/) by blending 715 parts of dihydroxyethyl methacrylate as a substitute for N-n-butyrodimethylacrylamide/J, ts. Copolymer resin solution (hydroxyl value 10 g) aSll was mixed with 33.3 FB of titanium dioxide, 770 parts of methyl ethyl keto, and a flow aid (trade name: Modaflow: 2/1B manufactured by Monsando) and kneaded in a porcelain pot (#) until the amount reached 10 parts or more. The acrylic copolymer resin rit**tioo part and the melamine tree of Comparative Example 1 were added to the combined and dispersed NluPase to form a uniform coating solution.

This was made into a slurry using a method similar to that used in the previous study to obtain a slurry-like paint with an average particle size of -7.

Zinc phosphate II &! Spray 1riit on a good dull steel plate, 1. S-Minute dragon Tsuten ink after death? O
Preheated at ℃ for 70 minutes. Thereafter, each was heated and dried at a predetermined temperature to form a coating film with a thickness of 3Sμ. Table 1 shows the heating drying conditions and physical property test results for m*.

(However, for the test piece to observe the appearance of the paint film, use a polished mild steel plate.)

Note 1 Smoothness of painted surface and condition of pinholes, underarms, etc. 260 degree bell face Tozawa value Note 3 Visual judgment of appearance during setting Da JIS
Notes based on the method of -5tioo S Gopan eye tag peel test Note 6 Using Erichsen testing machine Note 7 JIS-! ;QOOVc Note g
Contamination with marker ink Note 9 Condition of coating film after immersion in warm water for 2 days at 0°C (
Blister evaluation ◎ 100/100~90/1000
g9/100-40/100X! f9/100~0/100 Note lθ Humidity test <50℃, 9711 RH<)200
Evaluation of coating surface layer properties after hours is the same as Note 9.Note 1/Coating film condition after immersion in S-caustic soda aqueous solution for 10 hours at room temperatureNote/, 2 Game condition after immersion in aqueous solution at room temperature for 10 hoursNote/ , 3 According to the method of JIS-5uoo. Evaluation of secondary coating adhesion after suspension for 2' IO time ◎ (.. chestnut width) 0-/, 0■ 0 (-. chestnut width) 1. /~20−Δ−) and Chi! Adhesion test by peeling (one side peeling) 3. O ■ × (peel off one side) 3. Note/4 (Sunshine Weather Tester St time, presence or absence of 111 yoking, cracks, and blisters) Note/j Sunshine Weather Tester 1 ooo time: Note Hold in a constant temperature water bath at 50°C to gel or harden. Shen.

Condition of painted surface II: 60 hours of immersion in warm water at θ°C (1 cycle)
I (Check the cycle and display the number of previous cycles in which an error occurred.

Gloss value after racking/initial gloss value Indicates the number of days in which beatings, etc. occur.

As is clear from the above comparative test result table, the coating film obtained from the composition of the present invention did not cause any temporary rusting after application.
It also does not foam during heating and drying.

Furthermore, compared to the composition of the film obtained by Mon et al., it is denser and layered,
It had excellent flexibility, impact resistance, chemical resistance, stain resistance, water resistance, and weather resistance, and was particularly excellent in moisture resistance, corrosion resistance, and storage stability.

616-

Claims (1)

[Scope of Claims] (1) (Al(a) polyester resin with a hydroxyl value of 10 to 300...1s-qs weight), and (b) (1) IJ acid A hydroxyl group value of 3 to 3 obtained from a monomer mixture consisting of a group-containing α,β-monoethylenically unsaturated monomer and an α,β-monoethylenically unsaturated monomer other than (Itl General (1)) 15
0 phosphoric acid group-containing copolymer resin・・・・・・・・・g
(B) (+) α,β-monoethylenically unsaturated power A/
From a crosslinkable copolymer resin obtained from a monomer mixture of an N-alkoxymethylated monomer of &nic acid amide and (il) an α,β-monoethylenically unsaturated monomer other than (1) above. Fine powder thermosetting resin particles consisting of 0
．． An aqueous dispersion thermosetting coating composition consisting of a surfactant and/or thickener of 0.01 to 0.01 to 0.000 x t, and the required amount of water. (2) The mixing ratio of the prisoner and the above (B) is the same as the above (B).
20~go weight-1 above (B) ff O-20 weight-
A water-dispersed thermosetting coating composition according to claim V), in a proportion such that: ■ The monomer mixture constituting the phosphoric acid group-containing copolymer resin is: (1) Phosphoric acid group-containing α,β-monoelenic unplated monomer -・・・・・・o, oi -io type weight (i) α,β-monoethylenically unsaturated carboxylic acid・
・・・・・・・・・0. ! ;-10 weight-(ull α
, hydroxyalkyl ester of β-monoethylene unsaturated carboxylic acid...7 to 30 weight - 0v) Other than (1) and (il) 1st holl) above, both O and 1 & The water-dispersed thermosetting coating composition according to claim 1, comprising: a, p-monoethylenically unsaturated monomer 70-90% by weight. (The monomeric p-polymerization material constituting the crosslinkable copolymer resin is (+) N-alkoxymethylated a-mer of α,β-monoethylenically unsaturated carbonate amide...--・
5-30 weight - (II) α, β-monoethylenically unsaturated carboxylic acid 0. ! f-10 weight - (110 Copolymerizable α, β-monoethylenically unsaturated monomer other than the above (1) and (Q)...60 to 90 weight) Claim item υ) The moisture lk type mature heat-curable coating composition (3) (~(a) polyester resin with a hydroxyl value of 10 to 300.../S~95 weight-1 and (bl phosphoric acid group) Hydroxyl group value 3 obtained from a monomer mixture consisting of a containing α,β-monoethylenically unstable monomer and (if) an α,β-monoethylenically unsettled monomer other than the above (1) ~IS
O phosphoric acid group-containing copolymer resin......g!
;-! a mixture consisting of (by weight) and (1) an N-alkoxymethylated monomer of α,β-monoethylenic carboxylic acid amide, and (ill M (1) A crosslinkable copolymer resin obtained from a monomer mixture with an α,β-monoethylenically unsaturated monomer other than the above, and (b) a crosslinking agent mixture comprising a block isocyanate compound. Resin particles, 0 for the particles
．． O/~! ; 0 weight surfactant and/or thickener; and the required amount of water. (6) The proportion of the mixture of (A) and (B) is such that (A) 20~g5 weight - 1 spinning (g)) gθ~/S1 amount -. A water-dispersed, slightly thermosetting coating composition according to scope item (3). (7) The monomer mixture constituting the phosphoric acid group-containing copolymer resin has the following properties: (1) IJ group-containing α,β-monoethylenically unsaturated percentage weight: 0007 to 10% by weight −
(It) α,β-monoethylenically unsaturated carboxylic acid...0.5~/θweight- (II α,β-monoethylenically unsaturated carboxylic acid hydroxyalkyl ester of monoethylenically unsaturated carboxylic acid... ...7 to 30 weight - 0φ From the copolymerizable α,β-monoethylenically unplated monomer other than the above (IL (li) and (fl)...70 to 90 weight - The water-dispersed thermosetting coating composition according to claim (1), consisting of (υ) the monomer mixture constituting the crosslinkable copolymer resin: N-alco dimethylated monomer of Kojiwa carboxylic acid i...
... c., 5 to 30 weight - (If) α, β-monoethylenic non-kojiwa carbonacea ... 0. S~IO weight ratio (11D Copolymerizability α other than (1) and (+1) above
The water-dispersed thermosetting coating composition according to claim 3, comprising 60 to 90% by weight of a β-monoethylenically undiagnosed monomer. (q) The solid content weight ratio of the crosslinkable copolymer resin and the block isocyanate compound is 9q, 910. /~Jr.
! f/91. The water-dispersed thermosetting coating composition according to item (a), wherein the content is 1%.