JPS6034989B2 - 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 temporary rust prevention, corrosion resistance, chemical resistance, cold/heat cycle 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 with a thickness of less than 0 French. Furthermore, among water-based paints, water-soluble paints have a low solid content concentration during painting, so it is difficult to apply a thick film at once. The problem was that the durability could not be achieved. On the other hand, emulsion paints have the problem of poor water resistance, chemical resistance, etc. of the paint film because they use a large amount of surfactant. As a way to solve these problems, slurry paint (water-dispersed paint) is a method in which resin powder is suspended in water and applied like a water-based paint.
is proposed. 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 will occur during baking, so there is a drawback in terms of paint 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, a temporary rust preventive agent is often used in conjunction with the water-based paint, but using 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, is easy to work with, has no defects such as wrinkles during phosphorization, and has excellent gloss, smoothness, temporary rust prevention, corrosion resistance, chemical resistance, corrosion resistance, and cold and heat cycle resistance. The present invention provides a water-dispersible thermosetting coating composition having excellent coating performance. That is, the present invention provides a compound having an air value of 50 or less and a hydroxyl value of 50, which has Q.8 monounsaturated dicarboxylic acid as one of the constituent components in the weight percent of 1 to 1.
~250 Unsaturated polyester resin having a weight average molecular weight of 2,000 to 120,000 2
~4% by weight and 'ii'a' is a hydroxyalkyl ester of an 8-monoethylene unsaturated carboxylic acid...
...0.5 to 3% by weight {b' N-alkoxymethyl I○ mass of Q.8-monoethylene unsaturated carboxylic acid amide...
...・5~3% by weight'c} The above

[a}, {b} and'
. }Copolymerizable Q.8-monoethylene unsaturated monomer other than {a}. ．． ．． ．． ...... Monomer mixture consisting of 60 to 9% by weight......98 to 6% by weight, obtained by graft polymerization, hydroxyl value 10 to 15
0, acid value 3-40, weight average molecular weight 40,000-200
000 polyester modified vinyl resin...
...15-95% by weight'. ) [a) Phosphoric acid group-containing Q.3-monoethylene unsaturated monomer...0.01 to 1% by weight'
b1 Q・8-monoethylene unsaturated carboxylic acid...
...0.5-1% by weight [C} Q.Hydroxyalkyl ester of 3-monoethylene unsaturated carboxylic acid..........1-3% by weight 'd' above 'a}, { b', 'c' and {ii'{ii'
Copolymerizable Q/B monoethylene unsaturated monomer other than 'b'...・・・．・・・． Phosphate group-containing copolymer resin having a hydroxyl value of 3 to 150 and a weight average molecular weight of 8,000 to 70,000 obtained from a monomer polymer comprising 70 to 9% by weight... fine powder thermosetting resin particles consisting of a mixture consisting of 85 to 5% by weight and a blocked isocyanate compound; 0.01 to 5.0% by weight of surface activity based on the particles; The present invention relates to a water-dispersible thermosetting coating composition comprising: an agent and/or a thickener; and a required amount of water. The polyester-modified vinyl resin used in the present invention is obtained by graft polymerizing an unsaturated polyester resin with a Q/B-monoethylene unsaturated monomer mixture [the above-mentioned 'A' side]. It is characterized by providing vinyl resin with the excellent dispersibility, pigment dispersibility, and coating appearance that resins have. Therefore, it is necessary to use Q.8 monounsaturated dicarboxylic acid as a raw material for the unsaturated polyester resin used in the present invention. The component is 1 to 1 in the unsaturated polyester resin.
The reaction is carried out in a proportion of 10% by weight, preferably 3 to 7% by weight. That is, if the amount of this component is 1% by weight or less, the amount is not sufficient for the Q/B-monoethylene unsaturated monomer when producing the polyester-modified vinyl resin, and therefore the polyester modification is insufficient, resulting in The product has a blended composition of an unsaturated polyester resin and a polymer of Q/6-monoethylene unsaturated monomer, and the coating film may become white. Further, due to the difference in reactivity between the crosslinking reactive group and the blocked isocyanate compound, coating film performance, particularly adhesion, tends to deteriorate, which is not preferable. On the other hand, the component is 1
If it is 0% by weight or more, gelation occurs during the grafting reaction with the monomer polymer, which is not preferable. Specific examples of the Q.8-unsaturated dicarboxylic acid component include fumaric acid, (
Examples include (anhydrous) maleic acid, itaconic 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 resin used in the present invention, a carboxylic acid component other than the above-mentioned acid is preferably reacted in a proportion of 29 to 6% 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 methyltetrahydrophthalic acid (anhydride). acid,
Examples include methylhexahydrophthalic anhydride, imic acid anhydride, succinic acid (anhydride), adipic acid, sebacic acid, benzoic acid, para-tert-butylbenzoic acid, etc.
These may be used alone or in a mixture of two or more. In the synthesis of the unsaturated polyester resin used in the present invention, the polyhydric alcohol component is preferably reacted in a proportion of 30 to 7% by weight. Specific examples of the components include ethylene glycol, diethylene glycol, propylene glycol, neobentyl glycol, dipropylene glycol, glycerin, trimethylolethane, trimethylolproban, bentaerythritol, diventaerythritol, butanediol, Examples include bentanediol, hexanediol, 1,4-cyclohexanedimethanol, (hydrogenated) bisphenol A, and the like. These may be used alone or in combination with a mixture of two or more thereof, and if necessary, a glycidyl ester of tertiary synthetic saturated fatty acid (Cardular E: manufactured by Shell Chemical Co., Ltd., trade name). In addition, animal and vegetable oils, their fatty acids, petroleum resins, rosin, phenol resins, epoxy resins, etc. can also be used as modified raw materials for unsaturated polyester resins, if necessary.
The unsaturated polyester resin in the present invention is produced by a single-stage reaction or a multi-stage reaction by a known method, and the reaction method is not limited. Further, a polymerization solvent described below can be used as a diluent if necessary. The acid value of the unsaturated polyester resin of the present invention is 50 or less (resin solid content: hereinafter all acid values of the present invention are expressed in the same way), and the hydroxyl value is 50 to 250 (resin solid content: hereinafter the hydroxyl group of the present invention). All prices are displayed in the same way),
The weight average molecular weight ranges from 2,000 to 120,000. The weight average molecular weight was measured by gel permeation chromatography (Model A801 manufactured by Toyo Soda). Hereinafter, the weight average molecular weight in the present invention was measured in the same manner. In the present invention, when the acid value of the unsaturated polyester resin becomes 50 or more, the alkali resistance etc. in the final coating film performance after graft polymerization of the 8-monoethylene unsaturated monomer mixture decreases. In addition, if the hydroxyl value is lower than 50, the crosslinkability between the polyester-modified vinyl resin graft-polymerized with the Q.8-monoethylene unsaturated monomer mixture and the blocked isocyanate compound described below tends to be insufficient, and If it is higher, the water resistance of the resulting coating film tends to decrease due to an increase in the number of polar groups, which is not preferable. In addition, if the weight average molecular weight is lower than 2000, the properties of the polyester resin cannot be fully exhibited, and if it exceeds 120000, the molecular weight of the polyester resin is too high and modified with a Q.3-monoethyletho unsaturated monomer mixture. In this case, the viscosity becomes too high, which impairs workability, which is not preferable. The polyester-modified vinyl resin in the present invention has [ii}'ii}{a
}Hydroxyalkyl ester of Q.8-monoethylenically unsaturated carboxylic acid, {a'(ii) (b) N-alkoxymethylated monomer of Q.8-monoethylenically unsaturated carboxylic acid amide, and'i) {ii }{c} Said {a'
, 'b' and Q.8-monoethylene unsaturated monomers other than 'o)'a} described below are obtained by graft polymerization. The polyester-modified vinyl resin in the present invention must contain a hydroxyl group in the molecule in order to undergo a self-crosslinking reaction, including a crosslinking reaction with a phosphoric acid group-containing copolymer resin and a blocked isocyanate compound. . Therefore, a hydroxyalkyl ester of Q.B-monoethylene unsaturated carboxylic acid is used as a type of Q.8-monoethylene unsaturated monomer. The hydroxyalkyl ester monomer is preferably a B-monoethylene unsaturated monomer compound [(ii) above] so that the hydroxyl value of the polyester-modified vinyl resin is 10 to 150.

0.5 to 3% by weight in [ii} component]
It is particularly preferably used in an amount of 1 to 15% by weight. If the monomer is used in an amount exceeding 3% by weight, the polyester-modified vinyl resin will have a high viscosity, and the crosslinking density after the thermosetting reaction with the phosphoric acid group-containing copolymer resin and the blocked isocyanate compound will increase. If it becomes too high, the flexibility of the coating film,
This is not preferable since water resistance etc. tend to decrease. Specific examples of the monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate.
-Hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxybentyl (meth)acrylate, 6-hydroxyhexyl (
meth)acrylate, neobentyl glycol mono(meth)acrylate, 3-poxy-2-hydroxylpropyl(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, the N-alkoxymethylated monomer component of the Q.B-monoethylene unsaturated carboxylic acid amide used for graft polymerization with the unsaturated polyester resin is Q.8-
Necessary for crosslinking reaction of monoethylenically unsaturated carboxylic acid with hydroxyalkyl ester component and polyester resin component. This component is graft-polymerized in the Q.8-monoethylene unsaturated monomer mixture in a proportion of 5 to 3% by weight, preferably 10 to 2% by weight. If the content of this component is 5% by weight or less, the crosslinking reaction of the polyester-modified vinyl resin will be insufficient, resulting in a decrease in the solvent resistance of the coating film. Moreover, if it exceeds 3% by weight, gelation occurs during the graft polymerization reaction, which is not preferable. Specific examples of the component include N
-Methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-n-propoxymethyl (meth)acrylamide, N-isoproboxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-sec-butoxymethyl (meth)acrylamide ) acrylamide, N-t-butoxymethyl (meth)acrylamide, N-isobutoxymethyl (meth)
Examples include N-alkoxymethylated products of Q.8-monoethylene unsaturated carboxylic acid amides such as acrylamide, or N-methylolated products thereof, and these may be used alone or as a mixture of more than one kind. In the present invention, the hydroxyalkyl ester monomer of the Q-momonoethylene unsaturated carboxylic acid, the N-alkoxymethylated monomer of the Q-8-monoethylene unsaturated carboxylic acid amide, and the phosphoric acid group-containing monomer described below Q.8-
Monomers other than the monoethylenically unsaturated monomer [component 'A'] may be used in combination. The monomer is preferably used in a range of 60 to 9% by weight in the monomer mixture. Specific examples of the monomer include Q.8-monoethylene 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-phthyl(meth)acrylate, sec-butyl(meth)acrylate, t-butyl(meth)acrylate, isobutyl(meth)acrylate, n-hexyl(
Alkyl esters of acrylic acid or methacrylic acid such as meth)acrylate, 2-ethylhexyl(meth)acrylate, n-octyl(meth)acrylate, lauryl(meth)acrylate, tridecyl(meth)acrylate, and stearyl(meth)acrylate; Other N・N
'-Dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)
Examples include monomers such as dialkyl esters of fumaric acid such as acrylate, phenyl methacrylate, pendyl methacrylate, and geptyl fumarate, styreso, vinyltoluene, Q-methylstyrene, (meth)acrylonitrile, and vinyl acetate. . The above-mentioned monomers can be used singly or in an appropriate combination of two or more depending on the purpose and use of the coating composition. The polyester modified vinyl resin contains 2 to 4% by weight of the unsaturated polyester resin and 60 to 9% by weight of the monomer mixture.
It consists of a graft polymerization reaction product with neck weight%. The amount of modification of the unsaturated polyester resin is 2 to 4% by weight, preferably 5 to 3% by weight. If it is lower than 2% by weight, the foundationability of the PoIJ ester resin,
The excellent pigment dispersibility and coating film appearance cannot be fully demonstrated, and when the content exceeds 4% by weight, the hardness, stain resistance, etc., which are the characteristics of vinyl resins, are impaired. The polyester-modified vinyl resin used in the present invention is produced by conventional solution polymerization. For example, a method in which the remaining monomer (mixture) and a polymerization initiator are dropped into a mixture of an unsaturated polyester resin, a part of the monomer (mixture), and a polymerization solvent, and polymerization is performed; There is a method in which a polyester resin, a monomer (mixture), and a polymerization initiator are dropped and polymerized, but there is no particular restriction on the solution polymerization method. Generally, the polymerization temperature range is about 50 to 15 hours, and the polymerization reaction time is about 4 to 1 hour, depending on the temperature. The polymerization solvent used in the solution polymerization method is a water-soluble or water-miscible solvent, such as alcohols such as methyl alcohol, ethyl alcohol, in-propyl alcohol, n-propyl alcohol, ethylene glycol monomethyl, etc. Ethylene glycol derivatives such as ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate: diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, etc. Diethylene glycol derivatives: esters such as methyl acetate, ethyl acetate, and 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. Especially when the solubility in water is 20oo, it is 10
Preferably, the amount is about 3 to 3% by weight. The amount of the polymerization solvent used is preferably such that the nonvolatile content during production of the polyester-modified pinyl resin is 10 to 8% by weight, preferably 20 to 7% by weight. Examples of the polymerization initiator used include penzoyl peroxide, t-butyl perbenzoate, t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, t-butyl peroctate, and azo compounds such as azobisisobutyronitrile and azodiisobutyric acid nitrile. One or more of these polymerization initiators may be used in combination as appropriate. The polymerization initiator is used in an amount of about 0.1 to 15% by weight based on the nonvolatile content during production of the polyester-modified pinyl 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 transport 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 10 to 150, preferably 20 to 150.
100, and the acid value is in the range 3-40, preferably 5-30. If the acid value is lower than 3 to 4, the thermosetting properties will be insufficient, resulting in poor coating film hardness, water resistance, corrosion resistance, durability, etc. On the other hand, if the acid value is higher than 4, the coating film performance and storage stability will deteriorate. descend. Moreover, when the hydroxyl value is 10 or less, the crosslink density decreases, and the solvent resistance of the coating film decreases. On the other hand, if it is greater than 150, the paint film's susceptibility and water resistance will decrease. The weight average molecular weight of the polyester modified vinyl resin of the present invention is 4000
0-200000, preferably 50000-15000
It is within the range of 0. If the weight average molecular weight is 40,000 or less, the coating film and performance will not be sufficient, while if the weight average molecular weight is 200,000 or more, the smoothness of the coating film will be impaired, which is not preferable. Next, the phosphoric acid group-containing copolymer resin [component {o)] used in the present invention contains phosphoric acid group-containing Q.6-
A monoethylenically unsaturated monomer [component a)] and a Q/8-monoethylenic unsaturated monomer other than the above [component 'b], [c] and [o} (d) described below] It was obtained by copolymerizing. By introducing the phosphoric acid group-containing Q.8-monoethylene unsaturated monomer, even when the coating composition of the present invention 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 Q.8-monoethylene unsaturated monomer is present in an amount of 0.01 to 10.0% by weight, preferably 0.5% by weight in the monomer mixture.
~5. Use within a range of % 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 copolymerization reaction process. Further, since a sufficient effect can be obtained within 1% by weight, it is economically undesirable to use more than 1% by weight. Specific examples of the monomer include acrylic or methacrylic acids containing a hydroxyl group such as acidophosphoxyethyl (meth)acrylate, acidophosphoxypropyl (meth)acrylate, and 3-chloro-2-acidophosphoxypropyl methacrylate. Primary phosphate esters; bis(meth)acryloxyethyl phosphate, acrylic alcohol acid phosphate, vinyl phosphate, mono[2-hydroxyethyl (meth)acrylate] acid phosphite, etc., and their salts and esters, etc. It is one kind or a mixture of two or more kinds. Such monomers are produced by reacting a Q.3-monoethylene unsaturated monomer having a hydroxyl group with phosphoric anhydride and hydrolyzing the product, but other monomers such as orthophosphoric acid, metaphosphoric acid, It can also be produced using phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, etc. Phosphoric acid group-containing Q.8-monoethylene unsaturated monomer used as an essential component in the phosphoric acid group-containing copolymer resin [
Monomers other than {rho {a} component] include Q.8-monoethylene unsaturated carboxylic acid [{o} (b'component);
Hydroxyalkyl ester of Q.8-monoethylene unsaturated carboxylic acid [component 'k] and the above (ii)
``b}, [Ro The above-mentioned phosphoric acid group-containing copolymer resin needs to contain a hydroxyl group in the molecule in order to react with the above-mentioned polyester-modified vinyl resin and blocked isocyanate compound. Therefore, the above-mentioned polyester-modified vinyl resin In order to maintain a balance with the hydroxyl value of It is used in an amount of 1 to 3% by weight, preferably 2 to 15% by weight in the monomer polymer constituting the phosphoric acid group-containing copolymer resin. If the monomer is used in an amount exceeding 3% by weight If this happens, it becomes easy to gel during the copolymerization reaction, and the resulting phosphoric acid group-containing copolymer resin has a high viscosity, and the crosslinking density with the polyester-modified vinyl resin and blocked isocyanate compound becomes too high, making it difficult to coat. This is undesirable because it tends to reduce the film's susceptibility, water resistance, etc. Specific examples of monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl. (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxybentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate , neobentyl 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, etc. These may be used alone or as a mixture of two or more.As one component of the phosphoric acid group-containing copolymer resin used in the present invention, 0.5% of Q.8-monoethylene unsaturated carboxylic acid is used.
-1% by weight. The monomer has the effect of improving the compatibility between the phosphoric acid group-containing copolymer resin and the polyester-modified vinyl resin and promoting the crosslinking reaction. If the amount is less than 0.5% by weight, the effect will be weakened, and if it exceeds 1% by weight, the performance of the cured coating film will deteriorate, which is not preferable. Specific examples of the component 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 two or more. As a raw material for the phosphoric acid group-containing copolymer resin used in the present invention, 7 Q.8-monoethylene unsaturated monomers other than those mentioned above are used.
The reaction is carried out at a ratio of 0 to 9% by weight. Specific examples of the component include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate,
Isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate,
Alkyl esters of acrylic acid or methacrylic acid such as 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, and stearyl (meth)acrylate; other N/N' - Dialkyl fumaric esters such as dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl methacrylate, pendyl methacrylate, and geptyl fumarate, styrene, vinyltoluene, Q-methylstyrene, Examples include monomers such as (meth)acrylonitrile and vinyl acetate. The above monomers may be used alone or in an appropriate combination of two or more depending on the purpose and use of the paint mixture. The phosphoric acid group-containing copolymer resin of the present invention is produced by conventional solution polymerization. As the polymerization solvent used in the solution polymerization method, the above-mentioned water-soluble or water-temperature solvents are used. Further, 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. The polymerization temperature during production of the crosslinkable polymer resin is about 50 to 150°C, and the reaction time is about 4
-1 incubation time, and the polymerization solvent used at that time is used in such a range that the nonvolatile content during the resin production is 10 to 8% by weight, preferably 20 to 7% by weight. In this case, although a large amount of the phosphoric acid group-containing Q.8-monoethylene unsaturated monomer is used, it is better to lower the nonvolatile content. The amount of polymerization initiator used is about 0.1 to 15% by weight based on the nonvolatile content during production of the phosphoric acid group-containing copolymer resin.
The chain transfer agent is preferably used at the same time in an amount of about 0 to 5% by weight. The weight average molecular weight of the phosphoric acid group-containing copolymer resin of the present invention is 8
000-7000 ribs or 20000-50000
is within the range of If the weight average molecular weight is less than 8,000, the coating performance will be insufficient;
000 or more, smoothness will be impaired. Further, the hydroxyl value of the phosphoric acid group-containing copolymer resin of the present invention is 3 to 1.
The range is 50. When the hydroxyl value is 3 or less, the crosslink density decreases and the solvent resistance of the coating film decreases. On the other hand, if it is larger than 150,
The flexibility of the coating film decreases, and the water resistance also decreases. Since the phosphoric acid group-containing copolymer 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, the acid groups introduced into the phosphoric acid group-containing copolymer resin are neutralized with a basic compound to make the phosphoric acid group-containing copolymer resin more stable. It can be made of resin. Examples of the basic compound include inorganic alkalis such as sodium hydroxide and potassium hydroxide; water-soluble amines such as ammonia, monomethylamine, dimethylamine, trimethylamine, triethylamine, monoethylamine, mono-n-propylamine, and dimethyl-n-propylamine; mono-ethanol; Amine, diethanolamine, triethanolamine, N-methylethanolamine, N-aminoethylethanolamine,
N-methyldiethanolamine, monoisof. Examples include one or a mixture of two or more of water-soluble oxyamines such as bipropanolamine, diisopropanolamine, tripropanolamine, and hydroxylamine. When neutralizing using such a compound, it includes neutralizing some or all of the acid groups in the phosphoric acid group-containing copolymer resin, and furthermore, it includes neutralizing 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 resin composition or the performance of the coating film. Next, the blocked isocyanate compound [component {B)] used in the present invention is an isocyanate compound having two or more isocyanate groups in one molecule, and all of the isocyanate groups are masked with a blocking agent. isocyanate compound. The blocked isocyanate compound is necessary for the crosslinking reaction with the polyester-modified vinyl resin and the phosphoric acid group-containing copolymer resin, and is used to impart the excellent film resistance and chemical resistance of the isocyanate compound. It has characteristics. 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, 1
・5 Naphthylene diisocyanate, 4・4′・4″
Triphenylmethane triisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3-dimethyl-4,4-diphenylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, isophorone diisocyanate, lysine isocyanate, etc. An excess of polyisocyanate and the isocyanate compounds, such as ethylene glycol, propylene glycol, 1,3-butylene glycol, neobentyl glycol, 2,2,4-trimethyl 1,3
-2 obtained by addition reaction with low molecular weight polyols such as bentanediol, hexamethylene glycol, cyclohexanedimethanol, trimethylolpropane, hexanetriol, glycerin, bentaerythritol, etc.
It is an isocyanate compound obtained by blocking a polyisocyanate with a functional or higher functionality, a polyisocyanate having a biuret structure, a polyisocyanate having an allophanate bond, etc. with a blocking agent. The blocking agents include phenols such as phenol and cresol, alcohols such as methanol, benzyl alcohol, and ethylene glycol monoethyl ether, active methylenes such as methyl acetoacetate and dimethyl malonate, acetanilide, and acetic acid. Acid amide type such as amide, other imide type, amine type, imidazole type, urea type, carbamate type, imine type, oxime type, mercaptan type,
There are sulfite-based, lactam-based, etc. In the present invention, the weight ratio of the polyester-modified vinyl resin and the phosphoric acid group-containing copolymer resin is 15/85 to 95/5, preferably 30/7.
Used in a ratio of 0 to 90/10. If the polyester-modified vinyl resin is less than 15% by weight within the above range, one of the features of the present invention, such as the excellent visibility, pigment dispersibility, and coating film appearance, which the polyester resin has, will be impaired. On the other hand, if the amount of polyester-modified vinyl resin exceeds 9.5% by weight, the phosphoric acid group-containing copolymer resin will inevitably decrease, which will not only reduce the temporary rust prevention effect that is a feature of the present invention, but also reduce corrosion resistance and water resistance. Sex also gets worse. The crosslinking reaction in the composition of the present invention is carried out by hydroxyl groups in the polyester-modified vinyl resin and hydroxyl groups in the phosphoric acid group-containing copolymer resin, N-alkoxymethyl groups in the polyester-modified vinyl resin, and isocyanate groups in the blocked isocyanate compound. It will be done. The proportion of the mixture consisting of a polyester-modified vinyl resin and a phosphoric acid group-containing copolymer resin and the block isocyanate compound is [(hydroxyl group in the polyester-modified vinyl resin), (hydroxyl group in the phosphoric acid group-containing copolymer resin) )]/(isocyanate group in blocked isocyanate compound)=
The range is 1/0.1 to 1/1.2 (equivalent ratio). The equivalent weight ratio is approximately the following weight ratio. The solid content weight ratio of the mixture consisting of the polyester modified vinyl resin and the phosphoric acid group-containing copolymer resin and the blocked isocyanate compound is approximately 35/65 to 99.8/0.2.
This is the percentage of However, in the present invention, the N-alkoxymethyl group in the polyester-modified vinyl resin performs a self-crosslinking reaction, but also reacts with hydroxyl. It is preferable to use the hydroxyl group in the group-containing copolymer resin]/(isocyanate group in the blocked isocyanate compound)=1/0.2 to 1/0.8 (equivalent ratio). If the amount of the blocked isocyanate compound used is significantly small, the effect of improving the chemical resistance, weather resistance, etc. of the coating film, which is a feature of the present invention, will be poor. On the other hand, if it becomes significantly large, coating film performance such as water resistance will deteriorate due to the isocyanate groups that have not reacted with the hydroxyl groups in the resin. The softening temperature of the mixed resin particles of the mixture of the polyester-modified vinyl resin and the phosphoric acid group-containing copolymer resin and the blocked isocyanate compound used in the present invention is preferably 30 to 1000°. More preferably, it is 40 to 80 oo. Softening temperature is 30
If it is lower than qo, the storage stability of the paint tends to decrease, and if it is higher than 10,000, the smoothness of the coating film will be insufficient, which is not preferable. In addition, in the present invention, a known acid catalyst, a dissociation catalyst, and an epoxy resin are used to promote the crosslinking reaction between the mixture of the polyester-modified vinyl resin and the phosphoric acid group-containing copolymer resin and the blocked isocyanate compound, as necessary. It is also possible to use one or more types of coating film-forming resins such as cellulose resins, amino resins, and polyester resins. Next, a method for producing the water-dispersed thermosetting coating composition of the present invention will be explained. As a manufacturing method, the usual mechanical pulverization method used in the production of conventional powder paints and slurry paints can also be applied, but if the softening point is low, the stickiness of the resin particles is too high and the resin particles become powdered. This becomes difficult.
Therefore, the water-dispersed thermosetting coating composition of the present invention can be advantageously produced by a special method as described below. First, a predetermined amount of the polyester-modified vinyl resin and the phosphoric acid group-containing copolymer resin and, if necessary, a basic compound and a buffer that neutralize some or all of the acid groups in the phosphoric acid group-containing copolymer resin are added. . A mixed resin composition with a glycisocyanate compound, and if necessary, a curing catalyst, a dissociation catalyst, other coating film-forming resins, etc., are dissolved in the water-soluble solvent or water-temperature mixable solvent to form a resin solution, and if necessary, Add a pigment and knead and disperse to obtain a pigment dispersion. The solvent used in this case is the same as the polymerization solvent used in the solution polymerization method. In addition, the amount used is such that the non-dilute fraction of the resin solution or pigment dispersion is 3
They are used in proportions ranging from 0 to 8% 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 solvent or water-temperature-mixable 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 filtration step after emulsification. . Further, the emulsification of the resin solution or pigment dispersion can be carried out by dropping or pouring the solution or dispersion into water under severe agitation.
Methods such as mixing water and the solution or dispersion liquid with a line mixer can be used, but at this time, the temperature of the mixed liquid increases due to the damage, and the resin particles do not coalesce due to the softening of the resin. In order to prevent the mixture from becoming integrated and coarsening, it is preferable to cool the mixed liquid and maintain the liquid temperature at 30 qo or less. The mixing using the rope mixer or line mixer is carried out until the solvent in the emulsified 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-solvent mixture by filtration or centrifugation, and if necessary, water washing and separation are repeated a necessary number of times to obtain resin particles in the form of a slurry or a water-containing cake. In this way, preferably resin particles with an average particle size of between about 1 and 200 particles 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, such as a sand mill, usually used for manufacturing paints, is used.
Grind the resin particles using a ball mill, disperser, Sassmeyer mill, Sentry mill, etc. to reduce the average molecular diameter to approximately 1.
Adjust between ~50 Buddha. The thus obtained resin particles of the present invention contain a polyester-modified vinyl resin, a phosphoric acid group-containing copolymer 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, hydroxyl groups, amide groups, and isocyanate groups. Therefore, when the composition of the present invention is heated, a coating film having excellent performance can be obtained through crosslinking in the resin particles 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 molecular diameter of 1 to 50 mm. If the average particle diameter is smaller than 1 French, the particles tend to cohere with each other, and the particles tend to foam during film formation, which is undesirable. If the number is larger than 50, the resin particles tend to precipitate and coagulate during storage, making it impossible to obtain a smooth coating surface, which is not preferable. In particular, resin particles having an average molecular diameter of 5 to 30 mm 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. Moreover, the composition of the present invention has
Additives such as curing catalysts, organic and inorganic coloring and extender pigments, temporary rust preventive agents, fluidizing agents, antifoaming agents, anti-settling agents, preservatives, preservatives, etc., which are normally used in paints, if necessary. and other water-soluble resins, hydrosols, emulsion resins, and other coating film-forming resins.As mentioned above, the softening temperature of the resin particles is preferably 30 to 100 oo, so that heating of pigments, etc. in the paint can be included. Components that do not melt at the film forming temperature are preferably added to the resin particles in an amount of 5% by weight or less.The surfactants used in the present invention include nonionic surfactants, anionic surfactants, and cationic surfactants. Known surfactants such as surfactants and amphoteric surfactants can be used. Examples of nonionic surfactants include sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and polyoxyethylene sorbitol fatty acid ester. Oxyethylene fatty acid ester, polyoxyethylene alcohol ether, glycerin fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene castor oil derivative, polyoxyethylene alkylphenyl ether, alkyl phosphate ester, polyoxyethylene phosphorus As acid esters and anionic surfactants, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts, alkyl sulfosuccinates, N-acyl sarcosine salts, and as cationic surfactants,
Grade ammonium salts, pyridinium salts, etc. can be used. Nonionic surfactants are preferred from the viewpoint of dispersion stability of resin particles, coating film performance, etc., and those having an HLB of 8 to 18 are particularly preferred. Further, as the above-mentioned thickener used in place of or in combination with these surfactants, those conventionally used in water-based resin paints can be used. These include, for example, cellulose-based water-soluble resins such as methyl cellulose, ethyl cellulose, and hydroxyethyl cellulose; polyvinyl alcohol; polyethylene-based water moat resins such as polyethylene glycol ether and polyethylene oxide; methyl vinyl ether maleic anhydride copolymer. Water-dropping resins based on maleic anhydride copolymers such as ethylene maleic anhydride copolymers and styrene maleic anhydride copolymers; ammonium, amine salts and sodium salts of acrylic acid polymers;
bentonite, polyvinylpyrrolidone, alginate,
Examples include polyacrylamide and its partially hydrolyzed products, and naturally occurring water-soluble resins such as casein and gelatin. The above-mentioned surfactant and/or thickener is 0.01 to 5.0% for the fine powder resin particles. cloud amount% added. Addition amount is 0.
If it is less than 0.01% by weight, storage stability, painting workability, etc. will deteriorate, and 5. If the amount is more than 2% by weight, the smoothness, water resistance, etc. of the coating film will deteriorate, 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 water-insoluble after 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 90 to 30/10 by weight.
~70 is preferred. 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 surface of zero, phenomena such as smearing occur in the coating film, and to avoid this, several coats are required, causing problems in painting workability. On the other hand, if the amount of resin particles exceeds the above mixing ratio, it will be difficult to make the paint uniform by mixing, kneading, etc. during paint production, and the viscosity characteristics will not be suitable for various painting methods such as spray painting and electrostatic painting. This is undesirable because it comes off from the frame, resulting in poor painting workability and reduced practicality. The water-dispersed thermosetting coating composition of the present invention can be applied using various well-known coating methods such as brush coating, impregnation coating, spray coating, electrostatic coating, curtain flow coating, shower coating, and roll coating. It can be used. The conditions for heat curing after coating the coating composition vary depending on the content of the crosslinking functional group in the composition, the film thickness, etc., but are usually at an appropriate temperature in the temperature range of 120 to 200 qo. A cured coating film can be obtained by heat treatment for 10 to 40 minutes. The hardened coating strength obtained in this way suppresses temporary rusting on steel plates, and also improves adhesion to metal surfaces, corrosion resistance, water resistance,
It has excellent cold and heat cycle resistance. In addition, polyester resin has excellent maneuverability, pigment dispersibility, and coating appearance, and vinyl copolymer resin has excellent hardness and
It has excellent stain resistance, weather resistance and chemical resistance of isocyanate compounds, and does not cause foaming (flanks) that occurs during high-temperature baking.
It has excellent coating performance. 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 resin solution] {1' Unsaturated polyester resin No. 1 (hereinafter abbreviated as PE-1) 32.6 parts of isophthalic acid and 1 part of adipic acid were placed in a reaction vessel equipped with an attenuator, a thermometer, a cooling pipe, and a nitrogen gas introduction pipe.
8.7 parts, fumaric acid 3.0 parts, neobentyl glycol 29. Anchorage and 16.7 parts of trimethylolpropane were charged and reacted in a nitrogen gas atmosphere at 225° C. for about 8 hours to obtain a resin having an acid value of 15.1, a hydroxyl value of 155, and a weight average molecular weight of 6,700. This was diluted with methyl ethyl ketone to a non-volatile content of 60% to give PE-1. (2} Unsaturated polyester resin NO.
．． 2 (hereinafter abbreviated as PE-2) In a reaction vessel similar to that in which PE-1 was synthesized, 32.3 parts of isophthalic acid, 15.1 parts of adipic acid, 3.0 parts of fumaric acid, and neobentyl glycol pine were added. ．． $ part, trimethylolpropane 17.4
9.3 parts of glycidyl ester of tertiary synthetic saturated fatty acid (Cardular E: trade name manufactured by Shell Chemical Co., Ltd.) were charged and reacted for about 8 hours at 225q0 in a nitrogen gas atmosphere to give an acid value of 16.2 and a hydroxyl group. A resin having a value of 166 and 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. [31 Unsaturated polyester resin No.
．． 3 (hereinafter abbreviated as PE-3) 32 parts of ortho-phthalic anhydride in place of 32.6 parts of isophthalic acid in PE-1.
．． In the same manner except that 6 parts were used, under a nitrogen gas atmosphere,
22,500 for about 6 hours to obtain a resin having an acid value of 4, a hydroxyl value of 1, and a weight average molecular weight of 2,450. This was diluted with methyl ethyl ketone to a non-volatile content of 60% to give PE-3. [Method for producing polyester modified vinyl resin solution] (11) 30 anchorages of methyl ethyl ketone were placed in a reaction vessel equipped with a syringe, a thermometer, a lower funnel, a cooling tube, and a nitrogen gas introduction tube, and the temperature was raised to 80 qo. rear,
The following monomer, polyester resin and initiator mixture was added dropwise over 3 hours. 75 parts of methyl methacrylate, 14 parts of styrene, 165 parts of ethyl acrylate, 1 part of 2-hydroxyethyl methacrylate, 1 part of acrylic acid, 5 parts of N-butoxymethylacrylamide, the polyester resin (
PE-1) 50 parts, azopisisobutyronitrile 6 parts.
After finishing dropping, add 1 part of azobisisobutyronitrile,
After raising the reaction temperature to 870℃, the reaction was carried out for 4 hours, and the acid value was 16.2, the hydroxyl value was 40.5, and the weight average molecular weight was 6.
1500, and a non-volatile content of 57.5%, and the softening temperature of the resin was about 66-6800. This was named PE-AV-1. (2- Said PE-AV-1
In a reaction vessel similar to the one used to synthesize methyl ethyl ketone 2
After the temperature was raised to 80°C, the following monomer, polyester resin and initiator mixture was added dropwise over 3 hours. 60 parts of methyl methacrylate, 145 parts of styrene, 155 parts of ethyl acrylate, 5 parts of 2-hydroxyethyl methacrylate, 10 parts of acrylic acid, 50 parts of N-n-butoxymethylacrylamide, the polyester resin (P
E-2) Added 75 parts, 6 parts of azopisisobutyronitrile, and 1 part of azobisisobutyronitrile after the dropwise addition, raised the reaction temperature to 870℃, and conducted the reaction for 4 hours.
Acid value 17.4, hydroxyl value 67.0, weight average molecular weight 13
A resin solution of 5100 and 58.1% non-volatile content was obtained, and the softening temperature of the resin was about 67-6900. This was named PE-AV-2. (3' In production of polyester modified pinyl resin solution (2), 300 parts of methyl ethyl ketone, 15 parts of ethyl acrylate, 1 part of 2-hydroxyethyl methacrylate, 75 parts of N-butoxymethyl acrylamide, and the polyester resin (PE The reaction was carried out in the same manner except that -2) was changed to 5 anchorages, and a resin solution with an acid value of 16.8, a hydroxyl value of 42.0, a weight average molecular weight of 72,100, and a non-volatile content of 57.3% was obtained. The softening temperature was about 64 to 670. This was designated as PE-AV-3. [4' The PE-AV-
Into a reaction vessel similar to that in which 1 was synthesized, 28 liters of methyl ethyl ketone were charged, and after raising the temperature to 80 qo, the following monomer, polyester resin, and initiator mixture was added dropwise over 3 hours. Methyl methacrylate 50 parts, styrene 135 parts, ethyl acrylate 145 parts, 2-hydroxyethyl methacrylate 10 parts, acrylic acid lo
75 parts of Nn-butoxymethylacrylamide, 75 parts of the polyester resin (PE-3), and 6 parts of azobisisobutyronitrile. After the dropwise addition, 1 part of azobisisobutyronitrile was added, the reaction temperature was raised to 870°C, and the reaction was carried out for 4 hours to obtain an acid value of 15.1, a hydroxyl value of 61.0, a weight average molecular weight of 97500, A resin solution with a non-volatile content of 58.2% was obtained, and the softening temperature of the resin was approximately 63-65°C. This was named PE-AV-4. '5} Said PE-AV-1
In the synthesis, the reaction was carried out in the same manner except that N-n-butoxymethylacrylamide was replaced with N-t-butoxymethylacrylamide, and the acid value was 16.3.
A resin solution with a hydroxyl value of 37, a weight average molecular weight variation of 200, and a non-volatile content of 59.0% was obtained, and the softening temperature was approximately 64-6.
It was 70. This was named PEE-AV-5. '61 PE-A
49 parts of methyl ethyl ketone were placed in the same reaction vessel as the one in which V-1 was synthesized, and after raising the temperature to 80°C, the following monomer, polyester resin, and initiator mixture was added dropwise over 3 hours. 110 parts of methyl methacrylate, 90 parts of styrene, 95 parts of ethyl acrylate, 4 parts of butyl acrylate, 5 parts of n-butyl methacrylate, 3 parts of 2-hydroxypropyl methacrylate, 5 parts of acrylic acid, N-n-poxymethyl acrylamide 4
parts, 4 parts of the polyester resin (PE-2), and 7 parts of azobisisobutyronitrile. After dropping, add 1 part of azobisisobutyronitrile,
After raising the reaction temperature to 870℃, the reaction was carried out for 4 hours, and the acid value was 9.7 and the hydroxyl value was 9.7. ○Weight average molecular weight 7780
A resin solution with 0 and 50.2% non-volatile content was obtained, and the softening temperature of the resin was about 64-66 qo. PE-
It was named AV-6. The methyl ethyl ketone 39 base was placed in a reaction vessel similar to that in which PE-AV-1 was synthesized, and the temperature was raised to 8,000 ℃, and then the following monomer, polyester resin, and initiator mixture was added dropwise over a period of 3 hours. . 10 parts of methyl methacrylate, 117.5 parts of styrene, 6 parts of butyl acrylate, 75 parts of 2-ethylhexyl methacrylate, 2 parts of 2-hydroxyethyl acrylate, 7.5 parts of methacrylic acid, 6 parts of N-t-butoxymethylacrylamide. Anchor part, the polyester resin (PE
-3) 6 parts, 7 parts of azobisisoputilonitrile. After dropping, add 1 part of azobisisobutyronitrile,
After raising the reaction temperature to 87o0, the reaction was carried out for 4 hours, and a resin solution with an acid value of 12.0, a hydroxyl value of 63.0, a weight average molecular weight of 91,100, and a non-volatile content of 54.2% was obtained, and the resin softened. The temperature was approximately 66-68°C. This was named PE-AV-7. [8} The above PE-AV
24 parts of methyl ethyl ketone was put into a reaction vessel similar to that in which -1 was synthesized, the temperature was raised to 80 oo, and then the following monomer, polyester resin and initiator mixture was added dropwise over 3 hours. Methyl methacrylate 126.
5 parts, 2-ethylhexyl acrylate 1 base, 2-ethylhexyl methacrylate 11.5 parts, 2-hydroxyethyl methacrylate 45.5 parts, acrylic acid 5 parts,
75 parts of N-n-butoxymethylacrylamide, 126.5 parts of the above polyester resin (PE-1), and 6 parts of azopisisoputilonitrile. After the dropwise addition was completed, 1 part of azopisisobutyronitrile was added and the reaction temperature was raised to 870°C, and the reaction was carried out for 4 hours to give an acid value of 10.0 and a hydroxyl value of 11.
0, weight average molecular weight 78,000, and non-volatile content 59.
An 8% resin solution was obtained, and the softening temperature of the resin was approximately 70-7
The temperature was 4°C. This was named PE-AV-8. [Method for producing a phosphoric acid group-containing copolymer resin solution]'1} 0 parts of methyl ethyl ketone was put into a reaction vessel equipped with a flywheel, a thermometer, a dropping funnel, and a cooling tube, and the temperature was raised to 8,000. The following monomer and initiator mixture was added dropwise over 3 hours. 85 parts of methyl methacrylate, 16 parts of styrene, 5 parts of ethyl acrylate, 2-hydro. 25 parts of xishetyl methacrylate, 25 parts of 2-ethylhexyl acrylate, 14 parts of 2-ethylhexyl methacrylate, 5 parts of acidophosphoxyethyl methacrylate
1 part, 1 part acrylic acid, 1 part azobisisobutyronitrile
Foundation. After dropping, 1.5 parts of azobisisobutyronitrile was added, the reaction temperature was raised to 870°C, and the reaction was carried out for 4 hours, resulting in an acid value of 18.2, a hydroxyl value of 24, a weight average molecular weight of 37,600, and A resin solution with a nonvolatile content of 59.6% was obtained, and the softening temperature of the resin was about 72-74°C. PV-1 was obtained by adding 2/3 mole of triethylamine to the acid value of the resin solution to neutralize it. [2--A sparse portion of methyl ethyl ketone 34 was placed in a reaction vessel similar to that in which PV-1 was synthesized, and after raising the temperature to 80 CO, the following monomer and initiator mixture was added dropwise over 3 hours. Methyl methacrylate 11 parts, styrene 11 parts, ethyl acrylate 21 parts, 2-hydro. 5 parts of xyethyl methacrylate, 5 parts of acidophosphoxyethyl methacrylate, 5 parts of 3-chloro-2-acidophosphoxypropyl methacrylate, 1 part of acrylic acid, 1 part of azobisisobutyronitrile. After the dropwise addition, 1.5 parts of azopisisobutyronitrile was added, the reaction temperature was raised to 870°C, and the reaction was carried out for 4 hours. 59
．． An 8% resin solution was obtained and the softening temperature of the resin was approximately 74-7
The temperature was 6°C. PV-2 was obtained by adding 2/3 mole of triethylamine to the acid value of the resin solution to neutralize it. [3}
50 parts of methyl ethyl ketone was placed in a reaction vessel similar to that in which PV-1 was synthesized, and the temperature was raised to 80 oo.
The following monomer and initiator mixture was added dropwise over 3 hours. Methyl methacrylate 17 parts, styrene 50 parts, ethyl acrylate 175 parts, 2-ethylhexyl acrylate 2 parts, 2-hydroxyethyl methacrylate 60 parts
1 part, 7.5 parts of acidophosphoxyethyl methacrylate, 7.5 parts of 3-chloro-2-acidophosphoxypropyl methacrylate, 10 parts of acrylic acid, and 1 part of azobisisobutyronitrile. After the dropwise addition, 1.5 parts of azobisisobutyronitrile was added and the reaction temperature was raised to 870°C, and the reaction was carried out for 0 hours to give an acid value of 22.9 and a hydroxyl value of 5.
5 Weight average molecular weight 23000 and non-volatile content 52.6%
A resin solution with a softening temperature of about 73-76o is obtained.
It was o. PV-3 was obtained by adding 3'4 mol of triethylamine to the acid value of the resin solution to neutralize it. [4}
34 parts of methyl ethyl ketone were placed in a reaction vessel similar to that in which PV-1 was synthesized, and the temperature was raised to 80 qo.
The following monomer and initiator mixture was added dropwise over 3 hours. 190 parts of methyl methacrylate, 8 parts of styrene, 122.5 parts of ethyl acrylate, 5 parts of 2-hydroxyethyl acrylate, 2.5 parts of acidophosphoxyethyl acrylate, 50 parts of n-butyl methacrylate, 5 parts of acrylic acid, azo 10 parts of bisisobutyronitrile. After the dropwise addition, 1.5 parts of azobisisobutyronitrile was added, the reaction temperature was raised to 870°C, and the reaction was carried out for 4 hours, resulting in an acid value of 9.1, a hydroxyl value of 50, and a weight average molecular weight of 3290.
A resin solution with a nonvolatile content of 0 and 59.8% was obtained, and the softening temperature of the resin was about 73-75°C. This was designated as PV-4. [5-] A gourd of methyl ethyl ketone 34 was placed in the same reaction vessel as used for synthesizing PV-1, and after raising the temperature to 80 oo, the following monomer and initiator mixture was added dropwise over 3 hours. 10 parts of methyl methacrylate, 12 parts of styrene, 105 parts of ethyl acrylate, 4 parts of 2-hydroxypropyl methacrylate, 85 parts of isobutyl methacrylate, 42.5 parts of butyl acrylate, 5 parts of bismethacryloxethyl phosphate, 2 parts of acrylic acid. 5 parts, 1 part azobisisobutyronitrile. After the dropwise addition, 1.5 parts of azobisisobutyronitrile was added and the reaction temperature was increased to 870°C.
The reaction was carried out for 4 hours after raising the temperature to
A 9.3% resin solution was obtained and the softening temperature of the resin was about 75~
It was 770. This was designated as PV-5. '6} 34 parts of methyl ethyl ketone was placed in a reaction vessel similar to that in which PV-1 was synthesized, the temperature was raised to 80°C, and the following monomer and initiator mixture was added dropwise over 3 hours. 153.5 parts of methyl methacrylate, 75 parts of styrene,
55 parts of butyl acrylate, 35 parts of 2-hydroxyethyl methacrylate, 100 parts of n-butyl methacrylate, 7 parts of 2-ethylhexyl methacrylate, 4 parts of bisacryloxethyl phosphate, 7.5 parts of methacrylic acid
parts, 10 parts of azobisisobutyronitrile. After the dripping is finished,
After adding 1.5 parts of azobisisobutyronitrile and raising the reaction temperature to 87o0, the reaction was carried out for 4 hours. A 59.9% resin solution was obtained and the softening temperature of the resin was about 75-77q0. PV-6 was obtained by adding 2/3 mole of triethylamine to the resin solution to neutralize it. (7) Seventy-five centimeters of methyl ethyl ketone were placed in a reaction vessel similar to that in which PV-1 was synthesized, and the temperature was raised to 80°C, and then the following monomer and initiator mixture was added dropwise over 3 hours. 190 parts of methyl methacrylate, 55 parts of styrene, 195 parts of ethyl acrylate, 15 parts of 2-hydroxyethyl methacrylate, 4 parts of acidophosphoxyethyl methacrylate, 5 parts of acrylic acid, 1 part of azobisisobutyronitrile. After the dropwise addition, 1.5 parts of azobisisobutyronitrile was added, the reaction temperature was raised to 87q0, and the reaction was carried out for 4 hours. A resin solution with a nonvolatile content of 39.5% was obtained, and the softening temperature of the resin was about 73-70. PV-7 was obtained by adding 3'4 mol of triethylamine to the acid value of the above-mentioned Ju8pen liquid to neutralize it. [Solvent substitution method for blocked isocyanate compound] When a blocked isocyanate compound containing a hydrophobic solvent is used, the solvent in the emulsion fine particles is not extracted into water and the resin particles are removed in the step of forming resin particles. This is not preferable because the resin particles may coalesce or become integrated, impairing stability. Therefore, the blocked isocyanate compound was subjected to solvent substitution using the method described below, and was used in the present invention. Takenate B-82 SU [Manufactured by Takeda Pharmaceutical Company Ltd. Product name: Effective NC04.3%,
Non-volatile content 60% (Solvent: Supersol 1500/butyl acetate)] was placed in a vacuum dryer at 40°C and vacuum dried for 2 days (non-volatile content 92.6%), then methyl ethyl ketone was added to the non-volatile content. NCO diluted to 60%
-A. Example 1 Resin solution (PE-AV-1) 2
To 4 parts, 12 parts of titanium dioxide and 4 parts of methyl ethyl ketone were added, and after kneading and dispersing to 10 French or less (measured with a grind gauge; the same applies hereinafter) using a sand mill, a resin solution (PE-
AV-1) 33 parts, floccysocyanate compound (N
9 parts of CO-A), 14 parts of resin solution (PV-1), 0.5 parts of dibutyltin dilaurate (dissociation catalyst), and 3.5 parts of methyl ethyl ketone were added and mixed to form a uniform pigment dispersion. . This was dropped into 200 g of water at a temperature of 1 to 0 under a high-speed light to emulsify the pigment dispersion and extract the solvent into the water to form resin particles. Thereafter, heating in a furnace and washing with water were repeated to obtain a water-containing cake of resin particles with an average particle diameter of about 100 and a water content of about 50%. 10 parts of this water-containing cake, 0.5 parts of a 40% aqueous solution of a nonionic surfactant (trade name Emalgen 930, manufactured by Kao Atlas Co., Ltd., HLB15.1), 0.5 parts of an alkali salt thickener of an acrylic acid copolymer, Two parts of a 10% aqueous solution was added, and the resin particles were finely pulverized by dispersion kneading with a sand mill to obtain a slurry-like paint having an average particle diameter of 15 # and a pH of 7.6. Example 2 1 part of titanium dioxide was added to 24 parts of resin solution (PE-AV-2).
Add 4 parts of methyl ethyl ketone and grind with a sand mill.
After kneading and dispersing to below 0 French, resin solution (PE-AV-2) 2
6.5 parts, blocked isocyanate compound (trade name Kleran U-16109: manufactured by Bayer AG) 8 parts, resin solution (PV-3) 21.5 parts, dibutyltin dilaurate (dissociation catalyst) 0.5 parts, 3.5 parts of methyl ethyl ketone was added and mixed with Isozuka to obtain a uniform pigment dispersion. All of the following operations were carried out in the same machine as in Example 1 to obtain a slurry-like paint having an average resin particle diameter of 16 and a pH of 7.5. Example 3 1 part of titanium dioxide was added to 24 parts of resin solution (PE-AV-3).
2. Add 4 parts of methyl ethyl ketone and mix with a ball mill.
After kneading and dispersing to below 0 French, resin solution (PE-AV-3) 1
4 parts, blocked isocyanate compound (trade name Kleran U-16109: manufactured by Bayer AG) 3.8 parts, resin solution (PV-1) spots, dibutyltin dilaurate (dissociation catalyst) 0.5 parts, methyl ethyl ketone 3 Add .5 parts;
The mixture was mixed to form a uniform pigment dispersion. This was poured into 300 liters of water at a temperature of 20° C. under a high-speed lamp, and the pigment dispersion was emulsified and the solvent was extracted into the water to form resin particles. Thereafter, filtration in an oven and washing with water were repeated to obtain a water-containing cake of resin particles with an average molecular diameter of 150 and a water content of about 50%. Add 100 parts of this water-containing cake to a 40% aqueous solution of a nonionic surfactant (trade name: Emulgen 91).
Add 0.6 parts of HLB12.2 (manufactured by Shichioh Atlas Co., Ltd.) and 4 parts of an increasing agent (5% aqueous solution of hydroxyethyl cellulose), disperse and knead with a ball mill, and finely pulverize the resin particles to obtain an average molecular weight. A slurry paint having a diameter of 15 mm and a pH of 7.7 was obtained. Example 4 1 part of titanium dioxide was added to 24 parts of resin solution (PE-AV-4).
Gunho, flow aid (trade name Modaflow: manufactured by Monsanto)
Add 0.5 parts of methyl ethyl ketone and 3.5 parts of methyl ethyl ketone, knead and disperse with a sand mill to less than
-4) 16 parts, blocked isocyanate compound (NCO
-A) 13.3 parts, and 27 parts of resin solution (PV-2),
0.5 parts of dibutyltin dilaurate (dissociation catalyst) and 3.5 parts of methyl ethyl ketone were added and mixed to obtain a uniform pigment dispersion. All of the following operations were carried out in the same manner as in Example 1 to obtain a slurry-like paint having an average resin particle diameter of 15 French and a pH of 7.6. Example 5 In Example 1, except that the resin solution (PE-AV-1) was replaced with the resin solution (PE-AV-5) and the resin solution (PV-2) was replaced with the resin solution (PV-4). A slurry-like paint having an average particle size of 17 mm and a pH of 7.8 was obtained in the same manner. Example 6 In Example 4, 4 parts of the resin solution (PE-AV-4) was added to 465 parts of the resin solution (PE-AV-6).
A slurry-like paint having an average particle size of 17 mm and a pH of 7.7 was obtained in the same manner except that PV-2) was replaced with a resin solution (PV-6). Example 7 In Example 4, 4 parts of the resin solution (PE-AV-4) were added to 43 parts of the resin solution (PE-AV-7), and the resin solution (P
A slurry-like paint having an average particle size of 15 French and a pH of 7.8 was obtained in the same manner except that V-2) was replaced with a resin solution (PV-5). Example 8 In Example 1, the resin solution (PV-2) was changed to the resin solution (PV-2).
A slurry-like paint having an average particle size of 16 μm and a pH of 7.6 was obtained in the same manner except that PV-5) was used instead. Comparative Example 1 Polyester modified vinyl resin solution used in Example 1 (
From the composition of PE-AV-1), the modified polyester resin (
PB-1) and N-n-ptoxymethylacrylamide, the reaction was carried out in the same manner as in polyester modified vinyl resin solution production '11, and the acid value was 12.3 and the hydroxyl value was 27 (weight average molecular weight 17500)
A resin solution with a nonvolatile content of 58.4% was obtained. To 24 parts of the resin solution, 12 parts of titanium dioxide and 4.5 parts of methyl ethyl ketone were added, and after kneading and dispersing in a sand mill to a concentration of 10% or less, 44 parts of the resin solution and an average degree of integration of 2.5% were added.
1 part of a 60% methyl ethyl ketone solution of a butylated methylol melamine resin having a degree of etherification and a water-soluble component of 1% or less and 3.5 parts of methyl ethyl ketone were added and mixed to obtain a uniform pigment dispersion. All of the following are Example 1
In the same manner as above, a slurry paint having an average particle size of 15 French and a pH of 7.5 was obtained. Comparative Example 2 Polyester modified vinyl resin solution used in Example 3 (
From the composition of polyester resin (PE-AV-3)
2) and N-butoxymethylacrylamide, the monomer composition is all polyester-modified vinyl resin solution.
2.2, hydroxyl value 33, (weight average molecular weight 16200)
A resin solution with a nonvolatile content of 59.1% was obtained. To 24 parts of the resin solution, 12 parts of titanium dioxide and 4.5 parts of methyl ethyl ketone were added, and after kneading and dispersing in a ball mill into 10 mounds or less, 48 parts of the resin solution and a blocked isocyanate compound (trade name: Kleran U-1) were added. 6109:
(manufactured by Bayer AG), 0.5 parts of dibutyltin dilaurate (dissociation catalyst), and 3 parts of methyl ethyl ketone were added and mixed with a rope to form a uniform pigment dispersion. All of the following are Example 3
Using the same machine as above, a slurry paint having an average particle size of 15 and a pH of 7.3 was obtained. Comparative Example 3 Polyester modified vinyl resin solution used in Example 1 (
From the composition of PE-AV-1), the modified polyester resin (
The reaction was carried out in the same manner as in Polyester Modified Vinyl Resin Solution Production '1} except for the monomer composition except PE-1), and the acid value was 13.0 and the hydroxyl value was 30. Weight average molecular weight 4
1000 and non-volatile separation. A 7% resin solution was obtained. To 24 parts of the resin solution, 12 parts of titanium dioxide and 4.5 parts of methyl ethyl ketone were added, and after dispersing the rice bran to 101 or less using a ball mill, 56 parts of the resin solution and 3.5 parts of methyl ethyl ketone were further added, and the mixture was mixed. A uniform pigment dispersion was obtained. The following steps were carried out in the same manner as in Example 1, with an average particle diameter of 15.
A slurry paint of 7.4 was obtained. Comparative Example 4 1 part of titanium dioxide was added to 24 parts of resin solution (PE-AV-8).
After adding 4.5 parts of methyl ethyl ketone and dispersing with a sand mill to less than 10 parts, the resin solution (PE-AV-8
) and 3.5 parts of methyl ethyl ketone were added and mixed to obtain a uniform pigment dispersion. This was dropped into 200 liters of water at a temperature of 15 qo under high speed stirring to emulsify the pigment dispersion and extract the solvent into the water to form resin particles. Thereafter, filtration and washing with water were repeated to obtain a water-containing cake of resin particles with an average particle law of about 100 r and a water content of about 50%. The base of this water-containing cake 10' is a 40% aqueous solution of nonionic surfactant (trade name Emalgen 930, manufactured by Kao Atlas Co., Ltd., HLB 15.1) 0.3
part, 10% of alkali salt thickener of acrylic acid copolymer
Two parts of the aqueous solution was added, and the resin particles were pulverized by dispersion using a sand mill to obtain a slurry-like paint having an average particle diameter of 12r and a pH of 7.3. Comparative Example 5 Resin solution (PE-AV-1
), 12 parts of titanium dioxide and 4.5 parts of methyl ethyl ketone were added, and after dispersing the rice bran into 10 mounds or less using a sand mill, 51 parts of the resin solution (PE-AV-1) and the resin solution (
PV-7) and 3.5 parts of methyl ethyl ketone were added and mixed to obtain a uniform pigment dispersion. This was dropped into 200 parts of water at a temperature of 1530°C under high speed stirring to emulsify the pigment dispersion and extract the solvent into the water to form resin particles. Thereafter, filtration and washing with water were repeated to obtain a water-containing cake of resin particles with an average particle diameter of about 100 mm and a water content of about 50%. 10 parts of this water-containing cake
A 40% aqueous solution of this nonionic surfactant (trade name Emulgen 930, manufactured by Kao Atlas Co., Ltd., HLB 15.1) 0.
3 parts, 10 parts of alkali salt thickener for acrylic acid copolymer
% aqueous solution was added thereto, and the resin particles were finely pulverized by dispersing and kneading with a sand mill to obtain a slurry-like paint having an average particle size of 15 mm and a mottling of 7.7 mm. The slurry paint prepared in each of the above Examples and Comparative Examples was spray-painted onto a polished European steel plate.
After setting for 1 minute and ripening at 90oo for 10 minutes,
Each was heated and dried at a predetermined temperature to form a coating film with a thickness of about 35 mm. Table 1 shows the heating drying conditions and physical property test results for the coating film. Table 1 (Note 1) Visual judgment of appearance during setting ink (Run 2)
Visual judgment (Note 3) 60 degree specular gloss value (Note 4) Using Mitsubishi Pencil Uni, 4 for the paint film
Apply it at an angle of 50 degrees, press lightly forward, and the hardness of the pencil leaves no traces of the pencil on the paint film. (Note 5) Vertical tape peeling test. (Note 6)
By Eriksen test machine. (Note 7) JIS-K
-5400, 6, 13, 3B method. (Note 8) Ethyl acetate lapinque test 50 times ◎ Abnormality present ○ Slightly glossy and shrinking × Indicates large glossy shrinkage. (Note 9) Moisture resistance test (50℃, 97% RH<) 2
After 00 hours, goban tape peeling test ◎100/1
00~90/100○ 89/100~60/100 × 59/100~0/100 (Note 10) Salt water spray resistance: A test piece with a cross cut that reaches the substrate was tested using a salt water spray tester (JIS-Z-
2371) for 100 hours, the cross-cut portions were peeled off with cellophane tape. ◎ (During peeling: one side) 0 to 1.0 ribs △ (During peeling:
Medium) 2.1 to 3.0 ○( 〃 〃 ) 1.1
~2.0 ribs × (〃 ・″) 31 or more (Note 11)
Acid resistance test: 24 hours at 20℃ in 5 male sulfuric acid aqueous solution
After soaking for 48 hours, the appearance of the coating and the occurrence of blisters are determined. (Note 12) Alkali resistance test: 3* After soaking in a caustic soda aqueous solution at 20°C for 48 hours and 96 hours, judge the appearance of the coating film and the occurrence of blisters. (Note 13) Cold/heat cycle test: After immersing in -40°C dry ice-methanol solution for 15 minutes, the test piece is taken out and immediately immersed in 60°C salt water for 15 minutes.
After that, take out the test piece and leave it at room temperature for 10 minutes, then check the appearance of the paint film on the test piece (paint cracks), and if there are no abnormalities, the test is considered to have passed the first cycle. Regarding the cold/heat resistance cycle test, the slurry-like paint prepared in each example and comparative example was coated with Emalon CED-70 (
Dainippon Toyo Co., Ltd.'s trade name, urethane-based electrodeposition paint) was exposed under the following conditions, coated on a zinc phosphate chemically treated dull steel plate that was heated and dried, and then baked on a coated steel plate. (Dense electrodeposition 18〃, coating voltage 250V, energizing time 2 minutes, baking conditions 180℃ x 20 minutes) (Note 14)
Gloss after accelerated weathering test: JIS-D-0205
・7.6. Accelerated weathering test (test conditions: sunshine carbon weather meter) After 1000 hours, gloss measurement (6
0 degree specular gloss value). (Note 15) This indicates the number of days in which the composition is kept in a heated tank at 50°C to cause gelation or sedimentation.

Claims (1)

[Scope of Claims] 1 (A) (a) (i) One of the constituents is 1 to 10% by weight of α/β-unsaturated dicarboxylic acid, acid value 50 or less, hydroxyl value 50 to 250, weight average Molecular weight 2000-1
20,000 unsaturated polyester resin......2 to 40% by weight, and (ii) (a) hydroxyalkyl ester of α/β-monoethylenically unsaturated carboxylic acid......0.
5 to 30% by weight (b) N-alkoxymethylated monomer of α/β-monoethylenically unsaturated carboxylic acid amide...5 to 30% by weight (c) The above (a), (b) and (ro) ) Copolymerizable α/β-monoethylenically unsaturated monomers other than (a)……60
Monomer mixture consisting of ~90% by weight...98~60% by weight, obtained by graft polymerization, hydroxyl value 10~150
, acid value 3-40, weight average molecular weight 40000-2000
00 polyester modified vinyl resin...15 to 95% by weight (b) (a) Phosphoric acid group-containing α/β-monoethylenically unsaturated monomer...0.01 to 10% by weight (b) α/β
- Monoethylenically unsaturated carboxylic acid...0.5 to 10% by weight (c) Hydroxyalkyl ester of α/β-monoethylenically unsaturated carboxylic acid...1 to 30% by weight (d) (a) above, (b), (c) and (a)(ii)
Copolymerizable α/β-monoethylenically unsaturated monomers other than (b)……70 to 90% by weight obtained from a monomer mixture with a hydroxyl value of 3 to 150
, a phosphoric acid group-containing copolymer resin having a weight average molecular weight of 8,000 to 70,000...85 to 5% by weight, and (B) a blocked isocyanate compound. A water-dispersed thermosetting coating composition comprising: 0.01 to 5.0% by weight of a surfactant and/or thickener; and the required amount of water. 2 The mixing ratio of the above (A) and the above (B) is [the above (A)
)(a) and hydroxyl group in the mixture consisting of (A) and (b)]
/[Isocyanate group in (B) above]=1/0.1~
The water-dispersed thermosetting coating composition according to claim 1, wherein the ratio is 1/1.2 (equivalent ratio).