JPS6011068B2 - Water-based thermosetting resin coating composition - Google Patents

Description

[Detailed description of the invention] The present invention relates to a water-based thermosetting resin coating composition.

More specifically, the present invention relates to a water-based thermosetting resin coating composition with excellent coating film properties, corrosion resistance, and water resistance. In recent years, the demand for water-based paints has been increasing from the viewpoint of resource saving and pollution-free production.One type of water-based paint, the tsuki paint, was developed mainly to improve the anti-corrosion properties of automobile bodies. It has been put into practical use in a wide range of fields.

As such anti-friction paints, anionic electrodeposition paints using maleated oil-based resins, epoxy shester-based resins, or polybutadiene-based resins, which have good dew rating stability, pigment dispersibility, and hydrolysis resistance, are used.

However, with the recent proliferation of automobiles, corrosion caused by salt sprayed to prevent roads from freezing in winter has increased, and coatings obtained with conventional anionic electrodeposition paints no longer provide sufficient corrosion resistance. .

By the way, polycarboxylic acid resins having a skeleton of drying oil, alkyd resin, polybutadiene resin, epoxyester resin, polyacrylic acid ester, etc. are used as the resin for the anionic electrodeposition paint. Usually, these are neutralized with a basic compound such as an organic amine and made water-solubilized or water-dispersed. One of the reasons why such anionic electrodeposition paints have insufficient corrosion resistance is thought to be due to the presence of carboxyl groups in the cured coating film. Therefore, in recent years, cationic electrodeposition paints, which have particularly good corrosion resistance, have begun to be used. The resin for the cationic fin coating is as follows:
Polyamino resins with skeletons such as epoxy resins, urethane resins, and acrylic resins are used. Usually, these are neutralized with organic acids and made water-solubilized or water-dispersed. It is said that in such polyamino resins, the amino groups in the coating act as corrosion inhibitors, making it possible to obtain a coating film with a high degree of corrosion resistance. By the way, the following are typical examples of corrosion on automobile bodies in which the above-mentioned pigmented paints are mainly used: ), and corrosion progresses from the damaged area.
Chipping corrosion etc.

'2' So-called pitting corrosion that progresses from areas that have undergone impure chemical conversion treatment or incompletely painted areas.

In general, cationic electrodeposition paint coatings have effective anti-corrosion properties even on imperfectly chemically treated steel sheets.

However, the susceptibility to damage caused by external factors (see above 1) differs markedly depending on the type of resin skeleton. By the way, resin-based paints with an epoxy resin skeleton, which are mainly used in cationic electrodeposition paints, have poor flexibility and have poor corrosion resistance against damage caused by external factors such as chipping.

As a result of various studies on this type of paint, the present inventors focused on polyester resin, which generally has excellent coating film properties such as flexibility, and by incorporating this into the resin skeleton, it is less likely to be damaged by external factors. Furthermore, we have completed a water-based thermosetting resin coating composition that has excellent coating film properties and pigment dispersibility, as well as a high degree of corrosion resistance and water resistance. That is, the present invention has the following features: unsaturated polyester resin...2-4 pupil%; (ii). Tertiary amino group-containing Q,8-monoethylene unsaturated monomer...5 to 2% by weight,
oil) an N-alkoxymethylated monomer of a Q,8-monoethylene unsaturated carboxylic acid amide, and one or more Q,8-monoethylene unsaturated monomers other than the monomer and the above (ii) A monomer mixture consisting of...
...obtained by graft polymerization with 93 to 4% by weight,
Polyester used in the present invention relating to a water-based thermosetting resin coating composition comprising a polyester-modified vinyl resin having a hydroxyl value of 10 to 150, 'B' acid as a neutralizing agent, and {C' water as a diluent Modified vinyl resin and unsaturated polyester resin contain 8-monoethylene unsaturated monomer [
It is obtained by graft polymerization of the above-mentioned (ii) and 0ii), and it imparts to vinyl resin the excellent grindability, pigment dispersibility, corrosion resistance, and coating appearance that polyester resin has. There is a characteristic in doing.

Therefore, it is necessary to use Q,3-unsaturated 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.
It is preferable to react in a proportion of 10% by weight, preferably 3 to 7% by weight. That is, if this component is less than 1% by weight, Q,
The amount is not sufficient for the 3-monoethylenically unsaturated monomer and therefore the polyester modification is insufficient and the resulting product is a blend of the unsaturated polyester resin and the polymer of the Q,B-monoethylenically unsaturated monomer. The paint film may turn white. Further, due to the difference in reactivity with the cross-dip reactive group, the performance of the coating film, particularly the adhesion, tends to deteriorate, which is not preferable. On the other hand, if the amount of this component exceeds 1% by weight, gelation occurs during the reaction with the Q,8-monoethylene unsaturated monomer, which is not preferable. The Q, P-
Specific examples of unsaturated dicarboxylic ingredients 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, carvone brewing components other than the acid are preferably reacted in a proportion of 29 to 6% by weight.

Specific examples of the components include phthalic anhydride, isophthalic acid, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride. acid,
Methylhexahydrophthalic anhydride, imic acid anhydride, succinic acid (anhydride), adipic acid, sebacic acid, benzoic acid, paratertiary 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, dibropylene glycol, glycerin,
Trimethylol ethane, trimethylol propane, bentaerythritol, diventaerythritol, butanediol, bentanediol, hexanediol, 1,4
-Cyclohexane dimethanol, (hydrogenated) bisphe/
Examples include rule A. 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 20 or less (resin solid content; hereinafter, all indications of acid values in the present invention are the same), 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 molecular weight is preferably 2,000 to 80,000 in terms of weight average molecular weight. 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, if the acid value of the unsaturated polyester resin exceeds 20, the corrosion resistance etc. of the final coating film and performance after graft polymerization of the Q,8-monoethyletho unsaturated monomer will decrease.

Furthermore, if the hydroxyl value is lower than 50, the crosslinkability of the polyester-modified vinyl resin obtained by graft polymerization of the Q,8-monoethylene unsaturated monomer mixture tends to be insufficient, and if the hydroxyl value is higher than 250, the polar group This is not preferable because the water resistance of the resulting coating film tends to decrease as a result of increasing the amount. In addition, if the weight average molecular weight is lower than 2000, the properties of the polyester resin cannot be fully exhibited;
If it exceeds 000, the molecular weight of the polyester resin will be too high, and when modified with a Q,3-monoethylene unsaturated monomer mixture, the viscosity will be too high, which will impede workability, which is not preferable. The polyester-modified vinyl resin in the present invention has a third base added to the unsaturated polyester resin.
class amino group-containing Q,8-monoethylene unsaturated monomer,
Q, 8-monoethylene unsaturated carboxylic acid amide N-alkoxymethyl monomer and one or more other than the above. It is obtained by graft polymerization with an 8-monoethylene unsaturated monomer polymer.

The coating composition of the present invention is obtained by cationizing the tertiary amino groups in the polyester-modified vinyl resin using an acid as a neutralizing agent, and diluting the resin with water. Therefore, in order to contain a tertiary amino group, it is essential to introduce a 3-monoethylene unsaturated monomer into the polyester-modified vinyl resin.

The monomer is present in an amount of 5 to 2% by weight, preferably 6 to 1% by weight.
Use within the range. If the monomer is used in an amount less than 5% by weight, the water dilutability after cationization with an acid as a neutralizing agent will be insufficient. On the other hand, if it is used in an amount exceeding 2% by weight, the water resistance and corrosion resistance of the final coating film will decrease. Ta
Specific examples of the monomer include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dibutylaminoethyl (meth)acrylate, etc. These monomers may be used singly or as a mixture of two or more. Good too.

0 As the monomer to be graft-polymerized to the unsaturated polyester resin, in addition to the tertiary amino group-containing Q,P-monoethylene unsaturated monomer, N-alkoxy of Q,8-monoethylene unsaturated carboxamide Q,8-monoethylene unsaturated monomers other than those mentioned above are essential as the methyl b monomer.

Examples of Q,8-monoethylene unsaturated monomers other than those mentioned above include Q,8-monoethylene unsaturated carboxylic acids as described below, hydroxyalkyl esters of the carboxylic acids, and alkyl esters of acrylic acid or methacrylic acid. , quaternary ammonium salt-containing Q,8-monoethylene unsaturated monomers, and the like can be used singly or as a mixture of two or more. The tertiary amino group content in the polyester-modified vinyl resin of the present invention can be achieved by introducing an 8-monoethylene unsaturated monomer into the polyester-modified vinyl resin.
The group is cationized with an acid as a neutralizing agent and diluted with water. However, when the amount of acid as a neutralizing agent increases, the pH of the coating composition of the present invention decreases, causing acid corrosion of coating equipment, etc. Therefore, it is undesirable.

Therefore, if a Q,3-monoethylene unsaturated monomer containing a quaternary ammonium salt, which has the effect of imparting hydrophilicity, is introduced into the polyester-modified vinyl resin of the present invention, the introduced tertiary amino groups can be neutralized. This is preferable because only a small amount of acid is required and the pH of the coating composition of the present invention can be maintained at a value that provides good coating workability. The quaternary ammonium salt-containing Q,8-monoethylene unsaturated monomer is 1 to 1 in the Q,8-monoethylene unsaturated monomer compound [the above component (iii)]
It is used in an amount of 15% by weight, preferably in the range of 1.5 to 8% by weight. If the monomer is used in an amount less than 1% by weight, the effect will be poor, and if it is used in an amount exceeding 15% by weight, the water resistance and corrosion resistance of the final coating film will tend to decrease, both of which are undesirable. . Specific examples of the monomer include esters of 2-hydroxy-3-(meth)acryloxypropyltrimethylammonium chloride, glycidyltrimethylammonium chloride and Q,8-monoethylene unsaturated carboxylic acid, etc. They may be used alone or as a mixture of two or more. In addition, the polyester-modified pinyl resin in the present invention needs to contain a hydroxyl group in the molecule in order to undergo a crosslinking reaction (self-crosslinking reaction). Therefore, when the hydroxyl value of the unsaturated polyester resin is low, it is preferable to use a hydroxyalkyl ester of Q,8-monoethylene unsaturated carboxylic acid as a type of Q,8-monoethylene unsaturated monomer.

The hydroxyalkyl ester monomer is preferably used in the Q,8-monoethylene unsaturated monomer mixture [the above component (iii)] so that the hydroxyl value of the polyester-modified vinyl resin is 10 to 150. 3% by weight, particularly preferably in the range of 3 to 2% by weight.

If the monomer is used in an amount exceeding 3% by weight, the polyester-modified vinyl resin becomes highly viscous, and the crosslinking density after the thermosetting reaction becomes too high, resulting in poor coating film flexibility, water resistance, etc. This is undesirable as it leads to a decrease in the number of people.

Specific examples of the monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-hydro.

Xybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxybentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, neobentyl glycol mono(meth)acrylate ) acrylate, 3-butoxy 2-hydroxypropyl (meth)acrylate, 2-hydroxy-1-phenylethyl (meth)acrylate, polypropylene glycol mono(meth)acrylate, glycerin mono(meth)acrylate, etc. It may be used as a mixture of more than one species. In addition, the N-alkoxymethylated monomer component of the Q,8-monoethylene unsaturated carboxylic acid amide used for graft polymerization with the unsaturated polyester resin is a hydroxyalkyl monomer component of the Q,8-monoethylene unsaturated carboxylic acid. Necessary for crosslinking reaction with stell component and polyester resin component.

The component is Q,8-monoethylene unsaturated monomer compound 5
It is preferable to carry out the graft polymerization reaction at a proportion of 10 to 25% by weight, preferably 10 to 25% by weight. If the amount of this component is less than 5% by weight, the crosslinking reaction of the polyester-modified vinyl resin will be insufficient, and the solvent resistance and corrosion resistance of the coating film will deteriorate. Moreover, if it exceeds 3% by weight, gelation will occur during the graft polymerization reaction, which is not preferable.

Specific examples of this component include N-methoxymethyl (meth)
Acrylamide, N-ethoxymethyl (meth)acrylamide, N-n-propoxymethyl (meth)acrylamide, N-isobroboxymethyl (meth)acrylamide "N-n-ethoxymethyl (meth)acrylamide,
N-sec-butoxymethyl(meth)acrylamide,
N-t-butoxymethyl(meth)acrylamide, N-
Q, 8 of isobutoxymethyl (meth)acrylamide etc.
- N-alkoxymethylated products of monoethylenically unsaturated carboxylic acid amides; or N-methylolated products thereof, and these may be used alone or as a mixture of two or more. In the present invention, the quaternary ammonium salt-containing Q,8-monoethylene unsaturated monomer, the hydroxyalkyl ester monomer of Q,8-monoethylene unsaturated carboxylic acid, and the Q,8-monoethylene unsaturated Monomers other than the N-alkoxymethylated carboxylic acid amide monomer may be used in combination.

The monomer is preferably used in an amount of 25 to 9% by weight in the monomer mixture. Specific examples of the monomer include Q,B-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-butyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2- Alkyl esters of acrylic acid or methacrylic acid such as ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, and stearyl (meth)acrylate; other glycidyl (meth)acrylates , cyclohexyl (meth)acrylate, phenyl methacrylate, pendyl methacrylate, dialkyl esters of fumaric acid such as dibutyl fumarate, monomers such as styrene, vinyltoluene, Q-methylstyrene, (meth)acrylonitrile, pinylacetate, etc. Can be mentioned.

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, tertiary amino group-containing Q,
It consists of a graft polymerization reaction product of 5-2% by weight of an 8-monoethylene unsaturated monomer and 93-4% by weight of the monomer mixture.

The amount of modification of the unsaturated polyester resin is 2 to 4% by weight, preferably 3 to 25% by weight. If it is less than 2% by weight, the excellent properties of polyester resin such as malleability, pigment dispersibility, and coating film appearance cannot be fully demonstrated.
If the amount exceeds 4% by weight, the properties of vinyl resin such as hardness will be 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 saturated 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 from about 50 to 150 degrees, and the polymerization reaction time is from about 4 to 50 hours, depending on the temperature.

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

These polymerization solutions may be used alone or in an appropriate combination of two or more. The amount of the polymerization solvent used is such that the non-volatile content during production of the polyester modified vinyl resin is 10 to 8% by weight;
Preferably, it is used in a range of 20 to 7% by weight.

In addition, examples of the polymerization initiator used include penzoyl peroxide, t-butyl perbenzoate, t-
Examples include organic peroxides such as butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, and t-butyl baroctoate, and azo compounds such as azobisisobutyronitrile and azodiisobutyric acid nitrile.

These polymerization initiators may be used alone or in combination of two or more. The polymerization initiator is used in an amount of about 0.1 to 15% by weight based on the nonvolatile content during production of the polyester-modified vinyl resin. If necessary, chain transfer agents such as dodecyl mercaptan, 2-ethylhexyl thioglycolate, carbon tetrachloride, etc. may be used to adjust the molecular weight. The 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 group of the polyester modified vinyl resin of the present invention is 10-
15, preferably in the range of 30 to 100, and the acid value is preferably in the range of 20 or less, preferably 15 or less.

When the acid value is greater than 20, coating film performance and storage stability also decrease. In addition, if the hydroxyl value is less than 10,
The crosslink density decreases, and the solvent resistance and corrosion resistance of the coating film decreases. On the other hand, if it is larger than 150, the flexibility decreases,
The water resistance of the paint film decreases. The weight average molecular weight of the polyester modified vinyl resin of the present invention is 4000 to 80.
It is preferably in the range of 00 and preferably 5,000 to 50,000.

If the weight average molecular weight is less than 4,000, the performance of the coating film will be insufficient, while if the weight average molecular weight exceeds 80,000, the water dilutability of the resin and the smoothness of the coating film will be impaired, which is not preferable. Note that, as the acid for neutralizing the tertiary amino groups in the polyester-modified vinyl resin of the present invention, organic acids such as formic acid, acetic acid, propionic acid, lactic acid, and citric acid are used.

If necessary, the tertiary amino group may be quaternized by known methods. The amount of acid as the neutralizing agent is equal to or less than equimolar to the tertiary amine/group in the resin. The thus obtained coating composition of the present invention can be used in the form of an aqueous dispersion for various purposes and coating methods, but various organic solvents may be used in the process of obtaining the polyester-modified vinyl resin of the present invention. are used and therefore small amounts of organic solvents can be included in the coating composition.

However, the solvent used in this case is the water-soluble solvent or water-miscible solvent described above. Further, the content thereof is suitably 5% by weight or less based on the solid content of the resin. The water-based thermosetting resin coating composition of the present invention may contain one or more types of cationic or nonionic water-stable or water-dispersible resins, as long as the object of the present invention is not impaired. be.

Specific examples of the resin include epoxy resins containing amino/groups, phenol resins, urethane resins, polybutadiene resins, and melamine resins. In addition, coloring pigments, extender pigments, anticorrosive pigments, hardening accelerators, temporary rust preventive agents, flow aids, suspending agents, anti-static agents, preservatives, surface conditioners, antifoaming agents, etc. may be mixed as necessary. It can be enamelized by a secondary kneading method. The composition is suitable for decoating, but is also suitable for other applications such as air spray painting, immersion groove painting,
It is also suitable for conventional painting methods such as brush painting.

The composition of the present invention is a thermosetting agent, and its dawning conditions are determined by the content of crosslinkable functional groups in the composition, the presence or absence, type and amount of a curing accelerator, film thickness, etc. but,
It is usually 10 to 60 minutes at a temperature of 90 to 200 qo.
Thus, the coating composition of the present invention is highly crosslinked and can provide a coating film with extremely excellent corrosion resistance, water resistance, wire resistance, solvent resistance, and coating film properties. The details of the present invention will be shown below by way of examples. In addition, unless otherwise specified, “department”
and "%" indicate "part by weight" and "% by weight". [
Method for producing unsaturated polyester resin solution〕○ー Unsaturated polyester resin snake. 1 (hereinafter abbreviated as PEK-1)
32.6 parts of isophthalic acid and 18 parts of adipic acid were placed in a reaction bath equipped with a thermometer, a cooling tube, and a nitrogen gas introduction tube.
7 parts, fumaric acid 3.0 parts, neobentyl glycol 2
9. Ikaribe, prepare 167 parts of trimethylolpropane,
Approximately 8.5% at 225°C under a nitrogen gas atmosphere. The reaction was carried out for an hour to obtain a resin having an acid value of 13.3, a hydroxyl value of 144, and a weight average molecular weight of 8,900.

This was diluted with ethylene glycol monoethyl ether to a non-volatile content of 60% to obtain PBX-1. [21 Unsaturated polyester resin No. 2 (hereinafter abbreviated as PEK-2) In a reaction vessel similar to that in which PEK-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. ．． $ parts, 17.4 parts of trimethylolpropane, 9.3 parts of glycidyl ester of tertiary synthetic saturated fatty acid (Cardular E: trade name manufactured by Shell Chemical Co., Ltd.) and
The reaction was carried out at 25° C. for about 8.5 hours to obtain a resin having an acid value of 12.0, a hydroxyl value of 151, and a weight average molecular weight of 5,100.

This was diluted with ethylene glycol monoethyl ether to a non-volatile content of 60% to give PEK-2. J [
Method for producing polyester modified vinyl resin solution〕〇〇 285 parts of ethylene glycol monoethyl ether was placed in a reaction vessel equipped with a lighting machine, a thermometer, a dropping funnel, and a cooling tube, and the temperature was raised to 9000. After that, the following monomers,
The polyester resin and the initiator mixture were added dropwise over a period of 3 hours. 17.5 parts of methyl methacrylate, 100 parts of styrene, 12 parts of 2-ethylhexyl methacrylate
5 parts, 40 parts of dimethylaminoethyl methacrylate, 2
- 752 parts of hydroxyethyl methacrylate, N-n-
75 parts of butoxymethylacrylamide, 15 parts of a 50% aqueous solution of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride [Blenmar QA: trade name manufactured by NOF column], the above polyester resin (PEK
-31) 100 parts, 6 parts of azobisisoputyronitrile.
After dropping, add 0.5 part of azobisisobutyronitrile to 30
The reaction temperature was raised to 9500°C, and then 1.6 parts of azobisisobutyronitrile was added in 4 parts every 30 minutes, and the same At the reaction temperature,
The reaction was carried out for 4 hours, and a resin solution having an acid value of 1.8, a hydroxyl value of 85, a weight average molecular weight of 40,200, and a nonvolatile content of 59.2% was obtained. This was named PE-NC-1.

Ethylene glycol monoethyl ether 27 base was placed in a reaction vessel similar to that in which PE-NC-1 was synthesized, and the temperature was raised to 90°C, and the following monomers, polyester resin, and initiator were mixed. The liquid was added dropwise over 3 hours.

10 parts of methyl methacrylate, 100 parts of styrene, 2-
115 parts of ethylhexyl acrylate, 2-hydro.

5 parts of xyethyl methacrylate, 5 parts of dimethylaminoethyl methacrylate, 85 parts of N-n-poxymethyl acrylamide, 50 parts of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride.
% aqueous solution [Premmar QA: NOF ■Product trade name] 3
0 parts, 125 parts of the polyester resin (PEK-2),
6 parts of azobisisobutyronitrile. After the dropwise addition was completed, 0.5 part of azobisisobutyronitrile was added in two portions every 30 minutes, the reaction temperature was raised to 990°C, and then 1.6 parts of azobisisobutyronitrile was added. It was added in 4 portions every 30 minutes, and the reaction was further carried out for 4 hours at the same reaction temperature to obtain a resin solution with an acid value of 2.0, a hydroxyl value of 65, a weight average molecular weight of 35,500, and a non-volatile content of 59.3%. Ta. This was designated as PE-NC-2. '31 285 parts of ethylene glycol monoethyl ether was placed in a reaction vessel similar to that in which PE-NC-1 was synthesized, and the temperature was raised to 90°C, and the following monomers, polyester resin, and starting The agent mixture was added dropwise over 3 hours.

12 parts of styrene, 65 parts of dimethylaminoethyl methacrylate, 125 parts of 2-ethylhexyl acrylate,
2-Hydroxyethyl methacrylate 6 parts, N-n-
65 parts of butoxymethylacrylamide, 40 parts of a 50% aqueous solution of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride [Blenmar QA: trade name manufactured by NOF ■], the above polyester resin (PEK
-2) 75 parts, 6 parts of azobisisobutyronitrile.

After dropping, add 0.5 parts of azobisisoputilonitrile to 3 parts.
After the reaction temperature was raised to 9 to 0, 1.6 parts of azobisisoptylonitrile was added in 4 parts every 3 minutes. Further, the reaction was carried out for 4 hours at the same reaction temperature to obtain a resin solution having an acid value of 1.3, a hydroxyl value of 67, a weight average molecular weight of 11,700, and a nonvolatile content of 59.0%.

This was designated as PE-NC-3. [Preparation of mystery paints of Examples 1 to 4] Polyester modified vinyl resin (PE-NC-1 to 13)
13 parts of the mixture were added and mixed with a 10% acetic acid aqueous solution as a neutralizing agent so that the pH was within the range of 5.5 to 6.5, and then gradually diluted with 65 parts of ion-exchanged water.

After adding 20 parts of titanium white, 0.4 parts of carbon black, and 0.1 part of an antifoaming agent to the aqueous solution and dispersing it with a sand mill, the dispersion was further diluted with ion-exchanged water to a total of 512 parts. A water-based thermosetting coating composition of the present invention for electrodeposition coatings having a solid content of about 20% was obtained. (Preparation of performance test piece) While observing the coating composition for electrodeposition paint, 26 zinc phosphate-treated dull steel plates (0.8 x 70 x 15 squares) were placed in it.
Electrodeposition coating for 0.1 minute, then washing with ion-exchanged water,
It was dried at 180 qo for 20 minutes.

The voltage was set so that the film thickness after the competition would be 20 μm. The electrodeposited layer used in the above coating consisted of a 0 to 500 Y rectifier, a box-shaped electrodeposition tank made of approximately 3.5 mm polyvinyl chloride, a magnetic stirrer, and a carbon electrode plate (5 x 70 x 15 W,
The distance between the electrodes was approximately 10 skins). [Comparative example] 100 parts of polyptadiene (92.2% of 1,2 bonds, 7.8% of 1,4 bonds) with a number average molecular weight of 3150, 45 parts of maleic anhydride, Solvesso #150 [trade name manufactured by Esso Chemical ■] 100 parts of ditertiary butylated hydroxytoluene were added thereto, and the reaction was carried out for 6 hours while keeping the internal temperature at 175° C. under a nitrogen atmosphere.

Unreacted maleic anhydride and reaction solvent were removed under reduced pressure in a nitrogen atmosphere to obtain a reaction product.

The maleic anhydride addition rate was 13%. To 10 parts of the reaction product, 22 parts of stearyl alcohol was added, and the mixture was heated to 140°C while stirring.

After about 2 hours, it was confirmed from the infrared absorption spectrum of the reactant that stearyl alcohol and maleated polybutadiene had formed an ester bond. To 10 parts of the esterified product, 5 parts of ethylene glycomonoethyl ether were added and dissolved, and the carboxyl group was reduced to 0.
7 equivalents of triethylamine were added, and the mixture was further diluted with ion-exchanged water to a resin solid content of 30%.

After adding 20 parts of the aqueous solution, 16 parts of titanium white, and 1 part of carbon black and dispersing with a sand mill, the dispersion was diluted with ion-exchanged water to a solid content of about 12%, and used for decoating. provided.

Incidentally, the tortoise coating conditions and competition conditions of the above comparative example are as follows. Current application method: 180V for 2 minutes Test piece: Zinc phosphate treated dull steel plate solution Temperature: 25°C Branging conditions: After electrodeposition coating, washing with water and drying at 150°C for 30 minutes in the sun.

Dry film thickness: 21r The haze adhesion property values and various coating film performance test results conducted on the above samples are shown in Table 1.

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Claims (1)

[Claims] 1 (A) (i) Unsaturated polyester resin...2-
40% by weight, (ii) tertiary amino group-containing α,β-monoethylenically unsaturated monomer...5 to 20% by weight, (i
ii) N-alkoxymethylated monomer of α,β-monoethylenically unsaturated carboxylic acid amide, said monomer and one or more α,β-monoethylenically unsaturated monomers other than (ii) above. A monomer mixture consisting of a saturated monomer...93~
40% by weight, obtained by graft polymerization with a hydroxyl value of 1
A water-based thermosetting resin coating composition comprising a polyester-modified vinyl resin of 0 to 150, (B) an acid as a neutralizing agent, and (D) water as a diluent. 2 The unsaturated polyester resin has at least 1 to 10
2. The aqueous thermosetting resin coating composition according to claim 1, which contains % by weight of α,β-unsaturated dicarboxylic acid as one of the constituent components. 3 α that graft-polymerizes with the unsaturated polyester resin
, β-monoethylenically unsaturated monomer mixture is (a)
α,β-monoethylenically unsaturated monomer containing quaternary ammonium salt…1 to 15% by weight (b) Hydroxyalkyl ester of α,β-monoethylenically unsaturated carboxylic acid…1 to 30% by weight (c) N-alkoxymethylated monomer of α,β-monoethylenically unsaturated carboxylic acid amide...5 to 30% by weight (d) α, other than the above (a), (b) and (c), β
- The water-based thermosetting resin coating composition according to claim 1, comprising 25 to 93% by weight of monoethylenically unsaturated monomer.