JPS5853675B2 - Cationic electrodeposition paint composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a coating film with excellent anticorrosion properties without containing harmful rust preventive agents such as hexavalent chromium compounds, and provides an electrolytic coating film with excellent stability in an electrodeposition bath. The present invention relates to a coating composition.

It is widely known that cured products of epoxy resins such as bisphenol A/epichlorohydrin type epoxy resins have excellent anticorrosive properties and adhesion properties, and addition of this epoxy resin with primary or secondary amines. Methods of making substances water-soluble by neutralizing them with acids are also already known.

However, when a hardening agent such as a blocked polyisocyanate compound is added to a water-solubilized product of such an amine-added epoxy resin to form a vehicle component, and a vehicle component is electrodeposited, a smooth and practical film thickness (usually 20 ~25μ)
Moreover, even if a large amount of organic solvent is used to improve this defect and a coating film with a smooth and practical thickness is initially obtained, it may deteriorate over time. The coating becomes difficult to adhere to, and a practical film thickness cannot be obtained after a long period of time.

(The performance of a paint over time as described above is hereinafter referred to as ``operational stability.'' When the performance of a paint changes over time, it is said to have ``poor operational stability.''

) If you try to obtain a practical film thickness, increasing the voltage has the disadvantage of causing damage to the coating.

Possible reasons for this include a decrease in the fluidity of the resin due to evaporation of the solvent contained in the paint, or a change in the dispersion state of the resin.

The present invention aims to solve these problems and provide a resin composition for cationic electrodeposition coatings that provides a coating film with excellent coating surface condition and has excellent operational stability.

That is, the present invention provides (I) a reaction product of an epoxy resin and a basic amino compound and/or a derivative of the reaction product (hereinafter referred to as "r(A) 1 minute"), which is neutralized with an acid. a water-soluble or water-dispersible resin; (II) an addition polymer of ethylene oxide and/or propylene oxide having a number average molecular weight of 500 to 1000 and a solubility of 60 parts by weight or less per 100 parts by weight of water; The present invention relates to a cationic electrodeposition coating composition characterized in that it contains as a main vehicle component a mixture with a derivative of an addition polymer (hereinafter referred to as "component B").

A feature of the present invention is that a specific polyether compound is blended, and as a result, the coated surface condition and operational stability can be significantly improved.

The epoxy resin used in the production of component (4) of the present invention is preferably a polyepoxide of a polyphenol having two or more epoxy groups per molecule, such as an epoxy resin obtained from bisphenol A and epichlorohydrin, or an epoxy resin obtained from hydrogenated bisphenol A and epichlorohydrin. Alternatively, epoxy resins obtained from bisphenol A and β-methylepichlorohydrin, polyglycidyl ethers of novolak resins, and the like can be mentioned.

Among these, particularly preferred is bisphenol A
It is an epoxy resin obtained from and epichlorohydrin.

In combination with these polyphenol/epichlorohydrin type epoxy resins, a) ethylene glycol, propylene glycol,
b) polyglycidyl ethers of polyhydric alcohols such as glycerin or trimethylolpropane and epichlorohydrin; b) polyglycidyl esters of epichlorohydrin and polycarboxylic acids such as adipic acid, fucuric acid or dimer acids; C) cycloaliphatic olefins; Other epoxy resins such as polyepoxide obtained by epoxidizing 1.2-polybutadiene can also be used to the extent that they do not impair the corrosion resistance of the polyphenol or epichlorohydrin type epoxy resin (50% by weight or less of the total amount of epoxy resin).

As the basic amino compound to be reacted with these epoxy resins, compounds having a primary or secondary amine group are used, and water-soluble aliphatic amino compounds are particularly preferably used.

Examples include, for example, a) mono- and dialkylamines such as propylamine, butylamine, diethylamine, dipropylamine; b) mono- and di-alkylamines such as ethanolamine, propatoolamine, jetanolamine, dibrobanolamine. alkanolamine,
c) Alicyclic monoamines such as cyclohexylamine, pyrrolidine, morpholine, d) ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylene diamine, dipropylene triamine, butylene diamine, N-aminoethanolamine , diethylethylenediamine, diethylaminopropylamine, piperazine,
Examples include polyamines such as N-methylpiperazine and N-aminoethylpiperazine.

In addition, aniline, N
-Methylaniline, toluidine, benzylamine, m-
xylylenediamine, metaphenylenediamine, 4,4
- Aromatic amines such as soaminodiphenylmethane may also be used.

The aromatic amine is preferably used in an amount such that water dispersibility is not lost when the epoxy resin-amine adduct is neutralized with an acid.

The reaction between an epoxy resin and a basic amino compound occurs simply by mixing them at room temperature, and is an exothermic reaction.

Finally 50-1500C to complete this reaction.
It is preferable to heat to 70 to 130°C.

The amount of basic amino compound to be reacted with the epoxy resin is
The amount may be at least sufficient to make the reaction product water-soluble when solubilized with an acid.

Further, in the present invention, derivatives of the reaction product of an epoxy resin and a basic amino compound (epoxy resin-amine adduct) include: (1) a modified product obtained by reacting an epoxy resin with a basic amino compound and a fatty acid; An amide-modified product obtained by the reaction of the epoxy resin-amine adduct with a polyamide resin; a modified product obtained by the reaction of the polyisocyanate compound obtained by the reaction with the epoxy resin-amine adduct, ■ a reaction product of the modified product of (■) above and the partially blocked polyisocyanate compound used in (■), ■ the above Examples include reaction products of the amide-modified product of (1) and the partially blocked polyisocyanate compound used in (2).

The above fatty acids include safflower oil fatty acids, linseed oil fatty acids, soybean oil fatty acids, tall oil fatty acids, cottonseed oil fatty acids, coconut oil fatty acids, tung oil fatty acids, oicilla oil fatty acids, dehydrated castor oil fatty acids, and hydien fatty acids (trade name). ,
Examples include non-drying, semi-drying and drying oil fatty acids such as Soken Kagaku Co., Ltd.).

As a method for obtaining the modified product (2), the epoxy group of the epoxy resin and the fatty acid may be first reacted at 80 to 130°C, and then the amine may be reacted, or the amine may be reacted first to form the epoxy-amine adduct. After obtained, this may be reacted with a fatty acid.

In the latter case, the amine used is preferably a secondary amine.

18 To react a hydroxyl group or an amino group with a fatty acid
The dehydration reaction may be carried out at 0 to 230°C for several hours.

As the polyamide resin in (2), for example, dicarboxylic acids such as phthalic acid, adipic acid, sepatic acid, and dimer fatty acids, and polyamines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, propylene diamine, and butylene diamine are used. An amine group-containing polymer obtained by condensation is preferable, and a polyamide obtained by further condensing an oligomer obtained by ring-opening polymerization of a lactam such as 5-caprolactam with a polyamine, or a substitute for the polyamine (this ethanol Polyester polyamides obtained using alkanolamines such as amines and propatool amines are used.

All of these contain amino groups and amide groups in their molecules that can react with epoxy groups.

The reaction between the epoxy resin-amine adduct and the polyamide resin is preferably carried out at 50-200°C, preferably 80-150°C, and the polyamide resin is added to the epoxy group in the epoxy resin-amine adduct.

(1) The partially blocked polyisocyanate compound herein is a polyisocyanate compound having an average of one or more blocked incyanate groups and more than O but one or less free isocyanate groups in one molecule.

The polyisocyanate used for this is m- or p-
- Fragrances such as phenylene diisocyanate, 4,4-phenylmethane diisocyanate, 2,4- or 2,6-t-lylene diisocyanate, m- or p-xylylene diisocyanate, hexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate polyisocyanates such as group or aliphatic diisocyanates, and adducts of excess of these diisocyanates with polyols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, as well as trimers of the above diisocyanates, etc. can be mentioned.

Volatile low-molecular active hydrogen compounds are used as blocking agents for polyisocyanates, examples of which include methanol, ethanol, propatool, butanol, hexanol, cyclohexanol, benzyl alcohol,
Aliphatic or aromatic monoalcohols such as ethylene glycol monoethyl ether (hereinafter abbreviated as cellosolve), hydroxy tertiary amines such as dimethyl or diethylaminoethanol, oximes such as acetoxime, methyl ethyl ketone oxime, and phenol. , cresol, etc.

Among these, aliphatic or aromatic monoalcohols are preferred.

The partially blocked polyisocyanate is obtained by reacting the polyisocyanate with a sufficient amount of blocking agent to provide more than O and no more than 1 free isocyanate group per molecule.

Since this reaction is highly exothermic, it is preferable to carry out the blocking agent dropwise into the polyisocyanate.

It is preferable to carry out the reaction at a temperature as low as possible, from 20 to 80°C, and to increase the difference in the reactivity of each isocyanate group in one molecule.

The reaction between the partially blocked incyanate compound and the epoxy resin-amine adduct is facilitated by heating at 40-130°C, preferably 60-110°C for 1-3 hours, so that the free isocyanate is converted into a hydroxyl group or Adds to amino group.

The reaction product (2) is obtained by addition reaction between the reaction product obtained in the above and the partially blocked isocyanate compound used in (2).

This reaction can be carried out by reacting the basic amino compound and fatty acid with the epoxy resin, and then reacting the partially blocked polyisocyanate at 40 to 130°C, preferably 60 to 110°C, or by changing the order of the reaction and reacting the partially blocked polyisocyanate with the epoxy resin. After reacting the reaction product between the amino compound and the partially blocked polyisocyanate, the fatty acid may be reacted with the partially blocked polyisocyanate.

(2) is obtained by addition reacting the reaction product obtained in (2) with a partially blocked isocyanate compound similar to that used in (2).

This reaction is carried out at 40-130°C, preferably at 60-110°C.
It will be held in

It can also be obtained by changing the reaction order and reacting the partially blocked polyisocyanate with the reaction product of the epoxy resin and the amino compound, followed by the reaction with the polyamide resin.

In this way, a reaction product of the epoxy resin and the basic amino compound and a derivative of the reaction product (component (A)) are obtained.

(4) The amine value (described later) of the component is 25 to 400, especially 5.
0-200 is preferred.

When the amine value is within this range, after neutralization with acid, the dispersibility in water is excellent, and the resulting coating film has improved corrosion resistance and electrodeposition efficiency.

Further, it is preferable that no unreacted basic amine compound remains in the component (4).

The component (4) thus obtained is neutralized with a water-soluble organic or inorganic acid such as formic acid, acetic acid, hydroxyacetic acid, propionic acid, butyric acid, lactic acid, or phosphoric acid, sulfuric acid, or hydrochloric acid during the preparation of the electrodeposition coating. Ru.

It is preferable that the amount of the neutralizing agent is at least as high as necessary for solubilizing or dispersing the resin in water and not more than the equivalent weight of the amino groups of the resin.

Component (B) of the present invention has a number average molecular weight of 500 to 10.0.
00 and a solubility of 60 parts by weight or less per 100 parts by weight of water, an addition polymer of ethylene oxide and/or propylene oxide and/or a derivative of the addition polymer.

Specifically, the derivatives of the addition polymer include monoalcohol type derivatives obtained by addition-polymerizing propylene oxide or ethylene oxide to monoalcohol, b) monoalcohol-type derivatives obtained by addition-polymerizing propylene oxide or ethylene oxide to diols such as ethylene glycol or propylene glycol, etc. c) glycerin,
Polyol-type derivatives made by adding propylene oxide or ethylene oxide to trivalent or higher alcohols such as trimethylolpropane, pentaerythritol, or sorbitol; d) Addition polymerization of propylene oxide or ethylene oxide to an alkylphenol having an alkyl group having 8 or more carbon atoms. Phenol type derivatives obtained by
e) Reacting an addition polymer of ethylene oxide (or) propylene oxide with an incyanate compound such as phenyl isocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4-phenylmethane diisocyanate, hexamethylene diisocyanate, inphorone diisocyanate, etc. The resulting urethane compound having no free isocyanate groups, and f) addition polymers of ethylene oxide and/or propylene oxide and non-drying, semi-drying, and drying oil fatty acids, resin acids such as abietic acid, phthalic anhydride, isophthalic acid. , succinic acid,
Examples include esterified products having no free carboxyl group obtained by reacting with (poly)carboxylic acids such as adipic acid.

In the present invention, the proportion of the polyether as the component (B) to the water-soluble or water-dispersible resin as the neutralized product of the component (A) is 0.5 to 30% by weight, particularly 3 to 20% by weight. A range is preferred.

If the amount is less than 0.5% by weight, the effects of (B) ff addition (improvement of coated surface condition and operational stability) will not be sufficiently apparent, and 30
If the weight is too heavy, the resulting coating film will not have sufficient hardness or water resistance.

The electrodeposition coating composition of the present invention achieves the object of the present invention by having the neutralized product of the above four components and component (I3) as the main components, but it is modified with a partially blocked polyisocyanate as component (A). When using a material that is not a fully blocked isocyanate compound, in addition to these main vehicle components, 50 parts by weight of a fully blocked isocyanate compound is added as a vehicle component per 100 parts by weight of the resin solid content in component (4) in order to improve curability. Parts by weight or less may be added.

As the completely blocked isocyanate compound, all polyisocyanate compounds and blocking agents used in the production of the partially blocked isocyanate compound can be used.

In addition, as the blocking agent, compounds having active methylene groups such as acetoacetate, malonate, acetylacetone, or derivatives thereof can be used.

The production of a completely blocked isocyanate compound involves mixing the polyisocyanate compound and an equivalent amount or more of the blocking agent at 20 to 1
The reaction is carried out by heating to 20°C, preferably 40 to 100°C, until there are no free incyanate groups.

In order to proceed with the reaction smoothly, an ester solvent such as cellosolve acetate or ethyl acetate, or a ketone solvent such as cyclohexanone or diethyl ketone, which is inactive to react with incyanate groups, may be used.

In addition, the coating composition of the present invention further contains a cationic or nonionic water-soluble or water-dispersible resin as a vehicle component within a range (usually 20% by weight or less) based on the total resin solid content that does not impair corrosion resistance. ) may be included.

The above-mentioned cationic or nonionic water-soluble or water-dispersible resins include methylolated phenolic resin, methylolated melamine resin, polyacrylamide, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl ether, dialkylaminoethyl methacrylate or dialkylaminopropyl methacrylate. Examples include copolymers, reaction products of glycidyl methacrylate copolymers and secondary amines, and the like.

The coating composition of the present invention can also be used as a clear coating, but it is usually used with the addition of a pigment.

As pigments, those commonly used in electrodeposition paints are used, such as coloring and extender pigments such as zinc oxide, titanium white, carbon black, talc, clay and mica, which may be used in any desired amount. I can do it.

The composition of the present invention may also contain additives such as surfactants that are normally used in cationic electrodeposition coatings.

The coating composition of the present invention is prepared by adding a pigment to the neutralized component (4), dispersing it, and then dissolving or dispersing it in water (B) for 1 minute after adding a resin if necessary. Alternatively, the pigment may be dispersed in a resin, neutralized, and diluted with water, or other means commonly used in the production of electrodeposition paints can be applied.

The electrocoating composition of the present invention has a pH of 3 to 8, preferably a pH of 3 to 8.
It is neutralized with the above-mentioned water-soluble organic acid or inorganic acid so that the pH is in the range of 5 to 7.

In addition, the total resin concentration in the composition of the present invention is 3 to 30 weight □
, particularly preferably 5 to 15% by weight.

Although a conventional apparatus can be used for electrodepositing the cationic electrodeposition coating composition of the present invention, the object to be coated is used as a cathode, and the anode is preferably a carbon plate.

The coating film deposited on the cathode is baked and hardened at usually 140 to 250°C, preferably 170 to 220°C.

The electrodeposition paint obtained from the composition of the present invention is suitable for coating easily corroded steel plates such as ordinary iron phosphate treated steel plates, iron phosphate treated steel plates, non-treated steel plates, etc. Provides sufficient corrosion resistance without containing it.

This is an advantage not available with conventional electrodeposition paints.

It is also suitable for coating substrates such as galvanized steel, tinned steel, aluminum, copper and copper alloys.

The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.

In the examples, all parts and % are by weight.

The amine value was measured according to the following method.

Method for measuring amine value: Take 0.2 to 0.3 g of a sample in a 100 d Erlenmeyer flask, heat, dissolve, cool, and titrate with an aqueous N/l0 HCl solution using bromophenol blue as an indicator. When the color changes from blue to yellow, Set as the end point.

The amine value is determined by the following formula.

Example 1 500 parts of bisphenol A type epoxy resin (trade name: Epicoat 1001, manufactured by Shell Chemical) having an epoxy equivalent of 500 was heated and dissolved in 200 parts of cellosolve acetate.
Add 105 parts of jetanolamine at 0°C and heat to 100°C.
The mixture was reacted for 2 hours to obtain an amine-added epoxy resin having an amine value of 90.

Next, tolylene diisocyanate, (2,4-TDI-8
Blocked isocyanate compound 264 obtained by adding 90 parts of Cellosolve dropwise to 174 parts of 0%, 2.6-TDI=20%) at 60°C over 2 hours, and reacting for an additional 2 hours.
1 part to the above amine-added epoxy resin at 80°C.
．． After reacting for 5 hours, a basic resin composition with an amine value of 52 and a solid content of 81% is obtained.

To 123 parts of this, 10 parts of polyethylene glycol having a number average molecular weight of 4,000, 3.3 parts of glacial acetic acid, and 114 parts of deionized water are added to obtain a composition of the present invention having a solid content of 40%.

Example 2 425 parts of bisphenol A type epoxy resin having an epoxy equivalent of 950 (trade name: Epicote 1004, manufactured by Shell Chemical) was heated and dissolved in 175 parts of Cellosolve, and the mixture was heated at 40°
Add 30 parts of ethylenediamine all at once at C, and add 4 parts at 30°C.
After reacting for a period of time, the mixture was further heated at 80° C. for 2 hours to obtain a basic resin composition having a solid content of 72% and an amine value of 120.

8.7 parts of lactic acid and 102 parts of deionized water are added to 139 parts of this mixture and mixed with stirring to obtain a cationic water-dispersible composition having a solid content of 40%.

A triol type polyether having a molecular weight of 4.500 obtained by adding propylene oxide and ethylene oxide to trimethylolpropane to 250 parts of this product (product name: Newpol TL-4500.Sanyo Chemical)
), 20 parts of hexamethylolmelamine, and 62 parts of deionized water to obtain a composition of the present invention having a solids content of 40%.

Example 3 Novolak phenolic epoxy resin with an epoxy equivalent of 250 (trade name: DEN442, manufactured by Dow Chemical) 2
50 parts, 100 parts of butyl cellosolve, conjugated fatty acid (
Product name 2) Add 105 parts of Heidiene (manufactured by Soken Kagaku ■) and heat and mix at 120°C. After reacting until the acid value becomes O, add 66 parts of jetanolamine and stir for 1 hour.
The reaction is carried out for 0 minutes to obtain a basic resin composition having an amine value of 80 and a solid content of 80.5.

3.5 parts of propionic acid and 120 parts of deionized water are added to 124 parts of this to prepare a cationic water dispersion.

Next, 20 parts of phenolic polyether (trade name: Neugen EA1 manufactured by Daiichi Kogyo ■) obtained by addition polymerization of ethylene oxide to octylphenol and 7.2 parts of coconut oil fatty acid
5 parts of a polyether compound obtained by esterifying 5 parts of 1 part in a conventional manner and deionized water to obtain a composition of the present invention having a solid content of 40%.

Example 4 Bisphenol A type epoxy resin having an epoxy equivalent of 915 (product name: Ehicoat OO4, manufactured by Shell Chemical) 1
After heating and dissolving 00 parts in 150 parts of cyclohexanone, adding 26.4 parts of diethylamine and reacting at 90'C for 2 hours, a dimer acid type polyamide resin (trade name Nido-
Add 90 parts of Might 24o1 (manufactured by Fuji Kasei) and heat to 110°C.
Let it react for 1 hour.

200 parts of this, 25 parts of acetic acid and 120 parts of deionized water,
The present invention had a solid content of 40% by adding 7.5 parts of polypropylene glycol having a number average molecular weight of 3,000 and 40 parts of completely blocked isocyanate obtained by reacting 180 parts of cellosolve with 174 parts of tolylene diisocyanate as a curing agent. Obtain a composition.

Example 5 Bisphenol A type epoxy resin having an epoxy equivalent of 200 (trade name: Epon 828, manufactured by Shell Chemical) 20
0 parts of diisopropanolamine, 51 parts of diisopropanolamine, and 170 parts of cellosolve acetate were heated and mixed and reacted at 80°C for 3 hours to obtain an amine-added epoxy resin.

Next, 74 parts of n-butanol was added dropwise to 164 parts of tolylene diisocyanate at 50°C over 2 hours, and the mixture was reacted at 60°C for 2 hours to obtain 238 parts of partially blocked isocyanate resin.

This was reacted with the above amine-added epoxy resin at 70°C for 2 hours.

To this was added 100 parts of diethylenetriamine dimer acid type polyamide resin (Persamide 11S1 manufactured by Daiichi General Corporation), and the mixture was further reacted at 80° C. for 2 hours.

This has a molecular weight of i, oo. polypropylene glycol 2
Polyurethanized polyol 1 obtained by reacting 0 part of tolylene diisocyanate with 24 parts of tolylene diisocyanate at 100°C for 4 hours
Add 0 parts.

2.5 parts of hydroxyacetic acid and 60 parts of deionized water are added to 124 parts of this to obtain a composition of the present invention having a solid content of 40%.

Example 6 Bisphenol-type epoxy resin having an epoxy equivalent of 485 (trade name: Araldite 6071, manufactured by Chipa Corporation) 50
0 part was heated and dissolved in 200 parts of cellosolve acetate, 73 parts of diethylamine was added at 80°C, and the mixture was reacted at 115°C for 2 hours to obtain an amine-added epoxy resin having an amine value of 90.

Next, 190 parts of partially blocked isocyanate obtained by reacting 16.8 parts of methylene diisocyanate and 94 parts of phenol at 120°C for 3 hours was heated and reacted with the above amine-added epoxy resin at 90°C for 1 hour to obtain an amine value of 80.
, a basic resin composition with a solid content of 80.5% is obtained.

4.0 parts of hydroxyacetic acid and 120 parts of deionized water are added to 124 parts of this to prepare a cationic water dispersion resin composition.

To 250 parts of this, 20 parts of polypropylene glycol with a molecular weight of 2,000, and 2 parts of partially blocked isocyanate obtained by blocking tolylene diisocyanate with cellosolve.
6 parts of polyurethanized polyol and 59 parts of deionized water obtained by reacting at 120°C for 4 hours.
1 part to obtain a composition of the present invention having a solids content of 40%.

Example 7 Bisphenol type epoxy resin having an epoxy equivalent of 200 (trade name: Epon 828, manufactured by Shell Chemical) 200
1 part was heated and dissolved in 120 parts of methyl isobutyl ketone, and 1
42 parts of jetanolamine was added at 00°C and the temperature was increased to 105°C.
The mixture was reacted for 2 hours to obtain an amine-added epoxy resin having an amine value of 120.

120 parts of this, 40 parts of acetic acid, 108 parts of deionized water,
50 parts of a triol type polyether (trade name: GF-3000, manufactured by Sanyo Chemical Co., Ltd.) with a molecular weight of 3,000 obtained by adding propylene oxide to glycerin, and phenol added to Desmodur L as a curing agent. Add 115 parts of blocked isocyanate (product name: AP Stable, manufactured by Nippon Polyurethane), solid content 40%
A composition of the present invention is obtained.

Comparative Examples 1-7 In each of Examples 1-7, the same compositions were prepared as Comparative Examples 1-7, except that no polyether polyol was added.

Using the cationic water-dispersed compositions of Examples 1 to 7 and Comparative Examples 1 to 7, 18 parts of red iron was added to 100 parts of each of the compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 7. , 9 parts of clay, and 3 parts of lead silicate were mixed in a ball mill for 20 hours, diluted with deionized water to prepare an electrodeposition bath with a solid content of 13%, and applied to an iron phosphate-treated steel plate at each voltage of 3. After electrodeposition for a minute and washing with water, it was baked at 180°C for 30 minutes.

Further, operational stability was evaluated by stirring each electrodeposition paint in an open state at 30° C. for one month, replenishing volatilization loss with deionized water, and conducting an electrodeposition test in the same manner as above.

Claims (1)

[Scope of Claims] 1(I) A water-soluble or water-dispersible resin obtained by neutralizing a reaction product of an epoxy resin and a basic amino compound and/or a derivative of the reaction product with an acid, and (II) ) The number average molecular weight is 500 to 10,000,
The vehicle is characterized by containing as a main component an addition polymer of ethylene oxide and/or propylene oxide and/or a mixture with a derivative of the addition polymer, the solubility of which is 60 parts by weight or less per 100 parts by weight of water. A cationic electrodeposition coating composition. 2. The electrodeposition coating composition according to claim 1, wherein the epoxy resin is a polyphenol polyepoxide having two or more epoxy groups per molecule. 3. The electrodeposition coating composition according to claim 2, wherein the epoxy resin is an epoxy resin obtained from bisphenol A and epichlorohydrin. 4. The electrodeposition coating composition according to claim 1, wherein the basic amino compound is a compound having a primary or secondary amino group. 5. The electrodeposition coating composition according to claim 1, wherein the basic amino compound is a water-soluble aliphatic amino compound. 6 Derivatives of reaction products between epoxy resins and basic amine compounds are added to epoxy resins with amino compounds, safflower oil fatty acids, linseed oil fatty acids, soybean oil fatty acids, tall oil fatty acids, cottonseed oil fatty acids, coconut oil fatty acids, tung oil fatty acids. Claim 1, 2, or 4 is a modified product obtained by reacting fatty acids such as fatty acids, oiticica oil fatty acids, dehydrated castor oil fatty acids, and bydiene fatty acids (trade name, manufactured by Soken Kagaku Co., Ltd.) Electrodeposition paint composition. 7. Claim 1, wherein the derivative of the reaction product between an epoxy resin and a basic amino group is a modified polyamide obtained by reacting the reaction product with a polyamide resin.
, the electrodeposition coating composition according to item 2 or 4. 8 A derivative of a reaction product between an epoxy resin and a basic amine group is combined with the reaction product, a modified product of the reaction product with a fatty acid, or a modified product of the reaction product with a polyamide resin, with an average of 1 per molecule. Claim 1, which is a modified product obtained by reaction of the following free isocyanate groups with a partially blocked polyisocyanate compound having one or more blocked isocyanate groups:
The electrodeposition coating composition according to item 2 or 4. 9 The polyamide resin contains one or more dicarboxylic acids of phthalic acid, adipic acid, and sepatic acid and one or two of ethylene diamine, hexamethylene diamine, diethylene triamine, triethylene tetramine, propylene diamine, and butylene diamine. The electrodeposition coating composition according to claim 7 or 8, which is a reaction product with more than one type of polyamine. 10 A derivative of an addition polymer of ethylene oxide and/or propylene oxide is obtained by converting the addition polymer into a monoalcohol, a diol, a polyalcohol having a valence of 3 or more, an alkylphenol having an alkyl group having 8 or more carbon atoms, an isocyanate compound, or a carboxylic acid. The electrodeposition coating composition according to claim 1, which is a modified one. 11 The ratio of the addition polymer of ethylene oxide and (or) propylene oxide and (or) the derivative of the addition polymer to the reaction product of the epoxy resin and the basic amino compound and (or) the derivative of the reaction product is 0, The electrodeposition coating composition according to claim 1, wherein the content is 5 to 30% by weight. 12 A patent containing 50 parts by weight or less of a fully blocked isocyanate compound as a vehicle component based on 100 parts by weight of the resin solid content of the reaction product of an epoxy resin and a basic amino compound and/or a derivative of the reaction product. The electrodeposition coating composition according to claim 1. 13. The electrodeposition coating composition according to claim 1, which contains a cationic or nonionic water-soluble or water-dispersible resin as a vehicle component in a solid content ratio of 20% by weight or less based on the total resin solid content. .