JPS6160874B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a cathodically deposited electrodeposition coating composition. A resin having a certain type of basic group forms a cationic resin in water, and when this is used for electrodeposition coating, the resin is deposited on the cathode. This type of cathodically deposited paint neutralizes a resin with acid groups with a base,
It is possible to eliminate the essential drawbacks of conventional water-soluble anodic electrodeposition paints, that is, elution of the metal to be coated into the paint bath and various problems caused by this. The present inventors researched such cathodic deposition type paints and previously found the general formula (In the formula, R ₁ , R ₂ , R ₃ , R ₄ and By dispersing or solubilizing it in water and using it in a cathode-deposited electrodeposition coating, it has excellent curing properties, and has excellent resistance to mechanical external forces such as impact or bending, as well as alkalinity, water resistance, and solvent resistance. We have already applied for a patent on a coating composition that can be used in cathodically deposited electrodeposition paints with high storage stability and which can provide coatings with excellent chemical resistance. (Japanese Unexamined Patent Publication No. 51-119727, Patent Application No. 51-138406) The above-mentioned basic group-containing polymers are characterized by forming a cured coating film mainly through oxidative polymerization of unsaturated groups during normal baking. However, the corrosion resistance was not necessarily sufficient. Therefore, as a result of intensive research in order to improve the corrosion resistance without losing the excellent curability and coating properties of the above-mentioned cathode-deposition resin, we decided to mix a glycidyl compound, which was changed with an amine compound, into the cathode-deposition resin. They discovered that corrosion resistance could be improved by using this method, and filed a patent application. (Patent Application No. 53-133772) However, the resin composition of the above-mentioned invention was poor and could not fully meet the strict requirements regarding corrosion resistance.After further research, it was discovered that the cathode-deposited resin contained only an unsaturated carboxylic acid. The inventors have arrived at the present invention, which shows that a cathodically deposited electrodeposition paint having extremely good corrosion resistance can be obtained when a glycidyl compound modified with is blended. Accordingly, an object of the present invention is to provide a cathodically deposited electrodeposition coating material which has further improved corrosion resistance. The purpose of the present invention is to contain (A) the general formula in a proportion of 0.05 to 0.5 mol per 100 g of the polymer as an essential component. (In the formula, R ₁ is a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 3 carbon atoms, and R ₂ is a hydrocarbon group having 1 to 20 carbon atoms.
R ₃ and R ₄ represent a hydrocarbon group having 1 to 20 carbon atoms, in which a hydrogen atom or a part thereof may be substituted with a hydroxyl group, and at least one of R ₃ and R ₄ represents the hydrocarbon group. It is a hydrogen group, and X represents a hydrogen atom or a bond, and when X is a bond, the carbon atom to which R ₁ is attached and the carbon atom adjacent to the carbon atom to which the hydrogen atom is attached both form part of the main chain. (can be formed) containing a basic group with a molecular weight of 300~
5000 conjugated diene polymer or copolymer 100 parts by weight and (B) general formula (In the formula, R ₅ and R ₆ are hydrogen atoms or carbon atoms 1
~10 alkyl group, n is an integer from 0 to 20, m
is 1 or 0, Y is a residue of an unsaturated carboxylic acid having 3 or 4 carbon atoms, and Y' is a hydrogen atom when m is 0, and Y when m is 1). Contains 3 to 100 parts by weight of
This is achieved by the cathodic deposition type electrodeposition coating composition of the present invention, in which component (A) is neutralized with an organic or inorganic acid and dissolved or decomposed in water together with component (B). The conjugated diene polymer or copolymer having a basic group as component (A) in the present invention is generally the same as the conjugated diene polymer or copolymer having an acid group such as a succinic acid group, for example, a maleic acid group or its anhydride. formula (In the formula, R ₂ , R ₃ , and R ₄ are the same as above.) It is synthesized by an imidization reaction with a diamine compound represented by the following formula. The conjugated diene polymer or copolymer having a molecular weight of 300 to 5,000, which is the starting material of the present invention, is produced by a conventionally known method. That is, using an alkali metal or an organic alkali metal compound as a catalyst, a conjugated diolefin having 4 to 10 carbon atoms alone, a combination of these diolefins, or a conjugated diolefin containing 50
A typical manufacturing method is anionic polymerization or copolymerization of aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, or divinylbenzene in an amount of mol % or less at a temperature of 0°C to 100°C. . In this case, in order to control the molecular weight and obtain a light-colored, low-weight product with little gel content, an organic alkali metal compound such as sodium benzyl is used as a catalyst, and a compound having an alkylaryl group, such as toluene, is used as a chain transfer agent. Chain transfer polymerization method (US Patent No. 3789090) or living polymerization method using a polycyclic aromatic compound such as naphthalene as an activator and an alkali metal such as sodium as a catalyst in a tetrahydrofuran solvent (Japanese Patent Publication No. 17485/1985) , No. 43-27432), or use a fusano group hydrocarbon such as toluene or xylene as a solvent, a dispersion of an alkali metal such as sodium as a catalyst, and control the molecular weight by adding an ether such as dioxane. Polymerization method (Special Publication No. 32-7446)
No. 33-1245, No. 34-10188) are suitable manufacturing methods. It is also produced by coordination anion polymerization using an acetylacetonate compound of a group 8 metal such as cobalt or nickel and an alkyl aluminum halide (Japanese Patent Publication No. 45
(No. 507, No. 46-30300) Low polymers can also be used. The next method for producing a conjugated diene polymer or copolymer having an acid group such as a succinic acid group, which is a starting material, is to add maleic acid to the conjugated diene polymer or copolymer at a temperature of usually 100 to 300°C. Conventionally known methods for adding maleic anhydride, citraconic acid, citraconic anhydride, etc. can be used (Japanese Patent Publication No. 46
- No. 11195). Furthermore, when performing these addition reactions, a method of preventing gelation reactions by allowing phenylene diamines, pyrogallols, naphthols, etc. to be present in the system (West German Publication No. 2362534) can also be preferably employed. The amount of acid groups such as maleic acid, maleic anhydride, citraconic acid, and citraconic anhydride to be added to the conjugated diene polymer or copolymer is 0.05 to 0.5 mol, preferably 0.1 to 0.25 mol per 100 g of the butadiene polymer or copolymer. It is. If the amount of the above acid group is less than 0.05 mol per 100 g of resin, the water solubility will be poor when the resin obtained by reacting with a diamine compound is neutralized with acid to make it water-soluble, and the amount of the above acid group is less than 0.5 mole. When the amount is more than mol, the water solubility is too good, and when formed into a coating film, the water resistance is poor and it cannot be used practically. The above general formula used when producing component (A) in the present invention

Examples of diamine compounds of [formula] are primary compounds such as β-hydroxyethylaminoethylamine, β-hydroxyethylaminopropylamine, methylaminoethylamino, ethylaminoethylamine, methylaminopropylamine, ethylaminopropylamine, and butylaminopropylamine. Diamine compounds having an amine and a secondary amine and/or compounds having a primary amine and a tertiary amine such as dimethylaminoethylamine, diethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine and dibutylaminopropylamine. R ₂ , R ₃ and R ₄ are generally alkyl groups, cycloalkyl groups, aryl groups, etc., but those in which 1 to 3 of the hydrogen atoms of these groups are substituted with -OH are also preferably used. In the present invention, a conjugated diene polymer or copolymer having an acid group is reacted with the above diamine compound alone or with a mixture of two or more diamine compounds. These reactions are imidization reactions between succinic acid groups and primary amine groups. The amount of the diamine compound to be used is preferably an equivalent molar amount to the succinic acid group of the conjugated diene polymer or copolymer having an acid group, but an excess of the amine compound is used and distilled off after the reaction. It is also possible. It is also possible to leave a carboxyl group by using an amine compound in an amount equal to or less than the molar amount of the succinic acid group. A diamine compound having a primary amine and a secondary amine and a diamine compound having a primary amine and a tertiary amine can also be used as a mixture. Usually, in this reaction, the molar ratio of the diamines used for the reaction and the molar ratio of the diamines introduced are approximately equal. It is also possible to replace a part of the diamine compound used with an alkanolamine having a primary amino group such as monoethanolamine. An alkanolamine having a primary amino group can be condensed with a succinic acid group of a conjugated diene polymer or copolymer by an imidization reaction similarly to a diamine compound, and a hydroxyl group is introduced. The imidization reaction between the conjugated diene polymer or copolymer having the above acid group and the diamine compound is 50 to 300
It is carried out at a temperature of 100-200°C, preferably 100-200°C. The imidization reaction can be carried out in the presence or absence of a solvent. When the viscosity of the conjugated diene polymer or copolymer having acid groups to be imidized is low, it is preferable not to use a solvent. When using solvents, benzene, toluene,
Hydrocarbon solvents such as silohexane and xylene,
Although it is possible to use a solvent that mixes with a conjugated diene polymer or copolymer having an acid group, such as an alcohol solvent such as butyl cellosolve, or an ether solvent such as diethylene glycol dimethyl ether, it is possible to use a hydrophilic solvent such as butyl cellosolve as described below. A method of water solubilization is preferred. In this way, the general formula (In the formula, R ₁ , R ₂ , R ₃ , R ₄ and X are the same as above) Containing a basic group with a molecular weight of 300 to 5000
A conjugated diene polymer or copolymer is produced. A novel aspect of the invention is that the composition comprises the ingredients described above.
(A) That is, together with resin (A), as component (B), the general formula (In the formula, R ₅ and R ₆ are hydrogen atoms or carbon atoms 1
~10 alkyl group, n is an integer from 0 to 20, m is 1 or 0, Y is a residue of an unsaturated carboxylic acid having 3 or 4 carbon atoms, and Y' is a hydrogen atom when m is 0. , when m is 1, it represents Y), and this reduces the excellent curability and film properties of cathodically deposited electrodeposition paints containing component (A) as an essential component. It is possible to obtain an electrodeposited paint which provides a coating film with markedly improved corrosion resistance while maintaining the corrosion resistance. The content of component (B) is in the range of 3 to 100 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of resin (A). If the content of component (B) is less than this, corrosion resistance will not be improved sufficiently, and if it is more than this, water dispersibility will deteriorate. To obtain the compound of component (B) above, use the formula (R ₅ and R ₆ are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably a methyl group or an ethyl group, n is an integer of 0 to 20, preferably 1 to 5, and m is 0
or 1, preferably 1) is used as a raw material. This glucidyl compound can be prepared by etherifying bisphenol with epichlorohydrin, usually in the presence of an alkali. Such bisphenol compounds include 2,2-bis(4'-
hydroxyphenyl)propane, 1,1-bis(4'-hydroxyphenyl)ethane, 1,1-bis(4'-hydroxyphenyl)isobutane, and the like. In many cases, further reaction of the above glycidyl ethers with bisphenols and the like, and then further reaction of this product with epichlorohydrin, synthesizes glycidyl compounds with somewhat higher molecular weights, which can be used. Next, the glycidyl compound is reacted with an unsaturated carboxylic acid having 3 or 4 carbon atoms at a temperature of 1 to 200°C, preferably 50 to 150°C. Unsaturated carboxylic acids having 3 or 4 carbon atoms include acrylic acid, methacrylic acid, crotonic acid, etc., and mixtures thereof can also be used. Appropriate catalysts such as tertiary amines and quaternary ammonium salts can be used for the reaction. The reaction can be carried out in the presence or absence of a solvent, but if a solvent is used, it should be the same type as the solvent used in the step of reacting the primary or secondary amine during the synthesis of the resin (A). can be used. In the above reaction, when using acrylic acid as the unsaturated carboxylic acid, for example, the reaction formula is as follows: Proceed according to. In the present invention, in the above glycidyl compound molecule,

[Formula] Substantially all of the group is reacted with the unsaturated carboxylic acid so that no group remains.

[Formula] Group (Y has the same meaning as above) taste).

[Formula] If the group remains, this group will react unfavorably with the basic group of the resin (A) when an acid is added later to make it water-solubilized, resulting in gelation and increased viscosity. So it cannot be water-solubilized. For example, even if water-solubilization is achieved, the aqueous solution changes over time, resulting in disadvantages such as unsteady electrodeposition characteristics or an inability to obtain an electrodeposited coating. Traditionally, bisphenol-type epoxy resins have been known as resins with excellent corrosion resistance. ), attempts have been made to use blocked isocyanate compounds as crosslinking agents. However, such paints require high temperatures of 200°C or higher to obtain practical hardness, and even if they can be cured at relatively low temperatures, they have drawbacks such as the inability to select a baking temperature within a narrow range. Furthermore, the bisphenol type epoxy resin must have a certain degree of high molecular weight under practical electrodeposition conditions, and the coating film inevitably tends to lack flexibility. Furthermore, when a blocked isocyanate is used in a resin having carbon-carbon double bonds, oxidative polymerization during baking tends to be inhibited, making it difficult to obtain a coating film with sufficient performance. Therefore, according to the present invention, the glycidyl compound

[Formula] Substantially all of the groups are

The compound (B) converted to [Formula] is used as a component of the cathodic deposition type electrodeposition paint, and the resin, (A)
Can be used in conjunction with resin (A), thereby
It is truly surprising that it has been found that it is possible to significantly improve the corrosion resistance of . In the present invention, in order to make the resin (A) and the compound (B) into an aqueous solution or disperse them in water, they are mixed in advance, and hydrochloric acid in an amount of 0.1 to 2.0 molar equivalent, preferably 0.2 to 1.0 molar equivalent to the amino group in the mixture, A method of neutralizing with an inorganic acid such as sulfuric acid or a water-soluble organic acid such as formic acid, acetic acid propionic acid, or lactic acid can be suitably used. These neutralizations are usually achieved by simply mixing the resin (A) and/or the compound (B) with the acid at room temperature. In the present invention, a dryer can be added to the composition obtained by dispersing the resin (A) and the compound (B) in water or forming an aqueous solution in this way. Salts of metals such as manganese, cobalt, zinc, and lead are used as dryers, but water-soluble manganese compounds are most suitable. Such water-soluble manganese, compounds such as manganese salts of relatively low-molecular organic acids such as manganese formate, manganese acetate, manganese propionate, manganese lactate, and manganese salts of inorganic acids such as manganese sulfate, manganese chloride, manganese nitrate, and manganese acetylacetonate are used. The amount of the manganese compound added is 0.01 to 5.0 parts by weight as manganese metal per 100 parts by weight of the resin (A), preferably 0.1 to 5.0 parts by weight.
1.0 parts by weight are used. When the resin (A) and compound (B) of the present invention are neutralized and dissolved or dispersed in water, dissolution or dispersion is facilitated, the stability of the aqueous solution is improved, the fluidity of the resin is improved, and the coating film is improved. For the purpose of improving smoothness, etc., ethyl cellosolve, propyl cellosolve, butyl cellosolve, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diacetone alcohol, which are water-soluble and can dissolve the resin (A) and compound (B) of the present invention, 4-
It is preferable to use 10 to 100 parts by weight per 100 parts by weight of the organic solvent such as methoxy-4-methylpentanone-2, methyl ethyl ketone, component (A) and component (B). A suitable pigment can be further blended into the cathodically deposited electrodeposition coating composition of the present invention. For example, one or more pigments such as iron oxide, lead oxide, strontium chromate, carbon black, titanium dioxide, talc, aluminum silicate, and barium sulfate can be blended. These pigments can be added to the composition of the present invention as they are, but a large amount of the pigments is added to a portion of the neutralized resins (A) and (B) and dispersed in water or made into an aqueous solution, and then mixed to form a paste. A masterbatch of the pigment can be obtained and this paste-like pigment can be added to the composition. Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. The physical properties of the coating films of Examples and Comparative Examples were tested in accordance with JIS-K-5400. Example 1 (1) Using sodium benzyl as a catalyst, butadiene was underpolymerized at 30°C in the presence of toluene as a chain transfer agent, resulting in a number average molecular weight of 2000 and a viscosity at 25°C.
A liquid polybutadiene with 120 poise and 65% 1.2 bonds was synthesized. (2) Next, 1000 g of this polybutadiene, 163 g of maleic anhydride, 10 g of xylene, and 2 g of Antigen 3C (trade name of Sumitomo Chemical) were placed in a reflux condenser.
Pour into a separable flask and place under nitrogen stream.
The reaction was carried out at 190°C for 5 hours. Next, unreacted maleic anhydride and xylene were distilled off under reduced pressure, and the acid value was 80.
A maleated polybutadiene was synthesized. (3) Maleated polybutadiene synthesized in (2) above
803 g and 156 g of butyl cellosolve were charged into a two-separable flask equipped with a reflux condenser and heated to 80° C. with stirring. Next, 78 g of dimethylaminopropylamine was added dropwise, followed by 23 g of monoethanolamine. Immediately after completion of dripping
The temperature was raised to 150°C, and the reaction was continued at 150°C for 4 hours. The produced water, butyl cellosolve and the terminally reacted amine were distilled off under reduced pressure to synthesize imidized polybutadiene having a tertiary amine group and a hydroxyl group. The amine value of this imidized polybutadiene (resin (A ₁ )) was 50. (4) 300 g of imidized polybutadiene obtained in (3) above.
After dissolving in 60g of butyl cellosolve, lactic acid 16.1
Neutralize with g and add deionized water to a solids concentration of 20
A wt% aqueous solution was prepared. 600 g of the above aqueous solution, 190 g of titania, 3.6 g of carbon black, 106.5 g of aluminum silicate, and 900 g of glass beads were placed in two stainless steel beakers and stirred vigorously for 2 hours using a high-speed rotating mixer. A pigment paste was produced. (5) On the other hand, the following compound obtained by reacting bisphenol A and epichlorohydrin in the presence of an alkali catalyst As a bisphenol type epoxy resin with an epoxy equivalent of 500 [trade name Epicote 1001
1000g of butyl cellosolve manufactured by Ciel Chemical Co., Ltd.
Add 137 g of acrylic acid, 0.2 g of hydroquinone and 5 g of N,N dimethylaminoethanol, heat to 100°C and react for 5 hours to obtain a butyl cellosolve solution of epoxy resin-acrylic acid adduct [Compound (B ₁ ) was synthesized. 150 g of imidized polybutadiene (resin (A ₁ )) with an amino value of 50 synthesized in (3) above and 50 g of the compound (B ₁ ) synthesized in (5) above were mixed with butyl cellosolve 30 g.
After dissolving the mixture in 100 g, 8.1 g of lactic acid was added to neutralize it.
Deionized water was added to prepare an aqueous solution with a solid content concentration of 20% by weight. Add 150 g of the pigment paste prepared in (4) above to this 20% by weight aqueous solution, stir well, and add manganese lactate.

[Formula] 6.7g was dissolved in deionized water to prepare an electrodeposition coating liquid with a solid content concentration of 15% by weight. A carbon electrode using the above paint liquid is used as an anode,
Untreated steel plate (G.3141 manufactured by Nippon Test Panel Co., Ltd.)
(SPCC-SD) 0.6 x 70 x 150 mm) was used as a cathode for cathodic deposition electrodeposition coating. The test results are shown in Table 1. Example 2 1000 g of bisphenol type epoxy resin (trade name Epicote 1004, manufactured by Ciel Chemical Co., Ltd.) having an epoxy equivalent of 1000 was dissolved in 214 g of butyl cellosolve, and 69 g of acrylic acid, 0.1 g of hydroquinone, and 5 g of N,N dimethylaminoethanol were dissolved. A butyl cellosolve solution of an epoxy resin-acrylic acid adduct [compound (B ₃ )] was synthesized under the same reaction conditions as in Example 1 (3). 150 g of imidized polybutadiene (resin (A ₁ )) with an amine value of 50 synthesized in Example 1 (3) and 50 g of the above compound (B ₂ ) were dissolved in 30 g of butyl cellosolve, and then 8.1 g of lactic acid was added to neutralize the solution. Deionized water was added to prepare an aqueous solution with a solid content concentration of 20% by weight.
To this 20% by weight aqueous solution, 150g of the pigment base prepared in Example 1 (4) was added, stirred thoroughly, and then deionized water in which 6.7g of manganese lactate was dissolved was added to prepare an electrodeposition coating liquid with a solid content concentration of 15% by weight. did. Electrodeposition coating was carried out in the same manner as in Example 1 using the above coating liquid. The results are shown in Table 1. Example 3 The polybutadiene with a number average molecular weight of 2000 synthesized in (1) of Example 1 was maleated to synthesize maleated polybutadiene with an acid value of 55. 1105 g of maleated polybutadiene and 221 g of butyl cellosolve were charged into a two-separable flask equipped with a reflux condenser and heated to 80° C. with stirring. Next, 110 g of dimethylaminopropylamine was added dropwise, and immediately after the addition was completed, the temperature was raised to 150°C, and the reaction was continued at the same temperature for 4 hours. Next, the produced water, butyl cellosolve and unreacted amine were distilled off under reduced pressure to synthesize imidized polybutadiene (resin (A ₂ )) having a tertiary amine group and having an amine value of 50. The above imidized polybutadiene (resin (A ₂ ))
After dissolving 150 g of the compound (B ₁ ) synthesized in Example 1 in 26 g of butyl cellosolve, 8.1 g of lactic acid was added for neutralization. Add deionized water to determine solids concentration
A 20% by weight aqueous solution was prepared. To this 20% by weight aqueous solution, 150g of the pigment paste prepared in (4) of Example 1 was added, stirred thoroughly, and then deionized water in which 6.7g of manganese lactate was dissolved was added to give a solid content concentration of 15% by weight. % electrodeposition paint was prepared. Electrodeposition coating was carried out in the same manner as in Example 1 using the above coating liquid. The results are shown in Table 1. Comparative Example 1 300 g of bisphenol type epoxy resin having an epoxy equivalent of 500 and 60 g of diethanolamine were reacted at 80% for 4 hours in the presence of 180 g of butyl cellulose, resulting in the reaction of both terminals.

[Formula] Substance of group all the targets

An amine compound (compound (B ₃ )) based on [Formula] was obtained. 150 g of the resin (A ₁ ) synthesized in Example 1 and 50 g of the above compound (B ₃ ) were added to 30 g of butyl cellosolve.
After dissolving it in water, 9.7 g of lactic acid was added to neutralize it. Add deionized water to make a 20% by weight aqueous solution, add 150 g of the pigment paste prepared in (1) of Example 1,
Furthermore, deionized water in which 6.7 g of manganese lactate was dissolved was added to prepare an electrodeposition coating liquid with a solid content concentration of 15% by weight. Table 1 shows the results of electrodeposition coating using the above coating liquid in the same manner as in Example 1. Comparative Example 2 600g of bisphenol type epoxy resin with epoxy equivalent of 500 and linseed oil fatty acid (L-70,
Acid value 193.1 mgKOH/g) was dissolved in 186 g of butyl cellosolve, 3 g of N,N dimethylaminoethanol was added, and the mixture was reacted at 110° C. for 4 hours to synthesize compound (B ₄ ). 150 g of the resin (A ₁ ) synthesized in Example 1 and 70 g of the above compound (B ₄ ) were added to 30 g of butyl cellosolve.
The solution was dissolved in water and 9.7 g of lactic acid was added to neutralize it. Comparative example 1
In the same manner as above, a 15% by weight electrodeposition coating liquid was prepared by adding the raw material paste and manganese lactate. Table 1 shows the results of electrodeposition coating. Comparative Example 3 800 g of bisphenol type epoxy resin having an epoxy equivalent of 500 and 91.3 g of acetic acid were dissolved in 178 g of butyl cellosolve, 4 g of N,N dimethylaminoethanol was added, and the mixture was reacted at 110°C for 6 hours to synthesize compound (B ₅ ). . 150 g of the resin (A ₁ ) synthesized in Example 1 and 50 g of the above compound (B ₅ ) were added to 30 g of butyl cellosolve.
The solution was dissolved in water and 9.7 g of lactic acid was added to neutralize it. In the same manner as in Comparative Example 1, a pigment base and manganese lactate were added to prepare a 15% by weight electrodeposition coating liquid. Table 1 shows the results of electrodeposition coating. As is clear from Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3, a specific compound obtained by reacting an unsaturated carboxylic acid with a resin made of amino group-containing polybutadiene and a glycidyl compound is an essential component. It is clear that cathodically deposited electrodeposition coating compositions provide marked improvement in corrosion resistance over untreated steel sheets without impairing the excellent physical properties of the former coating.

【table】

【table】

Claims (1)

[Claims] 1. As an essential component, (A) the general formula in a proportion of 0.05 to 0.5 mol per 100 g of the polymer; (In the formula, R ₁ is a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 3 carbon atoms, and R ₂ is a hydrocarbon group having 1 to 20 carbon atoms.
R ₃ and R ₄ represent a hydrocarbon group having 1 to 20 carbon atoms, in which a hydrogen atom or a part thereof may be substituted with a hydroxyl group, and at least one of R ₃ and R ₄ represents the hydrocarbon group. is _a hydrogen group; 100 parts by weight of a conjugated diene polymer or copolymer with a molecular weight of 300 to 5000 containing a basic group represented by (In the formula, R ₅ and R ₆ are hydrogen atoms or carbon atoms 1
~10 alkyl group, n is an integer from 0 to 20, m
is 1 or 0, Y is a residue of an unsaturated carboxylic acid having 3 or 4 carbon atoms, and Y' is a hydrogen atom when m is 0, and Y when m is 1). Contains 3 to 100 parts by weight of
and a cathodically deposited electrodeposition coating composition in which the component (A) is neutralized with an organic or inorganic acid and dissolved or decomposed in water together with the component (B). 2 (B) is a general formula (wherein R ₅ , R ₆ , m and n have the same meanings as above), the glycidyl compound represented by the general formula (In the formula, R ₇ and R ₈ are hydrogen atoms or methyl groups, and at least one of R ₇ and R ₈ represents a hydrogen atom.) Claim 1, wherein substantially all of the [Formula] groups in the glycidyl compound molecule are converted to [Formula] groups (where Y is the same as above)
Compositions as described in Section.