JPH0623321B2 - Improved cathodic deposition type electrodeposition coating composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a cathodic deposition type electrodeposition coating composition which is curable at low temperature, has excellent coating surface smoothness and corrosion resistance, and can be formed into a thick film.

[Problems to be Solved by Prior Art and Invention]

A resin having a certain type of basic group produces a cationic resin in water, and when electrodeposition coating is performed using this resin, the resin is deposited on the cathode. The essential drawbacks of conventional anodic deposition type electrodeposition coatings, which are water-soluble by neutralizing the resin possessed by a base, namely the elution of the metal to be coated into the coating bath and the various problems resulting therefrom, Can be resolved.

Various proposals have been made so far for such a cathodic deposition type paint.

In recent years, from the viewpoint of energy saving and labor saving, it is desired to perform low temperature baking, thicken the electrodeposition coating film to avoid the intermediate coating step, smooth the surface of the electrodeposition coating film to remove the water polishing step, etc. There is.

In particular, as a cathodic deposition type electrodeposition composition with excellent low-temperature curability, an acrylic (methacrylic) double bond with high reactivity with an amino group was introduced into an epoxy group-containing polymer compound such as polybutadiene that was epoxidized. A mold has been proposed (Japanese Patent Laid-Open No. 56-151777), but in this oxidation polymerization curing type, when the electrodeposition coating film is thickened, the internal curing of the coating film is insufficient, and practical corrosion resistance, physical properties, etc. Does not satisfy the characteristics of.

As a result of various studies, the present inventors have found that a resin having a specific oxidative polymerization ability is mixed with a compound containing an ester group capable of being crosslinked and hardened by a transesterification reaction, and oxidative polymerization and transesterification crosslinking are used together. As a result, the inventors have found that a cathodic deposition type electrodeposition coating composition is obtained which improves the internal curability of the coating film, is low-temperature curable, has excellent smoothness and corrosion resistance of the coating film, and can be thickened.

An object of the present invention is to provide a cathodic deposition type electrodeposition coating composition which is curable at a low temperature, has excellent smoothness and corrosion resistance on the coated surface, and can be formed into a thick film.

[Means for solving problems]

That is, the present invention provides (A) 5 with a molecular weight of 500 to 5000.
Polymer compound 100 having a carbon-carbon double bond having an iodine value of 0 to 500 and 0.5 to 12% by weight of oxirane oxygen
General formula per g [Wherein R ₁ and R ₂ represent a hydrocarbon having 1 to 20 carbon atoms, a part of which may be substituted with a hydroxyl group,
However, R ₁ and R ₂ can have a ring structure, and an unsaturated group can be contained in the ring structure. ] The amine compound represented by [In the formula, R ₃ and R ₄ represent a hydrogen atom or a methyl group. ] 100 parts by weight of a reaction product of an α, β unsaturated carboxylic acid represented by [Wherein R ₅ and R ₆ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n represents an integer of 1 to 20 and preferably 1 to 10], and substantially all of the epoxy groups of the epoxy resin represented by General formula [Wherein R ₁ and R ₂ represent a hydrocarbon having 1 to 20 carbon atoms, part of which may be substituted with a hydroxyl group, provided that R ₁ and R ₂ may have a ring structure, The structure may contain unsaturated groups. ] And / or the general formula [In the formula, R ₃ and R ₄ represent a hydrogen atom or a methyl group. ] The reaction product of the alpha, beta unsaturated carboxylic acid represented by 0 to 150 parts by weight.

(C) A non-acidic polyester compound of polycarboxylic acid, which has two ester groups in one molecule which can be cross-linked and cured by a transesterification reaction with the hydroxyl groups in the above components (A) and (B) when the coating film is heated by heat. It is a cathodic deposition type electrodeposition coating composition containing 5 to 200 parts by weight of the above compound.

The polymer compound having a carbon-carbon double bond with a molecular weight of 500 to 5,000 and an iodine value of 50 to 500, which is the starting material of the component (A) of the present invention, can be produced by a conventionally known method.

That is, as the alkali metal or organic alkali metal compound catalyst, a conjugated diolefin having 4 to 10 carbon atoms alone, or these diolefins, or an aromatic vinyl monomer in an amount of 50 mol% or less with respect to the conjugated diolefin, for example, styrene, A typical production method is a method of anionic polymerization or copolymerization with α-methylstyrene, vinyltoluene or divinylbenzene 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 polymer with less 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 chain-transferred. Chain Transfer Polymerization Method Using Agent (US Patent No. 378909)
No. 0) or a living polymerization method in which a polycyclic aromatic compound such as naphthalene is used as an activator in a tetrahydrofuran solvent and an alkali metal such as sodium is used as a catalyst (Japanese Patent Publication Nos. 42-17485 and 43-27432). Polymerization method in which aromatic hydrocarbons such as toluene and xylene are used as a solvent, a dispersion of an alkali metal such as sodium is used as a catalyst, and ethers such as dioxane are added to control the molecular weight (Japanese Patent Publication No. 32-7446). , Ibid 38-1
Nos. 245 and 34-10188) are suitable production methods.

Further, a low polymer produced by coordinated anionic polymerization using an acetylacetonate compound of a Group 8 metal such as cobalt or nickel and an alkylaluminum halogenide as a catalyst (Japanese Patent Publication Nos. 45-507 and 46-80300) is also used. You can

The component (A) of the present invention is epoxidized by a known method using a peroxide such as hydrogen peroxide or peracetic acid as the unsaturated compound, and after introducing 0.5 to 12% by weight of the oxirane oxygen group as oxygen, the general formula [Wherein R ₁ and R ₂ are the same as above], after reacting the amine compound in the presence or absence of a solvent at a temperature of 50 to 200 ° C. [Wherein R ₃ and R ₄ are the same as the above] and are produced by reacting an α, β unsaturated carboxylic acid at 100 to 200 ° C.

The oxirane oxygen content is 0.5 to 12% by weight, preferably 2 to
If the amount is less than 10% by weight, the addition of amine is insufficient and the water solubility is insufficient, which is not preferable as a coating material.

On the other hand, if the amount is larger than this, a large amount of unreacted epoxy groups remain and the stability of the paint is deteriorated.

Examples of amines used in the reaction include dimethylamine,
Examples thereof include aliphatic amines such as diethylamine, alkanolamines such as methylethanolamine and diethanolamine, and cyclic amines such as morpholine and piperidine.

The amount of amine added is 100 g of epoxidized polymer compound
30 to 300 mmol, preferably 50 to 200 mmol.

Examples of α, β unsaturated carboxylic acids include acrylic acid, methacrylic acid and crotonic acid.

The amount of α, β unsaturated carboxylic acid to be added is 0 to 200 mmol, preferably 50 to 150 mmol, as the amount of carboxylic acid per 100 g of the epoxidized polymer compound.

The component (B) of the present invention has the general formula [Wherein R ₅ and R ₆ are the same as above], the diglycidyl compound is represented by a temperature of 0 to 200 ° C.,
The general formula is preferably at 50 to 150 ° C. It can be obtained by reacting an amine compound represented by the formula [wherein R ₁ and R ₂ are the same as above] with substantially 2 mol (1.8 to 2.0 mol) per 1 mol of the glycidyl compound.

Examples of amines used in the reaction include dimethylamine,
Examples thereof include aliphatic amines such as diethylamine, alkanolamines such as methylethanolamine and diethanolamine, morpholine, cyclic amines such as piperidine.

In addition, the above diglycidyl compound has a general formula at a temperature of 0 to 200 ° C, preferably 50 to 150 ° C. [Wherein R ₃ and R ₄ represent a hydrogen atom or a methyl group], and α or β unsaturated monocarboxylic acid, for example, acrylic acid, methacrylic acid, crotonic acid or the like, is substantially added to 1 mol of the diglycidyl compound. The component (B) can also be produced by reacting with 2 mol (1.8 to 2.0 mol).

Further, after partially reacting the glycidyl compound with an amine compound, the remaining glycidyl group may be reacted with an α, β unsaturated molar carboxylic acid.

In carrying out the reaction of α, β and unsaturated molar carboxylic acid, in order to prevent side reactions, hydroquinone, methoquinone,
Use radical polymerization inhibitors such as N-phenyl / N'-isopropyl-P-phenylenediamine and P-benzoquinone.
It is preferable to add 0.01 to 1.0% by weight and use a suitable catalyst such as a tertiary amine or a quaternary ammonium salt. Further, the reaction can be carried out in the presence or absence of a solvent, but when a solvent is used, it is inactive to the reaction, and a solvent that can be used in the electrodeposition coating, for example, ethyl cellosolve, butyl cellosolve, ethyl acetate. Cellosolve, MI
It is practically advantageous to use an appropriate amount of BK or the like and mix it with the components (A) and (C) as it is without removing it after the reaction and use it as an electrodeposition coating composition.

In the present invention, the epoxy group of the above diglycidyl compound React with the carboxylic acid group so that It is preferably converted into a group.

If a large amount of the group remains, this group causes an unfavorable reaction with the basic group contained in the component (A) when it is solubilized by adding an acid later and causes gelation, resulting in too high viscosity. As a result, the aqueous solution changes with time even if it can be solubilized, resulting in certain electrodeposition characteristics or the inability to obtain an electrodeposition coating film.

The content of the component (B) is 0 with respect to 100 parts by weight of the component (A).
To 150 parts by weight, preferably 30 to 100 parts by weight.

When the content of the component (B) is higher than this, water dispersibility is deteriorated.

The component (C) of the present invention is a non-acidic polyester compound of polycarboxylic acid, and an ester group 1 which can be crosslinked and cured by a transesterification reaction with the hydroxyl group in the above components (A) and (B) when the coating film is heated by heat. It is a compound containing two or more per molecule, and when it is contained, the fluidity of the coating is improved and the smoothness and curability of the coating film are improved, especially the curability inside the coating film is improved and the corrosion resistance when thickened. In particular, it gives particularly preferable results to coating film performance such as physical properties.

The content of the component (C) is 5 to 200 parts by weight, preferably 10
To 100 parts by weight.

If the content of the component (C) is less than this, smoothness and curability are not sufficiently improved, and practical performance of the coating film cannot be obtained. Further, if it is more than this, water dispersibility is deteriorated.

The above component (C) has the general formula Wherein n has a value between 1 and 5 and R ₇ remains after reaction with a monoalcohol group having from 1 to 8 carbon atoms, or with one or more carboxylic acid groups. It is a polyol group, or a polyamine group, or a group of a polyepoxy compound, or a polyisocyanate group, and R ₈ is a linear or branched alkyl group having 1 to 8 carbon atoms. ] As a preferred example for obtaining the above compound, a diester compound of malonic acid and a monoalcohol such as methanol, ethanol or propanol, a glycol such as glycol, glycerin or trimethylolpropane is used as a diester compound 1 It can be obtained by carrying out a transesterification reaction while mixing moles and hydroxyl groups of the polyol in a proportion of 1 mole and distilling off the alcohol.

Alternatively, a polyamine such as ethylenediamine or hexamethylenediamine may be used in place of the above-mentioned polyol, mixed with the above-mentioned malonic acid diester compound, and the reaction may be carried out while distilling off the alcohol.

Further, as a compound of the component (C) other than the above, it is a non-acidic polyester compound of polycarboxylic acid, and is β-hydroxyl group, β-alkoxyl group, β-ester group, β-amide group, γ-hydroxyl group, γ-ester. Group, a δ-hydroxyl group, and a compound having at least two or more ester groups in one molecule, which are substituted with a substituent consisting of a mixture thereof, and particularly preferable substituents are β-hydroxyl group and β-alkoxyl group. is there.

Examples of suitable polycarboxylic acids or acid anhydrides for obtaining the above compounds include adipic acid, azelaic acid, phthalic acid, fumaric acid, itaconic acid, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, maleic anhydride. , Trimellitic anhydride, etc., and a polycarboxylic acid obtained by reacting a part of the carboxyl group of the above acid with a polyol having a functionality of 2 or more, such as adipic acid and trimethylolpropane 3: 1. In order to obtain an ester substituted with a β-hydroxyl group, such as those reacted in a molar ratio, 1-
It can be obtained by esterifying a monoepoxide such as 2 epoxybutane, propylene oxide and glycidyl versatate, or a 1-2 glycol such as ethylene glycol and propylene glycol.

In order to obtain an ester substituted with a β-alkoxyl group, it can be obtained by subjecting the above polycarboxylic acid to an esterification reaction with 1,2-glycol monoether such as ethyl cellosolve, butyl cellosolve phenyl cellosolve, methyl cellosolve and isopropyl cellosolve. Component (A), component (A), component (A), component (B) and component (C) in order to be water-soluble or water-dispersible in the present invention.
(B) and component (C) are mixed in advance, and then 0.1 to 2.0, preferably 0.2 to 1.0 molar equivalents of formic acid, acetic acid, propionic acid, water-soluble organic acid such as lactic acid relative to the amino group of component (A) It is preferable to neutralize with and water-solubilize.

In dissolving or dispersing the composition (A), (B) and (C) of the present invention in water, it facilitates dissolution or decomposition, improves the stability of the aqueous solution, improves the fluidity of the resin, the coating film For the purpose of improving the smoothness of the composition, ethyl cellosolve, propyl cellosolve, butyl cellosolve, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diacetone alcohol, 4-methoxy-4-methyl, which is water-soluble and can dissolve each resin composition. It is preferable to use 10 to 100 parts by weight of an organic solvent such as pentanone-2 and methyl ethyl ketone per 100 parts by weight of each resin composition.

The cathodic deposition type electrodeposition coating composition of the present invention may further contain a metal or a salt or complex of lead, zinc, iron, tin, manganese or cobalt as a curing catalyst.

Suitable examples include lead octylate, lead naphthenate, zinc octylate, manganese acetate, manganese lactate, cobalt acetate, cobalt lactate and the like.

The cathodic deposition type electrodeposition coating composition of the present invention may be further blended with a suitable pigment, for example, iron oxide, lead oxide, strontium chromate, carbon black, titanium dioxide, talc, aluminum silicate, barium sulfate. One or more can be mixed.

These pigments can be added as they are to the composition of the present invention.However, a large amount of pigment is added to a part of the component (A) which has been neutralized and dispersed or made into an aqueous solution in advance to form a paste-like master batch. The obtained pigment can be added to the composition.

〔Example〕

Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. The physical property tests of the coating films of Examples and Comparative Examples were performed according to JIS-K-5400.

Production Example 1 [Production of Component (A)] Nisseki Polybutadiene B-2000 (number average molecular weight 200)
0, 1.2 bond 65%) is epoxidized with peracetic acid,
Epoxidized polybutadiene (E ₁ ) with an oxirane oxygen content of 6.4% by weight was prepared. After charging 2,000 g of this epoxidized polybutadiene (E ₁ ) and 711.7 g of ethyl cellosolve into a 5 liter autoclave, dimethylamine 140.0
g, and after reacting at 150 ° C. for 5 hours, the unreacted amine was distilled off, and a solution of the amine adduct of polybutadiene (E
A) was produced.

Next, a mixture of 1423.5 g of the above solution (EA), 79.3 g of acrylic acid, 7.6 g of hydroxine and 26.4 g of ethyl cellosolve was added, and the mixture was further reacted at 120 ° C. for 3 hours and 45 minutes to obtain the resin of the component (A) of the present invention. A solution (A ₁ ) was prepared. This had an amine value of 98.1 mmol / 100 g, an acid value of 5.3 mmol / 100 g, and a solid content concentration of 75.0% by weight.

Production Example 2 [Production of Component (A)] Nisseki Polybutadiene B-1800 (number average molecular weight 180
0, 1.2 bond 64%) is epoxidized with peracetic acid,
Epoxidized polybutadiene (E ₂ ) with an oxirane oxygen content of 6.5% by weight was prepared.

1,000 g of this epoxidized polybutadiene (E ₂ ) and 377 g of ethyl cellosolve and 131.
Charge 0g into a 3 liter separable flask and mix at 170 ° C for 6
Reacted for hours.

After the reaction, the mixture was cooled to 120 ° C., a mixture of 81.4 g of acrylic acid, 8.8 g of hydroxin and 27.1 g of ethyl cellosolve was added, and the mixture was reacted at 120 ° C. for 4 hours to prepare a resin solution (A ₂ ) of component A of the present invention. did.

The amine value of this product is 108.1 mmol / 100g, and the acid value is 9.9 mmol /
100 g, and the solid content concentration was 75% by weight.

Production Example 3 [Production of Component (B)] The following compound obtained by reacting bisphenol A with epichlorohydrin in the presence of an alkali catalyst. As a solution, 1,000 g of a bisphenol type epoxy resin having an epoxy equivalent of 950 (trade name Epicoat 1004 manufactured by Yuka Shell Epoxy Co., Ltd.) is dissolved in 342.3 g of ethyl cellosolve, and 72 g of acrylic acid, 10 g of hydroquinone and N,
N dimethylaminoethanol (5 g) was added, the mixture was heated to 120 ° C. and reacted for 3 hours to synthesize a resin solution (B ₁ ) of the component (B) of the present invention.

Production Example 4 [Production of Component (B)] The following compound obtained by reacting bisphenol A with epichlorohydrin in the presence of an alkali catalyst. As a bisphenol type epoxy resin having an epoxy equivalent of 450 (trade name: Epicoat 1001 manufactured by Yuka Shell Epoxy Co., Ltd.), 1,000 g was dissolved in 407 g of MIBK, 211 g of diethanolamine was added, and the mixture was reacted at 100 ° C. for 3 hours, A resin solution (B ₂ ) of component (B) was produced.

The amine value of this product is 129 mmol / 100g, and the solid content concentration is 75.0.
% By weight.

Production Example 5 [Production of Component (C)] Mixing 480 g of malonic acid diethyl ester and 134 g of trimethylolpropane and gradually raising the temperature to 165 ° C. while carrying out the ethanol removal reaction, and then holding until 135 g of ethanol is distilled off. .

Next, after raising the degree of vacuum to distill off volatile components, 110 ° C
And add 156 g of ethyl cellosolve to obtain a solid concentration of 7
5% of the resin solution (C ₁ ) of the component (C) of the present invention was produced Production Example 6 [Production of component (C)] 129 g of trimellitic anhydride and glycidyl ester of versatic acid (cardura E-10 oiled shell) Co., Ltd.] 50
0 g was mixed and heated to 90 ° C. The evaporation reaction started and the temperature rose to 180 ° C. The mixture was cooled to 140 ° C., 2 g of benzyldimethylamine as a catalyst was added, and the reaction was carried out at 140 ° C. for 4 hours. The acid value at this time was 2 mmol / 100 g. The reaction product was cooled to 130 ° C. and 922 g of ethyl cellosolve was added to prepare a resin solution (C ₂ ) of the component (C) of the present invention having a solid content concentration of 75%.

Production Example 7 [Production of Component (C)] Adipic acid 438g Trimethylolpropane 134g Butylcellosolve 354g Dimethylbenzylamine 3g as a catalyst was added, and the reaction was carried out at 190 ° C for 6 hours while dehydration was performed.

The acid value at this time was 2.5 mmol / 100 g. This reaction 1
After cooling to 30 ° C., 269 g of ethyl cellosolve was added, and a resin solution (C ₃ ) of the component (C) of the present invention having a solid concentration of 75%
Was manufactured.

Production Example 8 [Production of Pigment Paste] 31.6 g of acetic acid was added to 1000 g of the solution of the amine adduct of polybutadiene (EA) produced in Production Example 1 to neutralize it, and deionized water was added to prepare a 25% by weight aqueous solution. This aqueous solution 40
0 g, carbon black 10 g, base lead silicate 30 g, titania 110 g, aluminum silicate 100 g and glass beads 50
Put 0 g in a 1 liter stainless beaker and stir vigorously for 2 hours with a high speed rotary mixer, then filter the glass beads,
A pigment paste (pp) having a solid content concentration of 53.8% by weight was prepared.

Example 1 400 g of (A ₁ ) produced in Production Example 1, 200 g of (B ₁ ) produced in Production Example 3 and 200 g of (C ₁ ) produced in Production Example 5 were mixed at 60 ° C. for 1 hour and then homogenized. After cooling to room temperature and adding 6 g of 20% lead octylate and 10.8 g of acetic acid for neutralization, deionized water was added with vigorous stirring to prepare a 25 wt% aqueous solution.

Next, deionized water containing 433 g of the pigment paste (PP) prepared in Preparation Example 8 and 1.0 g of manganese acetate was added to 2400 g of this aqueous solution.
34 g was added and mixed well to prepare an electrodeposition coating solution having a solid content of 20% by weight.

Using the above electrodeposition coating solution as a carbon electrode as an anode, zinc phosphate treated plate (Japan Test Panel Co., Bt3004, 0.8 × 70 ×
Cathode deposition type electrodeposition coating was performed with 150 mm) as the cathode. The test results are shown in Table-1.

Example 2 500 g of (A ₁ ) produced in Production Example 1, 200 g of (B ₂ ) produced in Production Example 4 and 100 g of (C ₂ ) produced in Production Example 6 were treated at 60 ° C.
After 1 hour of mixing and homogenizing, the mixture was cooled to room temperature, neutralized by adding 20% zinc octylate (3 g) and acetic acid (10.8 g), and deionized water was added with vigorous stirring to prepare a 25% by weight aqueous solution.

Using 2400 g of this aqueous solution, an electrodeposition coating solution was prepared under exactly the same conditions as in Example 1 and tested under the same conditions as in Example 1 and the results are shown in Table 1.

Comparative Example 1 600 g of (A ₁ ) produced in Production Example 1 and 300 g of (B ₁ ) produced in Production Example 3 were mixed at 60 ° C. for 1 hour to homogenize, then cooled to room temperature and neutralized with 12.2 g of acetic acid. After that, deionized water was added with vigorous stirring to prepare a 25 wt% aqueous solution.

Next, to 2400 g of this aqueous solution, 433 g of the pigment paste (PP) prepared in Preparation Example 8 and 1.0 g of manganese acetate were added 1734 g of deionized water.
Was added and mixed well to prepare a 20% by weight electrodeposition coating solution.

Using the above electrodeposition coating liquid as a carbon electrode as an anode, zinc phosphate treated plate (Japan test panel, Bt3004, 0.8 × 70 × 15
(0 mm) was used as a cathode, and cathodic deposition type electrodeposition coating was performed. The test results are shown in Table-1.

Comparative Example 1 is an example of the case where the C component (C ₁ ) of Example ₁ is not present.

Example 3 500 g of (A ₂ ) produced in Production Example 2 and 300 g of (B ₂ ) produced in Production Example 4 were mixed with 200 g of (C ₃ ) produced in Production Example 7 and mixed uniformly at 80 ° C. for 30 minutes. After that, cool to room temperature 20
% After adding 6 g of lead octylate and 18 g of acetic acid for neutralization, deionized water was added with vigorous stirring to obtain a solid content of 25
A wt% aqueous solution was prepared.

Next, to 2400 g of this aqueous solution, 346 g of the pigment paste (PP) prepared in Preparation Example 8 and 1.5 g of cobalt acetate were added deionized water.
1631 g was added and mixed well to prepare an electrodeposition coating solution having a solid content concentration of 18% by weight.

Using the above electrodeposition coating solution as a carbon electrode as an anode, zinc phosphate treated plate (Japan Test Panel Co., Bt3004, 0.8 × 70 ×
(160 mm) was used as a cathode, and cathodic deposition type electrodeposition coating was performed.

The test results are shown in Table-2.

Comparative Example 2 500 g of (A ₂ ) produced in Production Example 2 and 300 g of (B ₂ ) produced in Production Example 4 were mixed at 80 ° C. for 1 hour, cooled to room temperature and neutralized by adding 14.4 g of acetic acid. Deionized water was added with vigorous stirring to prepare an aqueous solution having a solid content concentration of 25% by weight.

Using 2400 g of this aqueous solution, an electrodeposition coating solution was prepared under exactly the same conditions as in Example 2 and tested under the same conditions as in Example 2 and the results are shown in Table 2.

This Comparative Example 2 is an example of the case where the C component (C ₂ ) of Example 3 is not present.

[Effects of the Invention] The composition of the present invention is low temperature curable, has excellent smoothness and corrosion resistance of the coating surface, and can be formed into a thick film as compared with the conventional cathodic deposition type electrodeposition coating composition, and can be used in the automobile industry and all other fields. It can be preferably used in the industrial field.

Claims (3)

[Claims] 1. A) (a) 5 with a molecular weight of 500 to 5000
A polymer compound having a carbon-carbon double bond having an iodine value of 0 to 500 and 0.5 to 12% by weight of oxirane oxygen. (B) General formula of 30 to 300 mmol per 100 g of the polymer compound [In the formula, R ₁ and R ₂ represent a hydrocarbon having 1 to 20 carbon atoms, a part of which may be substituted with a hydroxyl group, provided that R ₁ and R ₂ may have a ring structure, The structure may contain unsaturated groups. ] The amine compound represented by
General formula of 0-200 mmol per g [In the formula, R ₃ and R ₄ represent a hydrogen atom or a methyl group. ] 100 parts by weight of a reaction product of an α, β unsaturated carboxylic acid represented by 2. (B) General formula [Wherein R ₅ and R ₆ are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, n is an integer of 0 to 20], and substantially all the epoxy groups of the epoxy resin represented by the general formula An amine compound represented by [the same as (b) above] and /
Or general formula 0 to 150 parts by weight of a product reacted with an α, β unsaturated carboxylic acid represented by [the same as (c) above]. 3. A non-acidic polyester compound of (C) a polycarboxylic acid, which has an ester group which can be crosslinked and cured by a transesterification reaction with a hydroxyl group in the components (A) and (B) when the coating film is heated by heat. Cathode deposition type electrodeposition coating composition obtained by partially neutralizing a mixture of 5 to 200 parts by weight of a compound containing 2 or more compounds in the molecule with an organic acid and diluting with water