JPH027339B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a cathodically deposited electrodeposition coating composition with excellent low-temperature curability. 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 the resin with acid groups with a base,
It is possible to eliminate the essential drawbacks of conventional water-soluble anodic electrodeposition paints, that is, the elution of the metal to be coated into the paint bath and various problems caused by this. The present inventors have conducted research on such cathodic deposition coatings, and have previously introduced amino groups into unsaturated group-containing high molecular weight compounds such as low polymerization degree synthetic polymers having carbon-carbon double bonds, such as liquid polybutadiene. He discovered that a resin for cathodically deposited electrodeposition paints that gave excellent coating properties could be obtained by neutralizing it with an acid, and filed a patent application (Japanese Patent Laid-Open No. 119727,
−147638, Japanese Patent Publication No. 53-16048). Cathode-deposited electrodeposition coating compositions containing the above-mentioned resins as coating components cure mainly through oxidative polymerization of unsaturated groups contained in the resins, and provide coatings with excellent performance, but they do not take a practical curing time. Requires relatively high baking temperatures for hardening. As a result of research on lowering the baking temperature, the present inventors discovered that by adding a metal dryer such as a water-soluble manganese salt, the coating film could be cured at a relatively low baking temperature, and filed a patent application (Japanese Patent Laid-Open No. 53 −142444). In this case, a large amount of dryer is required, which causes problems such as deterioration of electrodeposition coating performance such as throwing power and the tendency for the coated surface to become rough. The present inventors also proposed a method for introducing highly reactive acrylic (methacrylic) double bonds into a resin and curing the resin at a relatively low baking temperature, and filed a patent application (Japanese Patent Application Laid-Open No. 151777-1982).
In this case, when a water-soluble manganese salt is added, a cathodically deposited electrodeposition paint that cures at a relatively low temperature of 160° C. and has excellent performance can be obtained. However, in recent years, there has been a desire to further lower the baking temperature from the perspective of energy conservation, and as a result of various studies, the present inventors found that
The inventors have discovered that the baking temperature can be further lowered by adding an oil-soluble manganese salt of a monoester of 1,2-dicarboxylic acid to a resin having a carbon-carbon double bond and an amino group, thereby achieving the present invention. Therefore, an object of the present invention is to improve the curability of the above-mentioned carbon-carbon double bond and amino group-containing polymer compound to provide a cathodically deposited electrodeposition paint having low temperature curability and excellent corrosion resistance. That is, the present invention comprises: (A) 100 parts by weight of a polymer compound having a molecular weight of 500 to 10,000 and an iodine value of 50 to 500, and an amino group of 30 to 300 mmol per 100 g; [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 the residue of an α,β unsaturated monocarboxylic acid having 3 or 4 carbon atoms, and Y′ is m is 0
When , it is a hydrogen atom, and when m is 1, it is Y.] A compound represented by or the general formula [In the formula, n' is an integer from 0 to 10, R ₇ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and Y represents a residue of an α,β unsaturated monocarboxylic acid having 3 or 4 carbon atoms. ] 3 to 100 parts by weight of a compound represented by (C) General formula [In the formula, R ₁ and R ₂ are a hydrogen atom or a carbon number of 1 to
20 alkyl groups, provided that R ₁ and R ₂ can each have a 6-membered ring structure or a fused ring structure having a 5-membered ring and a 6-membered ring, and the ring structure can also contain an unsaturated group. . R ₃ represents an organic residue having 1 to 20 carbon atoms which may contain an ether bond, an ester bond, and an unsaturated group.
X ₁ and X ₂ represent a hydrogen atom, an organic residue having 1 to 10 carbon atoms, or a bond, and when X ₁ and X ₂ are a bond, the carbons to which X ₁ and X ₂ are attached form a double bond with each other. This is a cathodically deposited electrodeposition coating composition with excellent low temperature curability, which contains as an essential component 0.2 to 20 parts by weight of an oil-soluble manganese salt of a monoester of a 1,2 dicarboxylic acid represented by the following formula. The starting material for component (A) of the present invention, a polymer compound having a carbon-carbon double bond with a molecular weight of 500 to 10,000 and an iodine value of 50 to 500, is produced by a conventionally known method. That is, a conjugated diolefin having 4 to 10 carbon atoms alone or a combination of these diolefins using an alkali metal or an organic alkali metal compound as a catalyst,
or an aromatic vinyl monomer, such as styrene, in an amount of 50 mol% or less based on the conjugated diolefin;
A typical manufacturing method is anionic polymerization or copolymerization of 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 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 (U.S. Patent No. 3789090) or living polymerization method (Japanese Patent Publication No. 1973-1983) 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.
17485, 43-27432) or aromatic hydrocarbons such as toluene or xylene as a solvent, a dispersion of an alkali metal such as sodium as a catalyst, and an ether such as dioxane added to control the molecular weight. Polymerization method (Special Publication No. 32-7446, No. 38)
-1245, No. 34-10188) are suitable manufacturing methods. It is also produced by coordination anionic polymerization using an acetylacetonate compound of a Group 8 metal such as cobalt or nickel and an alkyl aluminum halide (Japanese Patent Publication No. 45-507,
(No. 46-80300) Low polymers can also be used. Component (A) of the present invention, that is, a molecular weight of 500 to 10,000
Iodine number between 50 and 500 with carbon-carbon double bonds and
A polymer compound having 30 to 300 mmol of amino groups per 100 g is produced by a conventionally known method. For example, after adding maleic anhydride to a polymer compound with carbon-carbon double bonds, the general formula [Here, R ₁ is a hydrocarbon group having 1 to 20 carbon atoms,
R ₂ and R ₃ each have 1 to 1 carbon atoms, in which a hydrogen atom or a portion thereof may be substituted with a hydroxyl group.
20 hydrocarbon groups] A method of introducing an amino group by reacting a diamine compound represented by
147638, JP-A-53-8629, JP-A-53-63439) or a method of adding a primary or secondary amine after epoxidizing a polymer compound having a carbon-carbon double bond (JP-A-53-16048, JP-A-53-117030)
etc. are known. Component (B) of the present invention, that is, 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 the residue of an α,β unsaturated monocarboxylic acid having 3 or 4 carbon atoms, and Y′ is m is 0
When , it is a hydrogen atom, and when m is 1, it is Y.] or the following general formula (b') [In the formula, n' is an integer from 0 to 10, _R7 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and Y represents a residue of an α,β unsaturated monocarboxylic acid having 3 or 4 carbon atoms. ] Corrosion resistance is significantly improved by adding the compound. The content of component (B) is 100 parts by weight of resin (A),
It ranges from 3 to 100 parts by weight, preferably from 10 to 50 parts by weight. 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, the general formula [In the formula, R ₅ and R ₆ are hydrogen atoms or 1 carbon atom
-10 alkyl groups, preferably methyl or ethyl groups, 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 glycidyl 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,
etc. 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 0 to 200°C, preferably 50 to 150°C. Examples of unsaturated carboxylic acids having 3 or 4 carbon atoms include acrylic acid, methacrylic acid and crotonic acid, and mixtures thereof can also be used. Appropriate catalysts such as tertiary amines and quaternary ammonium salts can be used for the reaction. In addition, 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 when they can be cured at relatively low temperatures, they have the disadvantage that only a narrow range of baking temperatures can be selected. 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

Compound (B) converted to [Formula] can be used in combination with the resin (A) as a component of cathodic deposition type electrodeposition paint, thereby improving the excellent curability of resin (A). It is truly surprising that it has been found that the corrosion resistance of the coating can be significantly improved without any loss in coating properties. Component (C) of the present invention, that is, general formula [In the formula, R ₁ and R ₂ are hydrogen atoms or carbon atoms 1
~20 alkyl groups, provided that R ₁ and ₂ can each have a 6-membered ring structure or a fused ring structure containing a 5-membered ring and a 6-membered ring, and the ring structure may not contain an unsaturated group. can. R ₃ represents an organic residue having 1 to 20 carbon atoms which may contain an ether bond, an ester bond, and an unsaturated group. X ₁ and X ₂ represent a hydrogen atom, an organic residue having 1 to 10 carbon atoms, or a bond, and when X ₁ and X ₂ are a bond, the carbons to which X ₁ and X ₂ are attached form a double bond with each other. By adding 0.2 to 20 parts by weight of an oil-soluble manganese salt of a monoester of 1,2 dicarboxylic acid represented by It will be done. In general, manganese naphthenate, manganese octenoate, manganese acetylacetonate, etc. are known as oil-soluble manganese salts, but these manganese salts are weak acid manganese salts and can be exchanged with acetic acid as a neutralizing agent in an aqueous solution. A reaction occurs and gradually turns into a water-soluble manganese salt, which impairs the stability of electrodeposition paints. In addition, when water-soluble manganese salts are formed, water-soluble manganese salts increase the conductivity of the electrodeposition coating solution, causing rough skin, or water-soluble manganese salts accelerate curing compared to oil-soluble manganese salts. The use of manganese salts, which are weak acids, is not preferred even if they are oil-soluble, since their effectiveness is small and there are problems such as decreased curing properties. Since the oil-soluble manganese salt of the monoester of 1,2 dicarboxylic acid used in the present invention is a salt of a strong acid, it does not undergo an exchange reaction with the neutralizing agent such as acetic acid.
Since it is oil-soluble, it does not increase the conductivity of the electrodeposition coating liquid, so it can be used without causing the above problems. Component (C) used in the present invention, that is, general formula [In the formula, R ₁ , R ₂ , R ₃ , X ₁ and X ₂ are the same as above] The oil-soluble manganese salt of 1,2 dicarboxylic acid is produced by a conventionally known method. For example, the general expression

【formula】 【formula】

[expression] and

[Formula] [In the formula, R ₁₄ is 1 to 20 ether bonds in carbon,
Represents an organic residue that may contain an ester bond and an unsaturated group, R ₁₅ , R ₁₆ , R ₁₇ and
R ₁₈ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms] The so-called double decomposition method or acetylacetone manganese is a salt exchange reaction between the sodium salt of a monoester of a 1,2 dicarboxylic acid represented by the following formula and manganese sulfate, manganese chloride, etc. It is easily produced by an acid exchange reaction with a manganese salt of a weak acid such as manganese carbonate or manganese acetate. The amount of oil-soluble manganese salt added as component (C) of the present invention is
If it is less than 0.2 parts by weight, the effect of promoting curability is small, and if it is more than 20 parts by weight, curability is good, but water dispersibility, corrosion resistance, etc. are deteriorated, which is not preferable. The preferred range is 1 to 10 parts by weight, and the preferred amount of manganese metal is 0.05 to 0.5 parts by weight. In the present invention, in order to water-solubilize or water-disperse a composition consisting of component (A), component (B), and component (C), component (A), component (B), and component (C) are mixed in advance. After that, 0.1 to 2.0, preferably 0.2 to 1.0 molar equivalents of acetic acid, propionic acid,
It is preferable to neutralize with a water-soluble organic acid such as lactic acid to make it water-soluble. When neutralizing the resin compositions (a), (b) and (c) of the present invention and dissolving or dispersing them in water, the dissolution or dispersion is facilitated, the stability of the aqueous solution is improved, and the fluidity of the resin is improved. However, for the purpose of improving the smoothness of the coating film, ethyl cellosolve, propyl cellosolve, butyl cellosolve, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diacetone alcohol, 4-methoxy, which are water-soluble and can dissolve each resin composition, are used. ―
Organic solvents such as 4-methylpentanone-2 and methyl ethyl ketone were added at 10% per 100 parts by weight of each resin composition.
It is preferred to use ~100 parts by weight. 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 pigments may be added to a portion of component (A) that has been neutralized and dispersed in water or made into an aqueous solution and mixed to form a paste-like masterbatch. This pasty 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. Production example 1 Nisseki polybutadiene B-3000 (number average molecular weight
3000, 1.2 bond 68%) was epoxidized using peracetic acid to produce epoxidized polybutadiene (E ₁ ) having an oxirane oxygen content of 6.2%. 1000g of this epoxidized polybutadiene (E ₁ )
After charging 333g of ethyl cellosolve and 2 autoclaves, 49.7g of dimethylamine was added.
The reaction was carried out at 150°C for 5 hours. After distilling off unreacted amine, 81.9 g of acrylic acid, 7.5 g of hydroquinone
g and 70 g of ethyl cellosolve were added, and the mixture was further reacted at 150°C for 45 minutes to form the components of the present invention.
A resin solution (A ₁ ) of (A) was produced. This product had an amine value of 70 mmol/100g, an acid value of 10 mmol/100g, and a solids concentration of 75.0% by weight. Production example 2 Nisseki polybutadiene B-1800 (number average molecular weight
1800, 1.2 bonds (64%) was epoxidized using peracetic acid to produce epoxidized polybutadiene (E ₂ ) with an oxirane oxygen content of 6.5%. 1000g of this epoxidized polybutadiene (E ₂ )
Then, 358 g of ethyl cellosolve and 75.1 g of methylethanolamine were charged into 3 separable flasks and reacted at 150°C for 6 hours. After reaction, 120℃
Cool to 79.2g of acrylic acid, hydroquinone
A mixture of 7.2 g and 27 g of ethyl cellosolve was added and reacted at 120° C. for 8 hours to produce a resin solution (A ₂ ) of component (A) of the present invention. This product had an amine value of 62 mmol/100g, an acid value of 11 mmol/100g, and a solid content concentration of 75% by weight. Production example 3 Nisseki polybutadiene B-2000 (number average molecular weight
2000, 1.2 bond 65%) 1000g, maleic anhydride 168
g, xylene 10 g, and Antigen 3C (trade name) 2 g were placed in a two-separable flask equipped with a reflux condenser and reacted at 190° C. for 5 hours under a nitrogen stream. Next, unreacted maleic anhydride and xylene were distilled off under reduced pressure to synthesize maleated polybutadiene (M ₁ ) having an acid value of 143 mmol/100 g. Next, 1000 g of maleated polybutadiene (M ₁ ),
200g of ethyl cellosolve in a reflux condenser
The mixture was placed in a separable flask and heated to 80°C with stirring. Next, 149 g of β-hydroxyethylethylenediamine was added dropwise. 150℃ immediately after dropping
The reaction was continued at 150°C for 5 hours. The produced water, ethyl cellosolve and unreacted amine were distilled off under reduced pressure to synthesize imidized polybutadiene having a secondary amine group and a hydroxyl group. The amine value of this imidized polybutadiene is 132 mmol/
It was 100g. This imidized polybutadiene was dissolved in ethyl cellosolve so that the solid content was 75% by weight to produce a resin solution (A ₃ ) of component (A) of the present invention. Production Example 4 The following compound obtained by reacting bisphenol A and epichlorohydrin in the presence of an alkali catalyst As follows, 1000 g of bisphenol type epoxy resin [trade name Epicote 1001 manufactured by Ciel Chemical Co., Ltd.] having an epoxy equivalent of 500 was dissolved in 227 g of ethyl cellosolve, 137 g of acrylic acid, and 0.2 g of hydroquinone.
and 5 g of N,N dimethylaminoethanol were added, heated to 100°C and reacted for 5 hours to synthesize an ethyl cellosolve solution (B ₁ ) of the epoxy resin-acrylic acid adduct, which is the component (B) of the present invention. . Production Example 5 1000 g of a bisphenol type epoxy resin having an epoxy equivalent of 500 [trade name Epicote 1001, manufactured by Ciel Chemical Co., Ltd.] was dissolved in 288 g of ethyl cellosolve, and 164 g of methacrylic acid, 0.2 g of hydroquinone and N,N dimethylaminoethanol were added. The components of the present invention were added under the same reaction conditions as in Production Example 4.
An ethyl cellosolve solution (B ₂ ) of the epoxy resin-methacrylic acid adduct (B) was synthesized. Production example 6 4-methyltetrahydrophthalic anhydride 332.4g
and 286.4 g of 2-ethylhexanol were charged into a 3-separable flask with a bottoming valve and reacted at 120°C for 2 hours to half-esterify the succinic anhydride group, and then cooled to room temperature to form a 25% by weight aqueous solution of caustic soda 334
After neutralization, 1,238 g of an aqueous solution containing 1,000 g of benzene and 238 g of manganese chloride (MnCl ₂ 4H ₂ O) was added, and the mixture was stirred vigorously at room temperature for 1 hour, and then allowed to stand for 2 hours, resulting in separation into two layers. Therefore, the lower layer was cut off, 1000 g of deionized water was added, and the mixture was stirred vigorously at room temperature for 1 hour, then left to stand for 2 hours, and the lower layer was removed. Take out the upper layer and distill off benzene etc. under reduced pressure.

An oil-soluble manganese salt (C ₁ ) of component (C) of the present invention represented by the formula was produced. Production example 7 Maleic anhydride 196g, dodecyl alcohol 409g
g, 20 g of benzene was placed in a 3-separable flask with a bottoming valve and reacted at 125°C for 3 hours to half-esterify maleic anhydride, cooled to room temperature, and gradually added 334 g of a 25% by weight aqueous solution of caustic soda. 1,238 g of an aqueous solution containing 1,000 g of benzene and 238 g of manganese chloride (MnCl ₂ 4H ₂ O)
After stirring vigorously for 1 hour at room temperature, the mixture separated into two layers, so cut off the bottom layer.
1000 g of deionized water was added and the mixture was vigorously stirred at room temperature for 1 hour, then allowed to stand for 2 hours, and the lower layer was removed. Remove the upper layer and distill off benzene etc. under reduced pressure.

An oil-soluble manganese salt (C ₂ ) of component (C) of the present invention represented by the formula was produced. Production Example 8 356.4 g of anhydrous methyl-5-norbornene-2,3 dicarboxylic acid and 198.2 g of ethyl cellosolve were placed in a 3-separable flask with a bottom release valve and reacted at 120°C for 2 hours to half-esterify the succinic anhydride group. After cooling to room temperature, 334 g of a 25% by weight aqueous solution of caustic soda was gradually added to neutralize it, and then 1,268 g of an aqueous solution in which 800 g of benzene and 268 g of manganese sulfate (MnSO ₄ 4H ₂ O) were dissolved were added and stirred vigorously at room temperature for 1 hour. After that, the mixture was left to stand for 2 hours, and the mixture was separated into two layers, so the lower layer was cut off, 1000 g of deionized water was added, and the mixture was vigorously stirred at room temperature for 1 hour, then left to stand for 2 hours, and the lower layer was removed. Take out the upper layer and evaporate it under reduced pressure using benzene etc.

An oil-soluble manganese salt represented by the formula is synthesized, and then dissolved in ethyl cellosolve so that the solid content becomes 75% by weight, and a solution (C ₃ ) of the oil-soluble manganese salt of the component (C) of the present invention is prepared. Manufactured. The manganese content of (C ₃ ) was 7.0% by weight. Example 1 400 g of (A ₁ ) produced in Production Example, 108.4 g of (B ₁ ) produced in Production Example 4, and 18 g of (C ₁ ) produced in Production Example 6 were mixed until homogeneous, and then 8.4 g of acetic acid was mixed.
g was added and thoroughly stirred to neutralize. Next, deionized water was gradually added to prepare an aqueous solution with a solid content concentration of 20% by weight. 2000g of this 20% aqueous solution, 4g of carbon black, 20g of basic lead silicate and 2000 glass beads.
5 g was placed in a stainless steel beaker and stirred vigorously for 2 hours using a high-speed rotating mixer. After passing through glass beads, deionized water was added so that the solid content was 15% by weight to prepare an electrodeposition coating solution. Using the above electrodeposition paint solution, a carbon electrode was used as an anode, and a zinc phosphate treated plate (Japan Test Panel Co., Ltd.,
Bt3004, 0.8 x 70 x 150 mm) was used as the cathode for cathodic deposition electrodeposition coating. The test results are shown in Table-1. Comparative Example 1 A cathode-deposited electrodeposition coating solution was prepared under the same conditions as in Example 1, except that C ₁ produced in Production Example 6 was not added, and a test was conducted under the same conditions as in Example 1. The results are shown below. -1. Comparative Example 2 A cathode-deposited electrodeposition coating solution was prepared in the same manner as in Example 1, except that 1.56 g of manganese acetate was added in place of C ₁ produced in Production Example 6. The test was conducted under the following conditions and the results are shown in Table 1.

【table】

[Table] Example 2 After mixing 400 g of A ₂ produced in Production Example 2, 75 g of B ₂ produced in Production Example 5, and 7.2 g of C ₂ produced in Production Example 7 until uniform, 7.4 g of acetic acid was added. Stir thoroughly to neutralize. Next, deionized water was gradually added to prepare an aqueous solution with a solid content concentration of 25% by weight.
1000g of this 25% aqueous solution, carbon black
2.5g, basic lead silicate 25g and glass beads
1000 g of the mixture was placed in a stainless steel beaker and stirred vigorously for 2 hours using a high-speed rotating mixer. After passing through glass beads, deionized water was added to give a solid content concentration of 18% to prepare an electrodeposition coating solution. Using the above electrodeposition paint solution, a carbon electrode was used as an anode, and a zinc phosphate treated plate (Japan Test Panel Co., Ltd.,
Bt3004, 0.8 x 70 x 150 mm) was used as the cathode for cathodic deposition electrodeposition coating. The test results are shown in Table-2. Comparative Example 3 A cathode-deposited electrodeposition coating solution was prepared under the same conditions as in Example 2, except that C ₂ produced in Production Example 7 was not added, and a test was conducted under the same conditions as in Example 2. The results are shown below. - Shown in 2. Comparative Example 4 A cathode-deposited electrodeposition coating solution was prepared under the same conditions as in Example 2 except that 0.78 g of manganese acetate was added in place of C ₂ produced in Production Example 7. Tests were conducted under similar conditions and the results are shown in Table 2.

【table】

[Table] Example ₃ 400 g of A 3 produced in Production Example 3, 108.4 g of B ₁ produced in Production Example 4, and 17.1 g of C ₃ produced in Production Example 8.
After mixing until homogeneous, 15 g of acetic acid was added and thoroughly stirred to neutralize. Next, deionized water was gradually added to prepare an aqueous solution having a solid content concentration of 30% by weight. 1000g of this 30% aqueous solution, 3g of carbon black, 20g of basic lead silicate and 1000 glass beads.
3 g was placed in a stainless steel beaker and stirred vigorously for 2 hours using a high-speed rotating mixer. After passing through glass beads, deionized water was added to give a solid content concentration of 16% to prepare an electrodeposition coating solution. Using the above electrodeposition coating liquid, a carbon electrode was used as an anode, and a zinc phosphate treated plate (Japan Test Panel,
Bt3004, 0.8 x 70 x 150 mm) was used as the cathode for cathodic deposition electrodeposition coating. The test results are shown in Table-3. Comparative Example 5 A cathode-deposited electrodeposition coating solution was prepared under the same conditions as in Example 2, except that C ₃ produced in Production Example 8 was not added, and a test was conducted under the same conditions as in Example 3. The results are shown below. Shown in 3. Comparative Example 6 A cathode-deposited electrodeposition coating solution was prepared under the same conditions as in Example ₃ , except that 12 g of manganese acetate was added in place of the C3 produced in Production Example 8, and a cathode-deposited electrodeposition coating solution was prepared in the same manner as in Example 3. The test was conducted under various conditions and the results are shown in Table 3.

【table】

【table】

Claims (1)

[Scope of Claims] 1 (A) A carbon-carbon double bond with a molecular weight of 500 to 10,000 and an iodine number of 50 to 500 and 30 to 100 grams per 100 g.
Polymer compound with 300 mmol of amino groups
100 parts by weight (B) General formula [In the formula, R ₅ and R ₆ are hydrogen atoms or 1 carbon number
~10 alkyl group, n is an integer from 0 to 20, m
is 1 or 0, Y is the residue of an α,β unsaturated monocarboxylic acid having 3 or 4 carbon atoms, and Y′ is m is 0
When , it is a hydrogen atom, and when m is 1, it represents Y] A compound represented by, or a general formula [In the formula, n' is an integer from 0 to 10, R ₇ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and Y represents a residue of an α,β unsaturated monocarboxylic acid having 3 or 4 carbon atoms. ] Compound 3 to 100 parts by weight (C) General formula [In the formula, R ₁ and R ₂ are hydrogen atoms or carbon atoms 1
~20 alkyl groups, with R ₁ and
R ₂ can each have a 6-membered ring structure or a condensed ring structure having a 5-membered ring and a 6-membered ring, and the ring structure can also contain an unsaturated group. R ₃ represents an organic residue having 1 to 20 carbon atoms which may contain an ether bond, an ester bond, and an unsaturated group. X ₁ and X ₂ represent a hydrogen atom, an organic residue having 1 to 10 carbon atoms, or a bond, and when X ₁ and X ₂ are a bond, the carbons to which X ₁ and X ₂ are attached form a double bond with each other. A cathodically deposited electrodeposition coating composition with excellent low temperature curability, which contains as an essential component 0.2 to 20 parts by weight of an oil-soluble manganese salt of a monoester of a 1,2 dicarboxylic acid represented by the following formula.