JPH027338B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a cathodically deposited electrodeposition coating composition having 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 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 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 applied for a patent (JP-A-51-119727, JP-A-52
−147638, Japanese Patent Publication No. 53-16048). Cathode-deposited electrodeposition coating compositions containing the above-mentioned resins as coating film components are cured mainly through oxidative polymerization of unsaturated groups contained in the resins, and provide coatings with excellent performance. 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 carbon-carbon double bonds and sulfonic acid The present inventors have discovered that the baking temperature can be further lowered by adding an oil-soluble manganese salt of a polymer compound having a succinic acid group or a succinic acid group. 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. 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
Carbon-carbon double bonds with an iodine value of 50 to 500 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 represents a hydrocarbon group having 1 to 20 carbon atoms, in which a hydrogen atom or a portion thereof may be substituted with a hydroxyl group. ) 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 a hydrogen atom or a carbon number of 1 to
10 alkyl groups, 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 a hydrogen atom when m is 0, and Y when m is 1] or the following general formula (b′) [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. ] 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, 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 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. 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 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

The compound (B) converted into [Formula] is used as a component of the cathodic deposition type electrodeposition paint, and the resin,
(A), whereby the resin (A)
It is truly surprising that it has been found that it is possible to significantly improve the corrosion resistance of . Carbon-carbon double bonds of component (C) with a molecular weight of 300 to 3000 and an iodine number of 50 to 500 and 30 to 300 per 100 g
0.2 to 20 millimoles of oil-soluble manganese salt of a polymer compound having sulfonic acid groups or succinic acid groups.
By adding part by weight, curing properties are significantly accelerated, and a low-temperature curable cathodically deposited electrodeposition coating material can be obtained. 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 aqueous manganese salts, 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. In addition, since the manganese salt of the weak acid mentioned above does not substantially have unsaturated groups, it does not co-cure with the resin of component (A) or component (B), which causes a decrease in the performance of the baked coating film such as solvent resistance. It also becomes. Since the manganese salt of oil-soluble sulfonic acid or the manganese salt of succinic acid used in the present invention is a salt of a strong acid, it does not cause an exchange reaction with the neutralizing agent such as acetic acid, and since it has an unsaturated group, the component (A ) or co-cures with component (B) during baking, so it can be used without causing the above problems. (C) component used in the present invention, i.e. 300 to 3000
An oil-soluble manganese salt of a high molecular weight compound having a carbon-carbon double bond with a molecular weight of 50 to 500 and an iodine number of 30 to 30 mmol per 100 g of sulfonic acid or succinic acid groups is produced by a conventionally known method. . For example, after sulfonating or maleating the conjugated diolefin low polymer or co-low polymer used as the starting material for component (A) of the present invention, the sodium salt of these acid groups is combined with manganese sulfate, manganese chloride, etc. It is easily produced by a so-called double decomposition method using a salt exchange reaction or an acid exchange reaction with a manganese salt of a weak acid such as acetylacetomanganese, 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 composition (a) or (c) of the present invention and dissolving or dispersing it in water, it facilitates dissolution or dispersion, improves the stability of the aqueous solution, improves the fluidity of the resin, and improves the coating film. Ethyl cellosolve, propyl cellosolve, butyl cellosolve, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diacetone alcohol, 4-methoxy-4-, which are water-soluble and can dissolve each resin composition, are used for purposes such as improving the smoothness of the resin composition.
Organic solvents such as methylpentanone-2 and methyl ethyl ketone are added in an amount of 10 to 100 parts per 100 parts by weight of each resin composition.
Preferably, parts by weight are used. 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-2000 (number average molecular weight
2000, 1.2 bond 65%) was epoxidized using peracetic acid to produce epoxidized polybutadiene (E ₁ ) with an oxirane oxygen content of 6.3%. 1076g of this epoxidized polybutadiene (E ¹ )
After charging 108g of ethyl cellosolve into two autoclaves, add 40g of dimethylamine,
The reaction was carried out at 150°C for 5 hours. After distilling off the unreacted amine, a mixture of 95 g of acrylic acid, 8 g of hydroquinone and 260 g of ethyl cellosolve was added,
Further, the reaction was carried out at 150° C. for 45 minutes to produce a resin solution (A ₁ ) of component (A) of the present invention. The amine value of this product is 50 mmol/100g, and the acid value is 5 mmol/100g.
The solid content concentration was 75.0% by weight. Production example 2 Nisseki polybutadiene B-1500 (number average molecular weight
1500, 1.2 bond 63%) 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, 368 g of ethyl cellosolve and 105 g of diethanolamine were charged into 3 separable flasks and reacted at 150°C for 6 hours. After the reaction, cool to 120℃ and add 79g of acrylic acid and 7.3g of hydroquinone.
Add a mixture of and 26g of ethyl cellosolve,
A resin solution (A ₃ ) of component (A) of the present invention was prepared by reacting at 120° C. for 8 hours. The amine value of this product was 62 mmol/100 g, the acid value was 12 mmol/100 g, and the solid content concentration was 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, 803 g of maleated polybutadiene (M ₁ ),
156g of butyl cellosolve was added to the 2 tubes equipped with a reflux condenser.
The mixture was placed in a separable flask and heated to 80°C with stirring. Next, 78g of dimethylaminopropylamine
was added dropwise, and then 23 g of monoethanolamine was added dropwise. Immediately after the dropwise addition was completed, the temperature was raised to 150°C and the reaction was continued at 150°C for 4 hours. water produced under reduced pressure,
Butyl cellosolve and unreacted amine are distilled off,
Imidized polybutadiene having tertiary amine groups and hydroxyl groups was synthesized. The amine value of this imidized polybutadiene was 89 mmol/100 g.
This imidized polybutadiene has a solid content of 80% by weight.
A resin solution (A ₃ ) of the component (A) of the present invention was prepared by dissolving it in ethyl cellosolve so that the following was obtained. 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 Production Example 4.
An ethyl cellosolve solution (B ₂ ) of the epoxy resin-methacrylic acid adduct (B) was synthesized. Production example 6 Nisseki polybutadiene B-700 (number average molecular weight 700,
1.2 bond 52%) 1000g, maleic anhydride 117.3g,
1 g of Antigen 3C and 10 g of xylene were charged into a two-separable flask equipped with a reflux condenser and reacted at 195° 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 ₂ ) having an acid value of 107 mmol/100 g. 500 g of maleated polybutadiene (M ₂ ) and 148 g of ethyl cellosolve were reacted at 120°C for 2 hours to open the succinic anhydride groups, and then cooled to room temperature.
After neutralizing by gradually adding 100 g of a 22.5% by weight aqueous solution of caustic soda, deionized water was added so that the solid content concentration was 25% by weight to prepare an aqueous solution of maleated polybutadiene. Next, 74.5g of manganese sulfate (MnSO ₄ H ₂ O _4.5 )
After dissolving in 600g of water, add isopropyl alcohol.
600g and 1000g of benzene were added, and 2192g of the above maleated polybutadiene aqueous solution was prepared at room temperature while stirring.
was gradually added dropwise, heated to 60°C for 30 minutes after dropping, and left to stand for 1 hour. It separated into two layers, so the lower layer was cut off, 1000g of deionized water was added, heated to 60°C for 30 minutes, and left to stand for 1 hour. The lower layer was removed. The upper layer was taken out and benzene etc. were distilled off under reduced pressure to produce manganese salt of maleated polybutadiene by double decomposition method. This manganese salt of maleated polybutadiene was dissolved in ethyl cellosolve so that the solid content was 75% by weight to produce a solution (C ₁ ) of an oil-soluble manganese salt as component (C) of the present invention. The manganese content of (C ₁ ) was 2% by weight. Production Example 7 1000 g of Nisseki Polybutadiene B-1500, 117.3 g of maleic anhydride, 2 g of Antigen 3C, and 10 g of xylene were charged into a two-separable flask equipped with a reflux condenser and reacted at 195° 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 ₃ ) having an acid value of 107 mmol/100 g. 250 g of maleated polybutadiene (M ₃ ) and 220 g of ethyl cellosolve were placed in a separable flask equipped with a reflux condenser and a Liebig condenser, and reacted at 120°C for 2 hours to open the succinic anhydride groups. Add 175.7g of an aqueous solution containing 46.4g and heat to 120°C.
After ethyl cellosolve was distilled off at normal pressure, the pressure was further reduced to remove acetic acid and ethyl cellosolve, and a manganese salt of maleated polybutadiene was produced by an acid exchange method. This manganese salt of maleated polybutadiene was dissolved in ethyl cellosolve so that the solid content was 75% by weight to produce a solution (C ₂ ) of oil-soluble manganese salt as component (C) of the present invention. The manganese content of (C ₂ ) is
It was 3.6% by weight. Production example 8 Nisseki polybutadiene B-700 was placed in a separable flask equipped with a reflux condenser and a dropping funnel.
Collect 100g and add 1200ml of dehydrated dichloroethane to it.
was added to dissolve and cooled to 5°C. While maintaining the temperature at 5℃, add 11.4g of SO ₃ and 100g of dehydrated dichloroethane.
A SO ₃ dioxane (1:1) complex synthesized from 12.6 g of dehydrated 1,4 dioxane dissolved in 1 mL of the solution was added dropwise over 60 minutes under a nitrogen stream. After the dropwise addition was completed, the mixture was aged at the same temperature for 30 minutes to synthesize a solution of sulfonated polybutadiene (S ₁ ). Next, while 9.1 g of MnCO ₃ and 18.2 g of water were being vigorously stirred, the aged solution of (S ₁ ) was added dropwise to the second separable flask under a nitrogen stream over 5 minutes. After the dropwise addition was completed, the mixture was heated to 60°C for 30 minutes to complete hydrolysis. By distilling off the solvent from the reaction solution, a brown semisolid manganese salt of sulfonated polybutadiene was produced by acid exchange reaction. This manganese salt of sulfonated polybutadiene was dissolved in ethyl cellosolve so that the solid content was 75% by weight to produce a solution (C ₃ ) of oil-soluble manganese salt as component (C) of the present invention. The manganese content of (C ₃ ) is
It was 2.8% by weight. Example 1 400 g of A ₁ produced in Production Example 1, 10.8.4 g of B ₁ produced in Production Example 4, and 45 g of C ₁ produced in Production Example 6
After mixing until homogeneous, 6 g of acetic acid 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 0.9 g of manganese acetate was added in place of C ₁ produced in Production Example 6, under the same conditions as in Example 1. The test was conducted under the following conditions and the results are shown in Table 1.

[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 16.7 g of C ₂ produced in Production Example 7 until uniform, 7.4 g of acetic acid was added and the mixture was thoroughly mixed. Stir it to neutralize it. 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 2.5
g, 25 g of basic lead silicate and 1000 g of glass beads
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 in the same manner as in Example 2, except that 0.6 g of manganese acetate was added instead of C ₂ produced in Production Example 7, under the same conditions as in Example 2. The test was conducted under the following conditions and the results are shown in Table 2.

[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 30 g of C ₃ produced in Production Example 8
After mixing until homogeneous, 10 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 exactly 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 in the same manner as in Example 3, except that 0.84 g of manganese acetate was added in place of C ₃ produced in Production Example 8. The test was conducted under the following conditions and the results are shown in Table 3.

【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 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. ] Compound 3 to 100 parts by weight (C) A polymer having a molecular weight of 300 to 3,000 and an iodine value of 50 to 500, a carbon-carbon double bond, and 30 to 300 mmol of sulfonic acid group or succinic acid group per 100 g. A cathodically deposited electrodeposition coating composition with excellent low temperature curability, comprising 0.2 to 20 parts by weight of a molecular compound manganese salt.