JPH0238140B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a cathodically deposited electrodeposition coating composition having excellent low-temperature curability. Some resins having basic groups form cationic resins in water, and when electrodeposition coating is performed using these resins, the resins are deposited on the cathode. This type of cathodic deposition type paint neutralizes the base of resin with acid groups,
It is possible to eliminate the essential drawbacks of conventional water-soluble anodic deposition type 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 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 discovered a method of curing highly reactive acrylic (methacrylic) double bonds at a relatively low baking temperature by introducing a resin therein and filed a patent application (Japanese Patent Laid-Open No. 151777/1983).
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 saving, and as a result of various studies, the present inventors have found that by introducing a carbon-carbon conjugated double bond into the compound of component (A), the baking temperature can be further lowered. The present invention was achieved by discovering that it is possible to reduce the SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a cathodically deposited electrodeposition coating material having improved resin curability and low temperature curability and excellent corrosion resistance. That is, the present invention provides: (A)(1) A polymer compound having a molecular weight of 500 to 5000 and an iodine value of 50 to 500 and having 3 to 12% by weight of oxirane oxygen and a carbon-carbon double bond (2) The above (1) General formula of 30-300 mmol per 100 g of polymer compound [In the formula, R ₁ and R ₂ represent a hydrocarbon having 1 to 20 carbon atoms which may be partially substituted with a hydroxyl group; however, R ₁ and R ₂ can have a ring structure; Some of them may contain unsaturated groups. ] An amine compound represented by (3) 0 to 200 mmol of the general formula per 100 g of the polymer compound of (1) above [In the formula, R ₃ and R ₄ represent a hydrogen atom or a methyl group. ] α, β unsaturated carboxylic acid represented by (4) 20 to 50 per 100 g of the polymer compound of formula (1)
100 parts by weight of a reaction product of millimoles of unsaturated fatty acids with a molecular weight of 100 to 350 and containing 10% by weight or more of carbon-carbon conjugated double bonds (B) General formula [In the formula, R ₅ and R ₆ are hydrogen atoms or methyl groups, and n represents an integer of 0 to 20, preferably 1 to 10.] formula [In the formula, R ₇ and R ₈ represent a hydrogen atom or a methyl group. ] 10 to 200 parts by weight of a product obtained by reacting with an α,β unsaturated carboxylic acid represented by (C) Contains 0.005 to 1.0 parts by weight of a manganese salt of an organic acid or manganese dioxide (as a metal amount) as an essential component A cathode-deposited electrodeposition coating composition with excellent low-temperature curability, which is a starting material for component (A) of the present invention, has a carbon-carbon double bond with a molecular weight of 500 to 5,000 and an iodine value of 50 to 500. Molecular compounds are produced by conventionally known methods. 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,
Alternatively, an aromatic vinyl monomer, such as styrene, in an amount of 50 mol% or more 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 a low gel content, an organic alkali metal compound such as sodium benzyl is used as a catalyst, and a compound having an alkylaryl group,
For example, a chain transfer polymerization method using toluene as a chain transfer agent (US Pat. No. 3,789,090) or a living polymerization method using a polycyclic aromatic compound such as naphthalene as an activator and an alkali metal such as sodium as a catalyst in a tetrahydrofuran solvent. Legal (Tokuko Showa 42-
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 is obtained by epoxidizing the unsaturated compound using a peroxide such as hydrogen peroxide or peracid by a known method to introduce 3 to 12% by weight of oxirane oxygen groups as oxygen, and then forming a compound of the general formula [In the formula, R ₁ and R ₂ are the same as above] The amine compound represented by the formula is reacted at a temperature of 50 to 200°C in the presence or absence of a solvent, and then a carbon-carbon conjugated double compound with a molecular weight of 100 to 350 is reacted. join 10
It is produced by reacting unsaturated fatty acids containing more than % by weight at 100 to 200°C. At that time, the general formula [In the formula, R ₃ and R ₄ are the same as above] The α,β unsaturated carboxylic acids represented by the following may be reacted together. Examples of amines used in the reaction include aliphatic amines such as dimethylamine and diethylamine;
Examples include alkanolamines such as methyl ethanolamine and diethanolamine, and cyclic amines such as morpholine and piperidine. The amount of amine added depends on the epoxidized polymer compound.
30 to 300 mmol, preferably 50 to 200 mmol per 100 g. 10 carbon-carbon conjugated double bonds with molecular weight 100-350
Examples of unsaturated fatty acids containing more than % by weight include sorbic acid, Chinese tung oil fatty acid, sunflower oil fatty acid, and dehydrated castor oil fatty acid, and soybean oil fatty acid,
Conjugated fatty acids obtained by isomerizing linseed oil fatty acids and the like can also be used, and purified eleostearic acid and conjugated linoleic acid can also be used. Alternatively, a mixture may be used in which an unsaturated fatty acid having 10% by weight or less of carbon-carbon conjugated double bonds is mixed with an unsaturated fatty acid having many conjugated double bonds so that the total amount of conjugated double bonds is 10% by weight or more. be able to. Among them, dehydrated castor oil fatty acids are advantageous and preferred because they are easily available industrially. Examples of α,β unsaturated carboxylic acids include acrylic acid and methacrylic acid. The amount of the unsaturated fatty acid to be added is 50 to 50 as the amount of carboxylic acid per 100 g of the epoxidized polymer compound.
It is used in an amount of 200 mmol, preferably 50 to 150 mmol. The α,β unsaturated carboxylic acid can be used in amounts up to 200 mmol per 100 g of epoxidized polymeric compound. Component (B) of the present invention, that is, general formula [In the formula, R ₅ and R ₆ are hydrogen atoms or methyl groups, n
represents an integer of 0 to 20, preferably 1 to 10] A diglycidyl compound represented by the general formula and substantially 2 mol per molecule of the diglycidyl compound, [In the formula, R ₇ and R ₅ represent a hydrogen atom or a methyl group] When a product obtained by reacting with an α,β unsaturated carboxylic acid represented by the following formula is added, corrosion resistance and hardenability are significantly improved. The content of component (B) is 100 parts by weight of resin (A),
It ranges from 10 to 200 parts by weight, preferably from 30 to 100 parts by weight. If the content of component (B) is less than this, the improvement in corrosion resistance will not be sufficient, 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 methyl groups, n
represents an integer of 0 to 20, preferably 1 to 10] A diglycidyl compound represented by the following is used as a raw material.
This diglycidyl compound can usually be produced by etherifying bisphenol with epichlorohydrin in the presence of an alkali. Such bisphenol compounds include 2,2-
Bis(4'-hydroxyphenyl)propane, 1,
1-bis(4'-hydroxyphenyl)ethane,
These include 1,1-bis(4'-hydroxyphenyl)isobutane and bis(4'-hydroxyphenyl)methane. In many cases, further reaction of the diglycidyl ethers with bisphenols and the like, and then further reaction of this product with epichlorohydrin, yields diglycidyl compounds having somewhat higher molecular weights, which can be used. The general formula of the above diglycidyl compound is [In the formula, R ₇ and R ₈ represent a hydrogen atom or a methyl group] By reacting substantially 2 moles of the α,β unsaturated monocarboxylic acid represented by the following with respect to 1 mole of the diglycidyl compound, the component (B) can be manufactured. Examples of α,β unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, equimolar reaction products of fumaric acid and glycidyl (meth)acrylate, and maleic anhydride and hydroxy (meth)acrylate.
Equimolar reaction products of acrylates are used, and mixtures thereof can also be used. When carrying out the reaction, hydroquinone, methoquinone, N-phenyl,
It is preferable to add 0.01 to 0.1% of a radical polymerization inhibitor such as N'isopropyl-P-phenylenediamine and to use a suitable catalyst such as tertiary amines or quaternary ammonium salts. The reaction can also be carried out in the presence or absence of a solvent, but
When using a solvent, use an appropriate amount of a water-soluble solvent such as ethyl cellosolve, butyl cellosolve, or ethyl cellosolve acetate, which is inert to the reaction and can be used with electrodeposition paints, and do not remove it after the reaction. It is practically advantageous to mix it with component (A) and component (C) and use it in an electrodeposition coating. In the present invention, in the above diglycidyl compound molecule,

[Formula] Substantially all of the group is reacted with α, β unsaturated monocarboxylic acid so that no group remains.

[Formula] Convert to base It is preferable that

[Formula] If a large amount of 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-soluble, causing gelation and resulting in a decrease in viscosity. If it becomes too high, it will interfere with water solubilization. Even if water-solubilization is possible, the aqueous solution changes over time, resulting in disadvantages such as constant electrodeposition characteristics or failure 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 a carbon-carbon double bond, 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 diglycidyl 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 the resin (A) and forming a coating film. It is truly surprising that it has been found that its corrosion resistance can be significantly improved without any loss in properties. Component (C) of the present invention, that is, a manganese salt of an organic acid, includes water-soluble manganese salts such as manganese formate, manganese acetate, manganese lactate, manganese naphthenate, manganese octylate, and the general formula [In the formula, R ₁₀ and R ₁₁ are a hydrogen atom or a carbon number of 1 to
20 alkyl groups, with R ₁₀ and R ₁₁
can each have a 6-membered ring structure or a heterocyclic structure containing a 5-membered ring and a 6-membered ring, and the ring structure can contain an unsaturated group. R ₁₂ is an ether bond having 1 to 20 carbon atoms. , represents an organic residue which may contain 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 0.005 to 1.0 parts by weight of a metal amount of an oil-soluble manganese salt of a monoester of a 1,2 dicarboxylic acid or manganese dioxide shown in A type electrodeposition paint is obtained. If the amount of organic acid manganese salt or manganese dioxide (component (C) of the present invention) is less than 0.005 part by weight as a metal amount, the effect of promoting curability will be small, and if it is more than 1.0 part by weight, curability will be good. However, it is not preferable because it lowers water dispersibility, corrosion resistance, etc. The preferred range is 0.01 to 0.01 in terms of metal content.
It is 0.5 part 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 dissolving or dispersing the compositions (A), (B) and (C) of the present invention 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. For purposes such as improving the smoothness of
Organic solvents such as ethyl cellosolve, propyl cellosolve, butyl cellosolve, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diacetone alcohol, 4-methoxy-4-methylpentanone-2, and methyl ethyl ketone, which are water-soluble and can dissolve each resin composition, are used. It is preferable to use 10 to 100 parts by weight per 100 parts by weight of each resin composition. 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 incorporated. 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 dispersed or made into an aqueous solution in neutralized water and mixed to form a paste-like masterbatch. It is also possible to add this pasty pigment 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 6.4%. After charging 1000 g of this epoxidized polybutadiene (E ₁ ) and 333 g of ethyl cellosolve into two autoclaves, 70.9 g of dimethylamine was added and
The reaction was carried out at ℃ for 5 hours. After distilling off unreacted amine, 36g of acrylic acid, 140g of eleostearic acid,
Hydroquinone 7.5g and ethyl cellosolve
73.9 g of the mixture was added and further reacted 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 90.0 mmol/
100g, acid value was 7.8 mmol/100g, and solid content concentration was 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%. 1000 g of this epoxidized polybutadiene (E ₂ ), 358 g of ethyl cellosolve, and 75.1 g of methylethanolamine were charged into three separable flasks and reacted at 150° C. for 6 hours. After the reaction, it was cooled to 120°C, and 18.0 g of acrylic acid, 210.0 g of highly conjugated linoleic acid [trade name Hydien, manufactured by Soken Kagaku Co., Ltd.], 7.2 g of hydroquinone, and 69.2 g of ethyl cellosolve were added.
A mixture of the following was added and reacted at 120° C. for 4 hours to produce a resin solution (A ₂ ) of component A of the present invention. The amine value of this product was 57.6 mmol/100g, the acid value was 9.9 mmol/100g, and the solid content concentration was 75% by weight. Production example 3 Nisseki polybutadiene B-2000, (number average molecular weight
2000, 1,2 bonds 65%) 1000g, maleic anhydride
168 g of xylene, 10 g of xylene, and 2 g of Antigen 3C (trade name of Sumitomo Chemical) 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, and the acid value was 143 mmol/100 g.
A maleated polybutadiene (M ₁ ) was synthesized. Next, 1000 g of maleated polyptadiene (M ₁ ),
200g of ethyl cellosolve with a reflux condenser
The mixture was placed in a separable flask and heated to 80°C with stirring. Next, 146 g of N,N dimethylaminopropylamine 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 5 hours. Water, ethyl cellosolve and unreacted amine were distilled off under reduced pressure to synthesize imidized polybutadiene having tertiary amine groups. The amine value of this imidized polybutadiene was 132 mmol/100 g.
This imidized polybutadiene has a solid content of 75% by weight.
A resin solution (A ₃ ) of component (A) used in the comparative example of the present invention was prepared by dissolving it in ethyl cellosolve so as to have the following properties. Production example 4 Nisseki polybutadiene B-1800 (number average molecular weight
1800, 1.2 bonds (64%) was epoxidized using peracetic acid to produce epoxidized polybutadiene (E ₃ ) with an oxirane oxygen content of 6.4%. 1000 g of this epoxidized polybutadiene (E ₃ ), 358 g of ethyl cellosolve, and 75.1 g of methylethanolamine were charged into three separable flasks and reacted at 150° C. for 6 hours. After the reaction, cool to 120℃ and add 79.2g of acrylic acid and hydroquinone.
Add a mixture of 7.2g and 10g ethyl cellosolve;
A resin solution (A ₄ ) of component (A) used in a comparative example of the present invention was prepared by reacting at 120° C. for 4 hours. This product had an amine value of 65.4 gmmol/100g, an acid value of 10.0 mmol/100g, and a solid content concentration of 75% by weight. Production Example 5 The following compound obtained by reacting bisphenol A and epichlorohydrin in the presence of an alkali catalyst As, 1000 g of bisphenol type epoxy resin with an epoxy equivalent of 955 [trade name Epicote 1004 manufactured by Yuka Ciel Epoxy Co., Ltd.] was added to ethyl cellosolve.
336.7g, added 79.2g of acrylic acid, 12g of hydroquinone and 6g of N,N dimethylaminoethanol, heated to 100°C and reacted for 5 hours,
An ethyl cellosolve solution (B ₁ ) of an epoxy resin-acrylic acid adduct, which is a component used in Examples and Comparative Examples of the present invention, was synthesized. Production Example 6 The following compound obtained by reacting bisphenol A and epichlorohydrin in the presence of an alkali catalyst As, 1000 g of bisphenol type epoxy resin with an epoxy equivalent of 485 [trade name Epicote 1001 manufactured by Yuka Ciel Epoxy Co., Ltd.] was added to ethyl cellosolve.
Dissolve 156 g of acrylic acid, 10 g of hydroquinone and N,N dimethylaminoethanol in
5g was added, heated to 100°C and reacted for 5 hours, and the epoxy resin of the component used in the comparative example of the present invention -
Ethyl cellosolve solution of acrylic acid adduct (B ₂ )
was synthesized. Production example 7 Nisseki polybutadiene B-500 (number average molecular weight 500,
1000 g of 1.2 bond (51%), 117.3 g of maleic anhydride, 1 g of Antigen 3C, and 10 g of xylene were placed in 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 group, 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, dissolve 74.5 g of manganese sulfate (MnSO ₄ 4.5H ₂ O) in 600 g of water, and then add isopropyl alcohol.
600g and 1000g of benzene were added, and while stirring, 2192g of the aqueous maleated polybutadiene solution was gradually added dropwise at room temperature. After the dropwise addition, the mixture was heated to 60°C for 30 minutes and then allowed to stand for 1 hour. As a result, the lower layer was separated into two layers. After adding 1000g of deionized water and heating at 60°C for 30 minutes, the mixture was allowed to stand for 1 hour and the lower layer was removed. The upper layer was taken out and benzene etc. were distilled off under reduced pressure to produce a manganese salt of maleated polybutadiene by a reverse 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. Example 1 400 g of (A ₁ ) produced in Production Example 1, 240 g of (B ₁ ) produced in Production Example 5, and 25 g of butyl cellosolve were mixed until homogeneous, and then 8.6 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 25% by weight. 1000g of this 25% by weight aqueous solution, 2.5g of carbon black, 25g of basic lead silicate and glass beads.
After putting 1000 g into a stainless steel beaker and stirring vigorously for 2 hours with a high-speed rotating mixer, the glass beads were filtered and deionized water was added to make the solid content concentration 18% to prepare an electrodeposition coating solution. Using the above electrodeposition coating 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 a cathode for cathodic deposition electrodeposition coating. The test results are shown in Table-1. Comparative Example 1 Production Example 3 was used instead of (A ₁ ) produced in Production Example 1.
All procedures were carried out in Example 1 except for using (A ₃ ) produced in Example 1.
A cathode-deposited electrodeposition coating solution was prepared under exactly the same conditions as in Example 1, and a test was conducted under the same conditions as in Example 1. The results are shown in Table 1.

【table】

[Table] Example 2 After mixing 400 g of (A ₂ ) produced in Production Example 2, 120 g of (B ₂ ) produced in Production Example 6, and 19.5 g of (C ₁ ) produced in Production Example 7 until uniform. , acetic acid
6.9g 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, carbon black
4g, basic lead silicate 20g and glass beads 2000g
was placed in a stainless steel beaker and stirred vigorously for 2 hours using a high-speed rotating mixer. After filtering the glass beads, deionized water was added to give a solid content concentration of 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-2. Comparative Example 2 Production Example 4 was used instead of (A ₂ ) produced in Production Example 2.
All procedures were carried out in Example 2 except for using (A ₄ ) produced in Example 2.
A cathode-deposited electrodeposition coating solution was prepared under exactly the same conditions as in Example 2, and a test was conducted under the same conditions as in Example 2. The results are shown in Table 2.

【table】

【table】

【table】

Claims (1)

[Scope of Claims] 1 (A)(1) A polymer compound having a molecular weight of 500 to 5,000 and an iodine value of 50 to 500 and having a carbon-carbon double bond and 3 to 12% by weight of oxirane oxygen (2) The above ( General formula of 30 to 300 mmol per 100 g of the polymer compound of 1) [In the formula, R ₁ and R ₂ represent a hydrocarbon having 1 to 20 carbon atoms which may be partially substituted with a hydroxy group; however, R ₁ and R ₂ can have a ring structure; Some of them may contain unsaturated groups. ] Amine compound represented by (3) 0 to 200 per 100 g of the polymer compound of formula (1) above
General formula for millimoles [In the formula, R ₃ and R ₄ represent a hydrogen atom or a methyl group. ] α, β unsaturated carboxylic acid represented by (4) 200 to 50 per 100 g of the polymer compound of formula (1)
100 parts by weight of a reaction product of an unsaturated fatty acid with a millimole molecular weight of 100 to 350 and containing 10% by weight or more of carbon-carbon conjugated double bonds (B) General formula [In the formula, R ₅ and R ₆ are hydrogen atoms or methyl groups, and n represents an integer of 0 to 20, preferably 1 to 10.] general formula [In the formula, R ₇ and R ₈ represent a hydrogen atom or a methyl group. ] 10 to 200 parts by weight of a product obtained by reacting an α,β unsaturated carboxylic acid represented by (C) A low-temperature product containing 0.005 to 1.0 parts by weight of an organic acid manganese salt or manganese dioxide as an essential component as a metal amount A cathodically deposited electrodeposition coating composition with excellent curability.