JPH0637595B2 - Cathode electrodeposition coating composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a cathodic deposition type electrodeposition coating composition having excellent low temperature curability.

Problems to be Solved by the Prior Art and Invention Some resins having a basic group generate a cationic resin in water, and when electrodeposition coating is performed using this, the resin is deposited on the cathode. This type of cathodic deposition type coating is an essential drawback of the conventional, anodic deposition type electrodeposition coating which is made water-soluble by neutralizing a resin having an acid group with a base, that is, an object to be coated on a coating bath. Elution of metal and various problems caused by it can be solved.

The present inventors have studied such a cathodic deposition type coating,
A low degree of polymerization synthetic polymer having a carbon-carbon double bond before,
For example, it was found that a resin for cathodic deposition type electrodeposition coating which gives excellent coating properties can be obtained by introducing an amino group into an unsaturated group-containing high molecular weight compound such as liquid polyptadiene and neutralizing with an acid, and applied for a patent. (Japanese Patent Laid-Open No. 51-119
727, JP-A-52-147638, JP-A-53-16
048).

Cathode deposition type electrodeposition coating composition containing the above resin as a coating film component is mainly cured by oxidative polymerization of unsaturated groups contained in the resin to give a coating film having excellent performance such as end face coverage,
A relatively high baking temperature is required to cure in a practical curing time. As a result of research into lowering the baking temperature, the present inventors have found that the coating film is cured at a relatively low baking temperature by adding a metal drier such as a water-soluble manganese salt, and applied for a patent (Japanese Patent Laid-Open No. 53-53113). -142
444). 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 easy coating surface roughening. The present inventors have also found a method of introducing a highly reactive acrylic (methacrylic) double bond into a resin and curing the resin at a relatively low baking temperature, and applied for a patent (JP-A-56-151777). In this case, when a water-soluble manganese salt is added, it cures at a relatively low temperature of 160 ° C. and a cathodic deposition type electrodeposition coating having excellent performance can be obtained.

However, when bake-curing a coating film obtained by electrodeposition of these cathodic deposition type electrodeposition coatings, the curing reaction proceeds only by oxidative polymerization, so problems such as easier wrinkling on the surface or difficulty in curing inside There was a point.

As a result of various studies by the present inventors, the low temperature curable cathodic deposition type electrodeposition coating composition having the above-mentioned drawbacks is improved without inhibiting the oxidative polymerization property by adding a specific amount of aminoplast resin and having excellent performance. Reached

Therefore, an object of the present invention is to provide a low temperature curable cathodic deposition type electrodeposition coating composition having improved surface smoothness, excellent end face coverage and corrosion resistance.

Means for Solving the Problems The present invention provides (A) (1) 50-500 with a molecular weight of 500-5,000.
A polymer compound having an iodine value of carbon-carbon double bond and 3 to 12% by weight of oxirane oxygen (2) 30 to 3000 millimoles of the general formula per 100 g of the polymer compound, (In the formula, R ₁ and R ₂ represent a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group, or R ₁ and R ₂
Represents a ring structure containing nitrogen and optionally other heteroatoms. ) The amine compound represented by the formula (3) and (3) the compound represented by the general formula: (In the formula, R ₃ and R ₄ represent a hydrogen atom or a methyl group.)
Α, β unsaturated carboxylic acid represented by or molecular weight 10
100 parts by weight of a reaction product of an unsaturated fatty acid containing 0 to 350 carbon-carbon conjugated double bonds in an amount of 10% by weight or more, or a mixture thereof (B) 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) and 1.9 to 2.1 moles of the diglycidyl compound per molecule of the diglycidyl compound. General formula (In the formula, R ₃ and R ₄ represent a hydrogen atom or a methyl group.) An α, β unsaturated carboxylic acid represented by the formula, or a compound having a molecular weight of 100 to 350 and containing 10% by weight or more of a carbon-carbon conjugated double bond. 10 to 200 parts by weight of a reaction product of a saturated fatty acid or a mixture thereof (C) 2 to 30 parts by weight of an aminoplast resin (D) (1) an unsaturated monocarboxylic acid having 6 to 24 carbon atoms or a duplicate thereof, Or (2) a polymer compound having a carbon-carbon double bond having an iodine value of 50 to 500 with a molecular weight of 500 to 5000 and 40 to 400 mmol of the general formula per 100 g of the polymer compound; (Wherein R ₁₀ represents a hydrogen atom, a halogen atom, or a methyl group), a reaction product of an α, β unsaturated dicarboxylic acid or a derivative thereof such as a partial esterified product or a partially amidated product, or (1) Mixture of and (2) 0
30 parts by weight (E) Manganese salt, cobalt salt, copper salt, lead salt of organic acid,
A cathodic deposition type electrodeposition coating composition having excellent low-temperature curability, which contains 0.005 to 1.0 part by weight (as a metal amount) of manganese dioxide or a mixture thereof as an essential component.

500 to 5000 which is the starting material for the component (A) of the present invention
The polymer compound having a carbon-carbon double bond having an iodine value of 50 to 500 with a molecular weight of is produced by a conventionally known method.

That is, a conjugated diolefin having 4 to 10 carbon atoms alone, or a mixture of these diolefins, or an aromatic vinyl monomer such as styrene in an amount of 50 mol% or less with respect to the conjugated diolefin, using an alkali metal or an organic alkali metal compound as a catalyst. A typical production method is a method of anion-polymerizing or copolymerizing α-methylstyrene, vinyltoluene or divinylbenzene at a temperature of 0 ° C to 100 ° C. In this case, in order to control the molecular weight, to obtain a low-colored low polymer with less gel content, etc., an organic alkali metal compound such as benzyl sodium is used as a catalyst, and a compound having an alkylaryl group, for example, toluene is used as a chain transfer agent. Chain transfer polymerization method (US Pat. No. 3,789,090
Or a living polymerization method in which a polycyclic aromatic compound such as naphthalene is used as an activator in a solvent of tetrahydrofuran and an alkali metal such as sodium is used as a catalyst (Japanese Patent Publication Nos. 42-17485 and 43-27432), or Polymerization method in which aromatic hydrocarbons such as toluene and xylene are used as a solvent, a dispersion of an alkali metal such as sodium is used as a catalyst, and ethers such as dioxane are added to control the molecular weight (Japanese Patent Publication No. 32-7446). , Ibid 38-1
Nos. 245 and 34-10188) are suitable production methods. It is also produced by coordination anionic polymerization using an acetylacetonate compound of a Group 8 metal such as cobalt or nickel and an alkylaluminum halogenide as catalysts (Japanese Patent Publication Nos. 45-507 and 46-8030).
No. 0) low polymers can also be used.

The component (A) of the present invention is obtained by converting the unsaturated compound into hydrogen peroxide,
After being epoxidized by a known method using a peroxide such as peracid, 3 to 12% by weight of an oxirane oxygen group is introduced as oxygen, (In the formula, R ₁ and R ₂ are the same as the above), after reacting the amine compound in the presence or absence of a solvent at a temperature of 50 to 200 ° C. (Wherein R ₃ and R ₄ are the same as above), or α or β unsaturated carboxylic acid or a molecular weight of 10
An unsaturated fatty acid containing 0 to 350 carbon-carbon conjugated double bonds in an amount of 10 wt% or more or a mixture thereof is 100 to 2
It is produced by reacting at 00 ° C.

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

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

Examples of the α, β unsaturated carboxylic acid include alkaline acid, methacrylic acid and crotonic acid.

A carbon-carbon conjugated double bond having a molecular weight of 100 to 350
Unsaturated fatty acids containing by weight or more include sorbic acid, Chinese tung oil fatty acid, sunflower oil fatty acid, dehydrated castor oil fatty acid, and the like, and by isomerizing soybean oil fatty acid, linseed oil fatty acid, etc., conjugated conjugation Fatty acids can also be used, and purified eleostearic acid and conjugated linoleic acid can also be used. Further, a mixture in which an unsaturated fatty acid having 10% by weight or less of a carbon-carbon conjugated double bond is mixed with an unsaturated fatty acid having a large number of conjugated double bonds so that the total amount of conjugated double bonds is 10% by weight or more is also used. be able to. Among them, dehydrated castor oil fatty acid is advantageous and preferable because it is industrially easily available.

It is preferable to use such that the total amount of the α, β unsaturated carboxylic acid and the unsaturated fatty acid to be added is 50 to 150 mmol as the amount of carboxylic acid per 100 g of the epoxidized polymer compound.

Component (B) of the present invention, that is, the general formula (In the formula, R ₅ and R ₆ are a hydrogen atom or a methyl group, and n is 0.
To an integer of 20) per one molecule of the diglycidyl compound represented by the general formula (In the formula, R ₃ and R ₄ represent a hydrogen atom or a methyl group.) An α, β unsaturated carboxylic acid represented by the formula, or a compound having a molecular weight of 100 to 350 and containing 10% by weight or more of a carbon-carbon conjugated double bond. 1.9 saturated fatty acids or their mixtures
Addition of a compound produced by reacting ~ 2.1 mol significantly improves the corrosion resistance.

The content of the component (B) is in the range of 10 to 200 parts by weight, preferably 300 to 100 parts by weight, based on 100 parts by weight of the resin (A).

If the content of the component (B) is less than this range and the corrosion resistance is not sufficiently improved, if it is more than this range, the water dispersibility deteriorates.

To obtain the compound of the above component (B), a compound of the general formula (In the formula, R ₅ and R ₆ are the same as the above), and the diglycidyl compound is used as a raw material. The diglycidyl compound can usually be made by etherifying bisphenol with epichlorohydrin in the presence of alkali. Examples of the bisphenol compound include 2,2-bis (4'-hydroxyphenyl) propane, 1,1-bis (4'-hydroxyphenyl) ethane and 1,1-bis (4'-hydroxyphenyl) isobutane. is there. In many cases, the above-mentioned diglycidyl ether is further reacted with bisphenol to synthesize a diglycidyl compound having a somewhat higher molecular weight, and these compounds can be used.

The above diglycidyl compound has a general formula at a temperature of 0 to 200 ° C., preferably 50 to 150 ° C. (In the formula, R ₃ and R ₄ represent a hydrogen atom or a methyl group.) An α, β unsaturated monocarboxylic acid represented by: or a molecular weight of 100 to 350 and a carbon-carbon conjugated double bond of 10% by weight.
The unsaturated fatty acid containing the above or a mixture thereof is substantially 2 mol (1.9 to 2.1 mol) per mol of the diglycidyl compound.
Component (B) can be produced by reacting (mol).

The α, β unsaturated monocarboxylic acid or unsaturated fatty acid or mixture thereof used here is the same as that used for the synthesis of the component (A) described above.

In carrying out the reaction, 0.01 to 1.0% of a radical polymerization inhibitor such as hydroquinone, metoquinone, N-phenyl.N'-isopropyl-P-phenylenediamine is added to prevent side reactions, and tertiary amines are added. It is preferable to use a suitable catalyst such as or quaternary ammonium salt.
Further, the reaction can be carried out in the presence or absence of a solvent, but when a solvent is used, it is inactive to the reaction,
It is practically advantageous to use an appropriate amount of a solvent that can be used in the electrodeposition coating, for example, ethyl cellosolve, MIBK, etc., and mix it with other components as it is without removing it after the reaction and use it in the electrodeposition coating.

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

If a large amount of the group remains, this group causes an unfavorable reaction with the basic group of the resin (A) when it is solubilized by adding an acid to cause gelation, resulting in too high viscosity. As a result, water solubility is hindered. Even if water can be solubilized, the aqueous solution changes with time, which causes certain defects such as a certain electrodeposition characteristic or the inability to obtain an electrodeposition coating film.

By adding the component (C) of the present invention, that is, the aminoplast resin, a cathodic deposition type electrodeposition coating composition having excellent surface smoothness, corrosion resistance and low temperature curability can be obtained.

If the addition amount of the component (C) is less than 2 parts by weight, the effect of improving the surface smoothness and internal curability is small, and if it is more than 30 parts by weight, the corrosion resistance decreases and the heating loss during baking increases. Undesired phenomenon of occurs. A preferred range is 5 to 15 parts by weight.

Examples of aminoplast resins are ureas (including substituted ureas) and triazines such as melamine, benzoguanamine and reaction products of acetoguanamine with formaldehyde. These may be etherified with alcohols if desired. From the point of view of stability, substantially completely etherified products are preferred. A preferable example of the aminoplast resin is a reaction product of melamine and formaldehyde. The aminoplast resin is used in the methylol type, but is preferably at least partially in the ether type, that is, the etherifying agent has about 1 carbon atoms.
Used in ether form, which is 6 monohydric alcohols. Examples of suitable alcohols include methanol and butanol. The aminoplast resin can be prepared by a conventionally known method.

Component (D) of the present invention, namely (1) unsaturated monocarboxylic acid having 6 to 24 carbon atoms or a dimer thereof, or (2) carbon-carbon having a molecular weight of 500 to 5000 and an iodine value of 50 to 500. A polymer compound having a double bond and 40 to 400 mmol of the general formula per 100 g of the polymer compound, (Wherein R ₁₀ represents a hydrogen atom, a halogen atom, or a methyl group), a reaction product of an α, β unsaturated dicarboxylic acid or a derivative thereof such as a partial esterified product or a partially amidated product, or (1) The addition of the mixture of (2) and (2) is optional,
Addition of up to 30 parts by weight is preferable because smoothness and curability are further improved. However, if the addition amount exceeds 30 parts by weight, the corrosion resistance is deteriorated, which is not preferable, and more preferably 10 parts by weight or less.

Examples of unsaturated monocarboxylic acids having 6 to 24 carbon atoms or dimers thereof include tung oil fatty acid, linseed oil fatty acid, sunflower oil fatty acid, soybean oil fatty acid, dehydrated castor oil fatty acid, castor oil fatty acid, safflower oil fatty acid, So-called purified unsaturated fatty acids such as tall oil fatty acid, oleic acid, linoleic acid, linoleic acid, eleostearic acid, beef fatty acid, fish fatty acid, dehydrated castor oil fatty acid, conjugated unsaturated fatty acid obtained by isomerizing sunflower oil fatty acid, sorbin An unsaturated monocarboxylic acid such as acid or cinnamic acid can be used.

Furthermore, cyclic unsaturated monocarboxylic acids such as abietic acid and pimaric acid obtained from natural rosin, and synthetic drying oil fatty acids such as Hydiene (manufactured by Soken Chemical Co., Ltd.) can also be used. The dimer includes dimer acid obtained from tall oil fatty acid and the like, and dimer rosin obtained from rosin. The above unsaturated monocarboxylic acids or their dimers can be used alone or in admixture.

Examples of the polymer compound having a carbon-carbon double bond having an iodine value of 50 to 500 and a molecular weight of 500 to 5000 include natural oils such as linseed oil, tung oil and dehydrated castor oil, and synthetic drying oils such as liquid polybutadiene. Can be used.
Examples of the α, β unsaturated dicarboxylic acid include maleic acid, citraconic acid and chloromaleic acid. Typical examples of the reaction product of the polymer and the α, β unsaturated dicarboxylic acid are maleated polybutadiene and maleated linseed oil. Derivatives of these compounds, that is, half-esterified products, half-amidated products and the like can also be used.

The component (D) of the present invention may be a mixture of the above (1) and (2).

As the component (E) of the present invention, formic acid, acetic acid, lactic acid, naphthenic acid, octanoic acid and the general formula [In the formula, R ₇ and R ₈ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, provided that R ₇ and R ₈ each have a 6-membered ring structure or a heterocyclic structure containing a 5-membered ring and a 6-membered ring. And may contain an unsaturated group in the ring structure.

R ₉ 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 or a bond having 1 to 10 carbon atoms, and when X ₁ and X ₂ are a bond, X ₁
And the carbon attached to X ₂ can form a double bond with each other. ] Manganese salts, cobalt salts, copper salts, lead salts, and manganese dioxide of organic acids such as 1,2-dicarboxylic acid monoesters represented by the following can be used. By adding 0.005 to 1.0 part by weight of these metal compounds, the curability is remarkably promoted, and a low temperature curable cathodic deposition type electrodeposition coating composition is obtained.

If the added amount of the component (E) of the present invention is less than 0.005 parts by weight as the amount of metal, the effect of promoting curability is small, and
If the amount is more than 1.0 part by weight, the curability is good, but the water resistance and corrosion resistance are deteriorated, which is not preferable. The preferable range is 0.01 to 0.5 part by weight as the amount of metal.

In the present invention, the component (A), the component (B), the component (C),
In order to make the composition comprising the component (D) and the component (E) water-soluble or water-dispersible, the component (A), the component (B), the component (C), the component (D) and the component (E) are previously added. After mixing, it is preferable to neutralize with a water-soluble organic acid such as acetic acid, propionic acid or lactic acid in an amount of 0.1 to 2.0, preferably 0.2 to 1.0 molar equivalent to the amino group of the component (A) to make it water soluble. .

When the composition (A), (B), (C), (D) and the component (E) of the present invention are dissolved or dispersed in water, the dissolution or dispersion is facilitated, the stability of the aqueous solution is improved, and the resin For the purpose of improving the fluidity of the resin composition and improving the smoothness of the coating film, ethyl cellosolve, propyl cellosolve, butyl cellosolve, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diacetone are water-soluble and can dissolve each resin composition. alcohol,
It is preferable to use 10 to 100 parts by weight of an organic solvent such as 4-methoxy-4-methylpentanone-2 and methyl ethyl ketone per 100 parts by weight of each resin composition.

A suitable pigment may be further added to the cathodic deposition type 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 precipitated barium sulfate can be blended.

These pigments can be added to the composition of the present invention as they are, but each amount of the pigment is added to and mixed with a part of the component (A) neutralized and dispersed or made into an aqueous solution in advance,
A paste-like masterbatch can be obtained, and the paste-like pigment can be added to the composition.

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

Production Example 1 Nisseki Polybutadiene B-2000 (number average molecular weight 2,000,1,2 bond 65%) was epoxidized with peracetic acid to produce an epoxidized polybutadiene having an oxirane oxygen content of 6.4%.

After charging 1000 g of epoxidized polybutadiene and 354 g of ethyl cellosolve in 2 autoclaves, 62.1 g of dimethylamine was added and reacted at 150 ° C. for 5 hours. After distilling off unreacted amine, the mixture was cooled to 120 ° C., a mixture of 79.3 g of acrylic acid, 7.6 g of hydroquinone and 26.4 g of ethyl cellosolve was added, and the mixture was further heated at 120 ° C. for 3 minutes.
The reaction was carried out for 45 minutes to prepare a resin solution (A ₁ ) of the component (A) of the present invention. This had an amine value of 85.2 mmol / 100 g, an acid value of 10.0 mmol / 100 g, and a solid content concentration of 75.0% by weight.

Production Example 2 Nisseki Polybutadiene B-1800 (number average molecular weight 1,800,1,2 bonds 64%) was epoxidized with peracetic acid to produce epoxidized polybutadiene having an oxirane oxygen content of 6.5%.

1000 g of this epoxidized polybutadiene, 377 g of ethyl cellosolve and 131.
Charge 0 g into a 3 separable flask and mix at 170 ° C for 6
Reacted for hours. After the reaction, cool to 120 ° C., add a mixture of dehydrated castor oil fatty acid 140.0 g, hydroquinone 8.8 g and ethyl cellosolve 61.1 g and react at 150 ° C. for 2 hours, then cool to 120 ° C. and add acrylic acid 43.2 g Then, the mixture was reacted at 120 ° C. for 4 hours to produce a resin solution (A ₂ ) of component A of the present invention.

This product has an amine value of 99.0 mmol / 100g and an acid value of
9.0 mmol / 100 g, and the solid content concentration was 75% by weight.

Production Example 3 Nisseki Polybutadiene B-1800 (number average molecular weight 1,800,1,2 bond 64%) was epoxidized using hydrogen peroxide as a formic acid catalyst to produce epoxidized polybutadiene having oxirane oxygen content of 6.7% by weight. .

After 1,000 g of this epoxidized polybutadiene and 357 g of ethyl cellosolve were charged in 3 autoclaves, 74.6 g of dimethylamine was added and the mixture was reacted at 150 ° C. for 5 hours. After distilling off the unreacted amine, the mixture was cooled to 120, and a mixture of synthetic drying oil fatty acid (trade name Hydiene, manufactured by Soken Chemical Co., Ltd.) 140 g, hydroquinone 8.4 g and ethyl cellosolve 61.1 g was added, and the mixture was heated at 150 ° C. for 2 hours. After the reaction, the mixture was cooled to 120 ° C., 43.2 g of acrylic acid was added, and the mixture was reacted at 120 ° C. for 4 hours to prepare a resin solution (A ₃ ) of the component (A) of the present invention.

This product has an amine value of 93.6 mmol / 100g and an acid value of
9.8 mmol / 100 g, and the solid content concentration was 75% by weight.

Production Example 4 The following compound obtained by reacting bisphenol A and epichlorohydrin in the presence of an alkali catalyst As a raw material, 1000 g of a bisphenol type epoxy resin (trade name: Epicoat 1004, manufactured by Yuka Shell Epoxy Co., Ltd.) having an epoxy equivalent of 950 is used as ethyl cellosolve 343.
Dissolve in g, acrylic acid 76.3g, hydroquinone 10g
And 5 g of N, N-dimethylaminoethanol were added, and the mixture was heated to 100 ° C. and reacted for 5 hours to synthesize a resin solution (B ₁ ) of the component (B) of the present invention.

Production Example 5 The following compound obtained by reacting bisphenol A and epichlorohydrin in the presence of an alkali catalyst As an example, 1000 g of a bisphenol type epoxy resin having an epoxy equivalent of 485 (trade name: Epicoat 1001, manufactured by Yuka Shell Epoxy Co., Ltd.) was used as ethyl cellosolve 400.
Dissolve in g, dehydrated castor oil fatty acid 145.6g, acrylic acid 1
11.6 g, hydroquinone 10 g and N, N-dimethylaminoethanol 5 g were added and heated to 100 ° C. for 5
The resin solution (B ₂ ) of the component (B) of the present invention is reacted for a time.
Was synthesized.

Production Example 6 Nisseki Polybutadiene B-700 (Number average molecular weight 700,1,2 bond 52
%) 1000 g, maleic anhydride 117.3 g, antigen 3
1 g of C and 10 g of xylene were charged into a 2 separable flask equipped with a reflux condenser, and 195 under a nitrogen stream.
The reaction was carried out at 0 ° C for 5 hours. Then, unreacted maleic anhydride and xylene were distilled off under reduced pressure to obtain an acid value of 107 mmol / 10.
0 g of maleated polybutadiene (M) was synthesized.

Maleated polybutadiene (M) (500 g) and ethyl cellosolve (148 g) were reacted at 120 ° C. for 2 hours to open the succinic anhydride group and then cooled to room temperature to remove caustic soda.
After 100 g of a 22.5 wt% aqueous solution was gradually added to neutralize, deionized water was added to adjust the solid content concentration to 25 wt% to prepare an aqueous solution of maleated polybutadiene.

Next, 74.5 g of manganese sulfate (MnSO ₄ .4H ₂ O) was dissolved in 600 g of water, and then 600 g of isopropyl alcohol.
Then, 1000 g of benzene was added, and 2.192 g of the above maleated polybutadiene aqueous solution was gradually added dropwise at room temperature with stirring. After the completion of the addition, the mixture was heated to 60 ° C. for 30 minutes and allowed to stand for 1 hour. , Deionized water 1
000 g was added and the mixture was heated at 60 ° C. for 30 minutes and then left standing for 1 hour to remove the lower layer.

The upper layer was taken out and benzene and the like were distilled off under reduced pressure to produce a manganese salt of maleated polybutadiene by a metathesis method.

The manganese salt of maleated polybutadiene was dissolved in ethyl cellosolve so that the solid content was 75% by weight to prepare a solution (E ₁ ) of the oil-soluble manganese salt of the component (E) of the present invention. The manganese content of (E 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 4 and aminoplast resin (trade name Nicalac MX-45, manufactured by Sanwa Chemical Co., Ltd.) (C ₁ )
After 48 g were mixed until uniform, 8.1 g acetic acid was added and the mixture was thoroughly stirred and neutralized. Next, deionized water was gradually added to prepare an aqueous solution having a solid content concentration of 20% by weight.

2000 g of this 20% by weight aqueous solution, 4 g of carbon black, 20 g of basic lead silicate and glass beads 2000
5 g was placed in a 5 stainless beaker and stirred vigorously for 2 hours with a high speed rotating mixer, and then glass beads were filtered.
Next, add deionized water containing 0.32 g of manganese acetate as manganese metal so that the solid content concentration becomes 16.5% by weight,
The electrodeposition coating liquid was adjusted.

Cathode deposition type electrodeposition coating was carried out using the above electrodeposition coating solution using a carbon electrode as an anode and a zinc phosphate-treated plate as a cathode.
The test results are shown in Table-1.

Example 2 A cathodic deposition type electrodeposition coating solution was prepared under the same conditions as in Example 1 except that the amount of the (C ₁ ) component added in Example 1 was changed to 96 g, and a test was conducted under the same conditions as in Example 1. went. The results are shown in Table-1.

Comparative Example 1 A coating liquid was prepared and tested under the same conditions as in Example 1 except that the component (C ₁ ) in Example 1 was not added. The results are shown in Table-1.

Comparative Example 2 A coating solution was prepared and tested under the same conditions as in Example 1 except that the amount of the component (C ₁ ) added in Example 1 was 256 g. The results are shown in Table-1.

Example 3 400 g of (A ₂ ) produced in Production Example 2 and 400 g of (B ₂ ) produced in Production Example 5, and aminoplast resin (trade name U-VAN 120, manufactured by Mitsui Toatsu Co., Ltd.) (C ₂ ) 8
After mixing 0 g to homogeneity, add 9.6 g acetic acid,
Stir well to neutralize. Next, deionized water was gradually added to prepare an aqueous solution having a solid content concentration of 25% by weight. 1000 g of this 25 wt% aqueous solution, carbon black 2.5
g, basic lead silicate 25 g and glass beads 1000 g
Place 3 in a stainless beaker and use a high-speed rotating mixer for 2
After stirring vigorously for a time, the glass beads were filtered. Next, deionized water containing 0.13 g of manganese acetate as a manganese metal was added so that the solid content concentration became 18% to prepare an electrodeposition coating solution.

Cathode deposition type electrodeposition coating was performed using the above electrodeposition coating solution with a carbon electrode as an anode and a zinc phosphate treated plate as a cathode.
The test results are shown in Table-2.

Example 4 400 g of (A ₃ ) produced in Production Example 3, 400 g of (B ₂ ) produced in Production Example 5, 80 g of the (C ₂ ) component in Example 3, and 44 g of (E ₁ ) produced in Production Example 6. Was mixed until uniform, and 9.0 g of acetic acid was added, and the mixture was thoroughly stirred and neutralized. Next, deionized water was gradually added to prepare an aqueous solution having a solid content concentration of 30% by weight.

1000 g of this 30% by weight aqueous solution, carbon black 3
g, basic lead silicate 20 g and glass beads 1000 g
Was placed in a stainless beaker No. 3 and stirred vigorously for 2 hours with a high-speed rotating mixer, and then glass beads were filtered.
Then, deionized water containing 0.15 g of manganese acetate as a manganese metal was added so that the solid content concentration became 16%, to prepare an electrodeposition coating solution.

Cathode deposition type electrodeposition coating was carried out using the above electrodeposition coating solution using a carbon electrode as an anode and a zinc phosphate-treated plate as a cathode.
The test results are shown in Table-2.

Comparative Example 3 A coating liquid was prepared and tested under the same conditions as in Example 3 except that the component (C ₂ ) in Example 3 was not added. The results are shown in Table-2.

Comparative Example 4 A coating liquid was prepared and tested under the same conditions as in Example 4 except that the component (C ₂ ) in Example 4 was not added. The results are shown in Table-2.

Example 5 400 g of (A ₁ ) produced in Production Example 1, 400 g of (B ₁ ) produced in Production Example 4, aminoplast resin (trade name Nicalac MX-45, manufactured by Sanwa Chemical Co., Ltd.) (C ₁ ). 48
g and 60 g of decastor oil fatty acid (D) were mixed until uniform, and 6.1 g of acetic acid was added thereto, and the mixture was thoroughly stirred and neutralized. Next, deionized water was gradually added to prepare an aqueous solution having a solid content concentration of 20% by weight.

2000 g of this 20% by weight aqueous solution, 4 g of carbon black, 20 g of basic lead silicate and glass beads 2000
5 g was placed in a 5 stainless beaker and stirred vigorously for 2 hours with a high speed rotating mixer, and then glass beads were filtered.
Next, add deionized water containing 0.32 g of cobalt acetate as cobalt metal so that the solid content concentration becomes 16.5% by weight,
An electrodeposition coating solution was prepared.

Cathode deposition type electrodeposition coating was carried out using the above electrodeposition coating solution using a carbon electrode as an anode and a zinc phosphate-treated plate as a cathode.
The test results are shown in Table-2.

Front page continuation (72) Inventor Kouji Ito 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Within Japan Paint Co., Ltd. (72) Inventor Yu Otsuki 332-4 Noba-cho, Konan-ku, Yokohama-shi, Kanagawa (72) Invention Person Yoshihiko Araki 4-10-13 Minamiyukitani, Ota-ku, Tokyo

Claims (1)

[Claims] 1. A polymer compound having (A) (1) a carbon-carbon double bond having a molecular weight of 500 to 5,000 and an iodine value of 50 to 500, and 3 to 12% by weight of oxirane oxygen (2) 30-300 millimoles per 100 g of molecular compound, the general formula (In the formula, R ₁ and R ₂ represent a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group, or R ₁ and R ₂
Represents a ring structure containing nitrogen and optionally other heteroatoms. ) The amine compound represented by the formula (3) and (3) the compound represented by the general formula: (In the formula, R ₃ and R ₄ represent a hydrogen atom or a methyl group.)
Α, β unsaturated carboxylic acid represented by or molecular weight 10
100 parts by weight of a reaction product of an unsaturated fatty acid containing 0 to 350 carbon-carbon conjugated double bonds in an amount of 10% by weight or more, or a mixture thereof (B) 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) and 1.9 to 2.1 moles of the diglycidyl compound per molecule of the diglycidyl compound. General formula (In the formula, R ₃ and R ₄ represent a hydrogen atom or a methyl group.) An α, β unsaturated carboxylic acid represented by the formula, or a compound having a molecular weight of 100 to 350 and containing 10% by weight or more of a carbon-carbon conjugated double bond. Reaction product of saturated fatty acid or mixture thereof 10 to 200 parts by weight (C) Aminoplast resin 2 to 30 parts by weight (D) (1) Unsaturated monocarboxylic acid having 6 to 24 carbon atoms or dimer thereof Or (2) a polymer compound having a carbon-carbon double bond having an iodine value of 50 to 500 with a molecular weight of 500 to 5000 and 40 to 400 mmol of the general formula per 100 g of the polymer compound, (Wherein R ₁₀ represents a hydrogen atom, a halogen atom, or a methyl group), a reaction product of an α, β unsaturated dicarboxylic acid or a derivative thereof such as a partial esterified product or a partially amidated product, or (1) Mixture of and (2) 0
30 parts by weight (E) Manganese salt, cobalt salt, copper salt, lead salt of organic acid,
A cathodic deposition type electrodeposition coating composition having excellent low-temperature curability, which contains 0.005 to 1.0 part by weight (as a metal amount) of manganese dioxide or a mixture thereof as an essential component.