JP2519955B2 - Composition for electrodeposition paint - Google Patents

Description

TECHNICAL FIELD The present invention relates to a composition for an anodic deposition type electrodeposition coating composition, and more particularly to a composition for an anodic deposition type electrodeposition coating composition that cures at a low temperature or room temperature. In particular, by using the composition for electrodeposition coating composition of the present invention, it is possible to provide an anodic deposition type electrodeposition coating composition which cures at a low temperature without impairing various performances required for conventional electrodeposition coating compositions.

[Prior art and its problems] Compared to other coating methods, electrodeposition coating has many advantages such as high efficiency of use of paint and automation of painting work. It is used for painting various metal products. However, a thermosetting water-soluble paint is mainly used for the conventional electrodeposition coating, and it is necessary to bake at a relatively high temperature in order to cure the coating film after the electrodeposition coating.

For example, as the anodic deposition type electrodeposition paint, maleated oil,
Compounds having an acid group such as maleated liquid polybutadiene and epoxy ester are used, but generally 150
A baking temperature of ℃ or above is required.

Therefore, it has been difficult to apply to a coating object having a large heat capacity or a coating object incorporating rubber or plastic.
Further, baking at a high temperature causes a large energy loss and is economically disadvantageous.

Various proposals have been made to improve this drawback (for example, JP-A-61-12765, JP-A-59-122563, JP-A-61-247768, etc.), but low temperature curability and paint stability. The properties, the smoothness of the coated surface, and the various required performances of the coating film were not satisfied.

For example, JP-A-61-247768 described above discloses a room temperature curable water-based coating composition comprising a component obtained by introducing an acrylic acid ester group into maleated polybutadiene and a non-dispersible component which is an acrylic acid-added epoxy resin. Is disclosed. However, even after 24 hours after drying for 20 minutes at 80 ° C. for any of these compositions, for example, the coating film hardness is only about 3B to 6B in pencil hardness, which is still insufficient, and water dispersion The sex is not always good either.

Therefore, an object of the present invention is to provide a composition for an anodic deposition type electrodeposition coating composition which is excellent in performance required for these electrodeposition coating compositions and is also excellent in low temperature curability.

[Means for Solving Problems] According to the present invention, (A) a drying oil having a number average molecular weight of 500 to 10000 or a conjugated diene polymer or copolymer is modified, and a modified product Free carboxylic acid group of 10 to 300 mg KOH / g as an acid value per g, 10 meq or more of conjugated diene bond per 100 g of modified product, and the following formula (Wherein R ₁ and R ₂ are hydrogen atoms or methyl groups), 100 parts by weight of a modified product having an α, β-unsaturated monocarboxylic acid residue of 10 meq or more per 100 g of the modified product, and (B) cobalt. Containing 0.001 to 1.0 part by weight of an organic compound or inorganic compound of one or more metals selected from the group consisting of, manganese, iron, nickel, lead, zinc and chromium in terms of metal, (A) A composition characterized in that the modified carboxylic acid group of the modified component is at least partially neutralized with a base and dispersed or dissolved in water is used as a composition for electrodeposition coating.

That is, by introducing a conjugated diene group, an α, β-unsaturated monocarboxylic acid residue into a composition used for an anodic deposition type electrodeposition coating composition, and blending the metal compound, it is required for the electrodeposition coating composition. It is possible to obtain a composition for an anodic deposition type electrodeposition coating composition which is excellent in the above-mentioned performance and is also excellent in low-temperature curability.

Generally, it is considered that a coating composition obtained from a drying oil or a conjugated diene polymer is cured by oxidative polymerization of the unsaturated bond remaining in the main part or the branch part. However, the oxidative polymerizability of these remaining unsaturated bonds is low,
The desired cured coating film cannot be obtained unless it is baked at a relatively high temperature. Therefore, it has been proposed to add a transition metal compound as a dryer in order to improve this oxidative polymerization property, but sufficient low temperature curability was not obtained. It is surprising, however, that the composition of the present invention provided the desired low temperature curability due to the synergistic effect of the factors it possesses.

It is said that the curing mechanism by oxidative polymerization involves complicated factors such as absorption of oxygen, decomposition, generation of radicals, and polymerization. It is presumed that excellent low-temperature curability was realized because the above could be controlled synergistically with good balance.

 The present invention will be described in more detail below.

(1) Raw Material The drying oil and the conjugated diene polymer or the conjugated diene copolymer used in the component (A) of the present invention form the main part of the modified product. Specific examples of the drying oil (including semi-drying oil) include linseed oil, soybean oil, sesame oil, safflower oil, hempseed oil, cottonseed oil, tung oil, dehydrated castor oil, poppy oil, eno oil, corn oil, and tall oil. Examples thereof include oils, sunflower oils, walnut oils, rubber seed oils, rice bran oils, high-diene oils, and heat-polymerized oils thereof. These can be used alone or in combination of two or more.

As the conjugated diene polymer or the conjugated diene copolymer, specifically, a conjugated diene low polymer having 4 to 5 carbon atoms such as butadiene and isoprene, or a low polymerization degree copolymer of two or more of these conjugated dienes is used. Polymers, monomers other than these conjugated dienes having one or more of these conjugated dienes and an ethylenically unsaturated bond, especially isobutylene, diisobutylene, styrene, α-methylstyrene, vinyltoluene, divinylbenzene, etc. Examples thereof include low degree of polymerization copolymers with various aliphatic or aromatic vinyl monomers. In addition, a part of these conjugated diene polymers or copolymers modified with oxygen-containing and nitrogen-containing compounds, and a product having a carboxylic acid group introduced at the terminal of the molecular chain can also be used. These can be used alone, but can also be used as a mixture of two or more kinds.

Two or more types of these drying oils, conjugated diene polymers and conjugated diene copolymers can be mixed and used.

The drying oil and the conjugated diene polymer or conjugated diene copolymer used in the present invention are preferably those having an iodine value of 80 or more and a number average molecular weight of 500 to 10,000. When the iodine value is less than 80, it becomes difficult to introduce a necessary amount of functional group in the subsequent modification, for example, a necessary amount of α, β-unsaturated dicarboxylic acid anhydride necessary for water dispersion. The upper limit of the iodine value is not particularly limited. When the number average molecular weight is lower than 500, the curability at low temperature is deteriorated.
In addition, when the number average molecular weight is higher than 10,000, problems such as deterioration of smoothness of the obtained coating film occur.

The conjugated diene polymer or conjugated diene copolymer, which is a particularly preferable raw material in the present invention, is a butadiene-based polymer obtained by polymerizing or copolymerizing at least 50 mol% of butadiene. Further, among these, the preferred butadiene-based polymer has a vinyl group (1,2-bond) of 50 to 70 mol%.
It is a butadiene-based polymer containing. Those having a vinyl group in this range are suitable because they have a good balance between the smoothness of the coated surface obtained using the vinyl group and the physical properties of the coating film.

(2) Addition of α, β-unsaturated dicarboxylic acid anhydride Further, in the present invention, the raw material of the component (A) has a free carboxylic acid group. At least a part of the acid group is neutralized with a base to improve the dispersibility or solubility of the modified product in water. Therefore, the amount of the acid group is 10 to 300 mg KOH / g as an acid value per g of the modified product. The amount of acid groups is 10mgKOH /
If it is less than g, the affinity for water is insufficient, and 300 mgKOH / g
If the amount is larger than the above values, the water resistance of the cured coating film is impaired, which is not preferable.

As a method for imparting a free carboxylic acid group to the raw material, a conventionally known method is used, for example, acrylic acid, α, β-unsaturated mono- or dicarboxylic acid such as maleic anhydride, or an anhydride thereof. By adding to the raw material, a free carboxylic acid group can be introduced.

In the present invention, the α, β-unsaturated dicarboxylic acid anhydride is subjected to an addition reaction because it is convenient for improving the water affinity with the obtained free acid carboxylic acid and for the subsequent modification treatment.

Here, as the α, β-unsaturated dicarboxylic acid anhydride to be added to the drying oil, the conjugated diene polymer and the conjugated diene copolymer, specifically, maleic anhydride, citraconic acid anhydride, chloromaleic acid anhydride, etc. may be mentioned. Can be mentioned.

Usually, this addition reaction is performed at a reaction temperature in an appropriate inert solvent.
It is performed at 100 ° C to 250 ° C. At this time, it is appropriate to add 0.1 to 0.2 parts by weight of hydroquinone, catechols, diphenylamine derivatives and the like as an antigelling agent.

The amount of these α, β-unsaturated dicarboxylic acid anhydrides to be added is appropriately determined so that the acid value per modified product is 10 to 300 mg KOH / g, preferably 20 to 200 mg KOH / g. To be done.

The modified product (A) of the present invention is obtained by adding the above α, β-unsaturated dicarboxylic acid anhydride, and then adding an alcohol having a conjugated diene bond and the α, β-represented by the formula (II).
Method of reacting with unsaturated monocarboxylic acid hydroxyalkyl ester, or another method, modification with alcohol having conjugated diene bond and α, β-unsaturated monocarboxylic acid residue represented by the above formula (I) It can also be manufactured by

First, a method for synthesizing an alcohol having a conjugated diene bond and an α, β-unsaturated monocarboxylic acid hydroxyalkyl ester represented by the above formula (II) will be described.

Next, a method for synthesizing an alcohol having a conjugated diene bond and an α, β-unsaturated monocarboxylic acid residue represented by the formula (I) will be described.

(3) Conjugated Diene-Containing Alcohol Here, the conjugated diene bond means an aliphatic carbon-carbon double bond composed of two groups, that is, a total of four carbon atoms, which are conjugated with each other. A conventionally known method is used to introduce this conjugated diene bond, but it is preferable to modify it with an alcohol having a conjugated diene bond because of the ease of reaction, that is, the already added acid anhydride group can be utilized. .

As the alcohol containing the conjugated diene, 2,4
Examples include dipenten-1-ol and sorbin alcohol.

In addition, it can also be obtained by reacting a conjugated fatty acid with a diol or monoepoxy compound having two aliphatic hydroxyl groups by an esterification reaction. Examples of such conjugated fatty acids include eleostearic acid and conjugated linoleic acid, and tung oil fatty acid and dehydrated castor oil fatty acid containing a large amount of these conjugated fatty acids.

Examples of diols that undergo esterification reaction with these conjugated fatty acids include saturated glycols such as ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol, and 3-butene-1,2.
And unsaturated glycols such as diols. The esterification reaction between these diols and the conjugated fatty acid is generally well known, but is carried out while dehydrating using a base, an acid or a tin compound as a catalyst. Particularly preferred is a method of reacting in the presence of an excess of diols in order to prevent the formation of diesters, and removing unreacted diols by distillation after the reaction.

Further, an alcohol containing a conjugated diene can also be obtained by reacting the conjugated fatty acid with a monoepoxy compound. Examples of such a monoepoxy compound include:
Examples thereof include aliphatic monoepoxy compounds such as ethylene oxide, propylene oxide and butylene oxide, aromatic monoepoxy compounds such as styrene oxide, and monoglycidyl compounds such as phenylglycidyl ether. The reaction between these monoepoxy compounds and the conjugated fatty acid is also 60 to 180 ° C. according to a conventionally known method.
At this temperature, it is possible to easily react with a base such as an amine as a catalyst, and as a result, an alcohol containing a conjugated diene bond can be obtained.

(4) Alcohol having conjugated diene bond and α, β-unsaturated monocarboxylic acid residue Here, alcohol having conjugated diene bond and α, β-unsaturated monocarboxylic acid residue represented by the above formula (I). Can be manufactured as follows.

That is, α, β such as acrylic acid alkyl ester or methacrylic acid alkyl ester containing an epoxy group
-Unsaturated monocarboxylic acid alkyl ester, for example, glycidyl methacrylate or glycidyl acrylate is used as a monoepoxy compound, eleostearic acid or conjugated linoleic acid, and tung oil fatty acid or dehydrated castor oil fatty acid containing a large amount of these conjugated fatty acids. It is obtained by reacting with the conjugated fatty acid of 1 to form an ester bond. The reaction conditions of the epoxy group and the acid group at this time are the same as the reaction conditions of reacting the alcohol having a conjugated diene bond with the acid anhydride group adduct described in (3) above.

Further, a glycidyl ester obtained by reacting these conjugated fatty acids with halohydrin such as epichlorohydrin is used, and this is also used as a monoepoxide for α, β-
It can also be obtained by reacting with an unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid or crotonic acid under the same conditions to form an ester bond.

(5) Production of Modified Product of Component (A) The drying oil, the conjugated diene polymer and the conjugated diene copolymer to which the α, β-unsaturated dicarboxylic acid anhydride is added described in (2) above are added to the above (3). The modified product of the component (A) can be produced by reacting the alcohol having a conjugated diene bond described in 1) with the α, β-unsaturated monocarboxylic acid hydroxyalkyl ester represented by the following formula (II).

(In the formula, R ₁ and R ₂ are a hydrogen atom or a methyl group, and R ₃ is an alkyl group having a carbon number of 2 or more) By reacting the α, β-unsaturated monocarboxylic acid hydroxyalkyl ester, the above formula (I The α, β-unsaturated monocarboxylic acid residue of 1) can be introduced into the raw material of the present invention.

Examples of the α, β-unsaturated monocarboxylic acid hydroxyalkyl ester include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl crotonic acid, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate. Is mentioned.

Since the reaction of the alcohol having a conjugated diene and the α, β-unsaturated monocarboxylic acid hydroxyalkyl ester of the above formula (II) is an ester forming reaction between an acid anhydride group and an alcohol, they are performed separately or simultaneously. The drying oil, the conjugated diene polymer and the conjugated diene copolymer to which the α, β-unsaturated dicarboxylic acid anhydride described above in (2) is added can be reacted. These reactions are of the same kind, and it is usually economical to react them at the same time.

Another method for producing a modified product of the component (A) of the present invention is a drying oil, a conjugated diene polymer and a conjugated diene copolymer to which the α, β-unsaturated dicarboxylic acid anhydride described in (2) above is added. To the alcohol having the conjugated diene bond obtained in (4) and the α, β-unsaturated monocarboxylic acid residue represented by the formula (I).

The above-mentioned two kinds of reactions are both the reaction between the acid anhydride group in the acid anhydride group adduct and the alcohol, and the reaction between the acid anhydride group in the acid anhydride group adduct and the alcohol is 0 to 120 according to a conventionally known method. It easily reacts by forming an ester bond in the temperature range of ° C. If a base such as amines or inorganic alkali is used as a catalyst, the reaction can be carried out at a low temperature. Also in this reaction, the above α,
It is preferable to use an antigelling agent or a polymerization inhibitor such as hydroquinone, catechols and diphenylamine derivatives used in the addition of the β-unsaturated dicarboxylic acid anhydride.

Further, various solvents inert to this reaction can be used. When a solvent is used, it is convenient to use a solvent that can be used in the next step of solubilizing the component (A) described below, because the solvent can be used without separation after the reaction.

The amount of the conjugated diene bond and the amount of the α, β-unsaturated monocarboxylic acid residue represented by the above formula (I) in the obtained modified product (A) are all based on 100 g of the modified resin of the component (A). Should be 10 meq or more. If this amount is too small, sufficient low temperature curability cannot be obtained. The upper limit is not particularly limited. When some of the acid anhydride groups are reacted with the alcohols mentioned above, the residual acid anhydride groups can also be reacted with water, alcohols, secondary amines or mixtures thereof.

(6) Component (B) The component (B) is indispensable for promoting the oxidative polymerization curing reaction of the component (A) and achieving low temperature curing. The metal compound that can be used for this purpose is an organic compound or an inorganic compound of one or more metals selected from the group consisting of cobalt, manganese, iron, nickel, lead, zinc and chromium. Are organic acid salts of metals, metal complexes having acetylacetone as a ligand, and metal oxides such as manganese dioxide. Examples of the organic acid in the organic acid salt include organic acids such as formic acid, acetic acid, lactic acid, naphthenic acid and octenoic acid. Suitable organic acid metal salts include cobalt and manganese naphthenates, octenoates, and the like, and metal complexes include acetylacetonate complexes of these metals. The metal compound as the component (B) can be added during dispersion or dissolution of the component (A) in water, or can be added in advance during the synthesis of the component (A).

The amount of component (B) used is calculated as metal (component) (A).
It should be in the range of 0.001 to 1.0 parts by weight, preferably 0.02 to 0.5 parts by weight, per 100 parts by weight of the modified products. When the compounding amount of the metal compound is less than this range, the low temperature curability is not sufficient, and when it is too large, the smoothness and corrosion resistance of the obtained coating film are deteriorated, and neither is practical.

(7) Electrodeposition coating composition In the present invention, the composition containing the above-mentioned components (A) and (B) as essential components is neutralized with a base to disperse the modified product of component (A) in water. Alternatively, it is dissolved to obtain a composition for electrodeposition coating.

In order to disperse or dissolve the component (A) in water, a base sufficient to neutralize at least 20% of the free carboxylic acid groups in the component (A) is required. If the amount of the base is less than that, water solubility or water dispersibility is poor and the practicality as an electrodeposition coating cannot be endured. Examples of the base used for neutralization include ammonia, amines, alkali metal hydroxides, alkali metal carbonates or bicarbonates, and the like. Examples of the amine include primary, secondary or tertiary amines such as diethylamine, triethylamine, etc .; primary, secondary, tertiary alkanolamines or cycloamines,
For example, monoethanolamine, diethanolamine, triethanolamine, N, N-dimethylethanolamine; aromatic amines, for example, amines such as N, N-dimethylbenzylamine are used. Further, as the alkali metal hydroxide, sodium hydroxide, potassium hydroxide and the like; and as the alkali metal carbonate or bicarbonate, sodium carbonate, sodium bicarbonate and the like can be used. Among these bases, triethylamine is preferable.

If necessary, various organic solvents may be added to water for the purpose of improving water solubility or water dispersibility and adjusting the flowability of the coating material. Examples of this organic solvent include cellosolve-based solvents such as ethyl cellosolve and butyl cellosolve; glyme-based or diglyme-based solvents such as ethylene glycol dimethyl ether; and diacetone alcohol, 4-methoxy-4-methylpentanone-2, methyl ethyl ketone, and the like. A water-soluble organic solvent is exemplified, and the non-water-soluble organic solvent is xylene,
Aromatic hydrocarbons such as toluene; methyl isobutyl ketone, 2-ethylhexanol and the like are exemplified.

Further, the composition of the present invention is often used by incorporating various pigments and additives therein. As the pigment, titania, red iron oxide, color pigments such as carbon black, extender pigments such as aluminum silicate and precipitated barium sulfate,
And there are rust preventive pigments such as strontium chromate and basic lead silicate. Also, known emulsifiers and antioxidants can be used. The amount of the pigment used for the composition of the present invention is
It is 0 to 150 parts by weight, preferably 20 to 50 parts by weight, relative to 100 parts by weight of the composition of the present invention.

A conventionally known method can be applied to the electrodeposition coating operation itself performed using the composition of the present invention.

That is, the component (A), the component (B) and the pigment in the composition of the present invention are diluted with water or water containing the above-mentioned organic solvent so as to be contained in the electrodeposition bath so as to be 2 to 30% by weight. The article to be coated is immersed in this as an anode, and a coating film is deposited on the surface of the article to be coated by applying a suitable voltage to the other cathode. Usually 10 to 30μ by this electrodeposition coating
A coating film having a thickness of 1 is formed. After washing with water if necessary,
The coating film can be cured by heating at a temperature of around 80 ° C. Of course, if necessary, it can be heated and cured at a higher temperature.

The electrodeposition coating film obtained by using the composition of the present invention is cured at a low temperature, and if left at room temperature thereafter, the coating film hardness is further improved in a very short time and has a practically sufficient hardness.

[Effects of the Invention] The composition of the present invention has an unsaturated monocarboxylic acid residue and a conjugated diene bond, and by incorporating a metal compound, the performance of the conventional electrodeposition coating composition is improved by the synergistic effect of each component. In addition to this, it is a composition for electrodeposition coating composition which is excellent in low-temperature curability.

[Examples] Hereinafter, the contents of the present invention will be described more specifically with reference to production examples, examples, and comparative examples of the present invention.

1) Production of α, β-unsaturated dicarboxylic acid anhydride addition resin Production Example 1 Nisseki Polybutadiene B-700 (manufactured by Nippon Petrochemical Co., Ltd.,
Number average molecular weight = 700, vinyl 55%, trans 16%, cis 1
6%) 2000 g, maleic anhydride 778 g, Antigen 6C (Sumitomo Chemical Co., Ltd., N-methyl-N '-(1,3-dimethylbutyl) -p-phenylenediamine) 4 g and xylene 20
Charge 3 g into a 3 l separable flask and in a nitrogen stream at 195 ° C.
And reacted for 5 hours. Next, unreacted maleic anhydride and xylene were distilled off under reduced pressure to produce maleated liquid polybutadiene (M1) having a half acid value of 160 mgKOH / g.

Production Example 2 Nisseki Polybutadiene B-1500 (manufactured by Nippon Petrochemical Co., Ltd.,
Number average molecular weight = 1500, vinyl 65%, trans 14%, cis
16%) 2000 g, maleic anhydride 326 g, Antigen 6C (Sumitomo Chemical Co., Ltd., N-methyl-N '-(1,3-dimethylbutyl) -p-phenylenediamine) 4 g and xylene
Charge 20g into a 3l separable flask and place under a nitrogen stream for 195
The reaction was carried out at 0 ° C for 5 hours. Next, unreacted maleic anhydride and xylene were distilled off under reduced pressure to produce a maleated liquid polybutadiene (M2) having a half acid value of 80 mgKOH / g.

Production Example 3 200 g of dehydrated castor oil, Nisseki Polybutadiene B-2000 (manufactured by Nippon Petrochemical Co., Ltd., number average molecular weight = 2000, 65% vinyl,
Trans 14%, cis 16%) 800g, maleic anhydride 130g,
Antigen 6C (Sumitomo Chemical Co., Ltd., N-methyl-N'-
(1,3-Dimethylbutyl) -p-phenylenediamine) 2
g and xylene 10g into a 2l separable flask,
The reaction was carried out at 195 ° C. for 5 hours under a nitrogen stream. Then, unreacted maleic anhydride and xylene were distilled off under reduced pressure to obtain a half acid value.
80 mg KOH / g maleated resin (M3) was produced.

2) Production of conjugated diene bond-containing alcohol Production Example 4 Hydiene 500 (Soken Chemical Co., Ltd., conjugated fatty acid, conjugated linoleic acid 55%, acid value 198 mg KOH / g) 1000 g and triethylamine 72 g were placed in a separable flask with a cooling tube, Heated to 80 ° C. Next, 205 g of propylene oxide
Was placed in a dropping funnel with a stopper and was added dropwise to the separable flask over 2 hours. Then heat at 80 ℃ for 2 hours,
An alcohol (H1) containing a conjugated diene bond was produced. The acid value of this product is 1.8 mg KOH / g, and the hydroxyl value is 270 meq / 100 g.
Met.

Production Example 5 1000 g of dehydrated castor oil fatty acid (manufactured by Soken Chemical Co., Ltd., conjugated linoleic acid 42%, acid value 198 mg KOH / g), 531 g of phenylglycidyl ether and 72 g of triethylamine were placed in a separable flask equipped with a cooling tube, and the mixture was kept at 80 ° C. for 3 days. The mixture was heated for an hour to produce a conjugated diene bond-containing alcohol (H2). This product had an acid value of 1.0 mgKOH / g and a hydroxyl value of 210 meq / 100 g.

Production Example 6 Hydiene (Soken Chemical Co., Ltd., conjugated linoleic acid 60
%, Acid value 198 mg KOH / g) 1000 g, glycidyl methacrylate 503 g, hydroquinone 5 g and triethylamine 72 g
In a separable flask with a cooling tube, and under a nitrogen stream.
By heating at 80 ° C. for 3 hours, an alcohol (H3) containing a conjugated diene bond and a methacrylic acid ester bond was produced. This product had an acid value of 3.0 mg KOH / g and a hydroxyl value of 220 meq / 100 g.

3) Production of Modified Resin Production Example 7 500 g of maleinized liquid polybutadiene (M1) produced in Production Example 1, 215 g of diacetone alcohol and Production Example 4
The conjugated diene bond-containing alcohol (H1) (519 g) prepared in (4) was placed in a separable flask equipped with a cooling tube and placed under a nitrogen stream for 12 hours.
It heated at 0 degreeC for 2 hours, and manufactured the modified resin (A1) containing a conjugated diene bond and an acid group. The acid value of this product is 65 mg
KOH / g and nonvolatile content were 79%.

Production Example 8 In Production Example 7, cobalt naphthenate (cobalt content 8
%) Was added in the same manner as in Production Example 7 to produce a resin composition (A2) containing a conjugated diene bond and an acid group. The acid value of this product was 64 mgKOH / g, and the nonvolatile content was 78.6%.

Production Example 9 500 g of maleated liquid polybutadiene (M2) produced in Production Example 2, 134 g of diacetone alcohol, 93 g of hydroxyethyl methacrylate, 15 g of manganese naphthenate (manganese content 8%) and 14.5 g of triethylamine were placed in a separable flask with a cooling tube. The mixture was heated at 80 ° C. for 2 hours in a nitrogen stream to produce a modified resin (A3) containing a methacrylic acid ester bond and an acid group. The acid value of this thing is
It was 55 mgKOH / g and the nonvolatile content was 78.7%.

Production Example 10 Maleated liquid butadiene (M2) produced in Production Example 2
500g, ethylene glycol dimethyl ether 156g, 2-
Hydroxyethyl methacrylate 46.5 g, cobalt acetylacetonate (cobalt content 22.9%) 3.1 g and the conjugated diene bond-containing alcohol (H
129g of 1) is taken into a separable flask with a cooling tube,
The mixture was heated at 80 ° C for 2 hours under a nitrogen stream to produce a modified resin (A4) containing a conjugated diene bond, a methacrylic acid ester bond and an acid group. The acid value of this product was 55 mgKOH / g, and the nonvolatile content was 79.8%.

Production Example 11 500 g of the maleated resin (M3) produced in Production Example 3, 171 g of ethylene glycol dimethyl ether, 41.5 g of 2-hydroxyethyl acrylate, 3.2 g of manganese acetylacetonate (manganese content 21.7%) and Production Example 5 were produced. 154 g of conjugated diene bond-containing alcohol (H2) was placed in a separable flask equipped with a cooling tube and heated under a nitrogen stream at 80 ° C for 2 hours to obtain a modified resin (A5) containing a conjugated diene bond, an acrylic ester bond and an acid group. Was manufactured. The acid value of this product was 48.5 mg KOH / g and the nonvolatile content was 79.5%.

Production Example 12 500 g of maleated resin (M3) produced in Production Example 3, 197 g of ethylene glycol dimethyl ether, 3.6 g of cobalt acetylacetonate (cobalt content 22.9%) and conjugated diene bond and methacrylic acid ester group produced in Production Example 6 302 g of the contained alcohol (H3) was placed in a separable flask equipped with a cooling tube and heated under a nitrogen stream at 120 ° C for 2 hours to produce a modified resin (A6) containing a conjugated diene bond, a methacrylic acid ester bond and an acid group. did. The acid value of this product was 44 mgKOH / g, and the nonvolatile content was 79.5%.

The amount of free carboxylic acid groups, the amount of conjugated diene bonds, and the amount of α, β-unsaturated monocarboxylic acid residues of the modified resins produced in each production example are summarized in the table below.

4) Examples and Comparative Examples Example 1 400 g of a modified resin (A4) having a conjugated diene bond containing 1000 ppm of cobalt based on the resin solid content produced in Production Example 10, an α, β-unsaturated bond and an acid group, and triethylamine 23.3.
After g was placed in a 2 liter separable flask and stirred for 30 minutes at 50 ° C., 1177 g of deionized water was gradually added and dissolved uniformly to prepare an aqueous solution for electrodeposition having a solid content concentration of about 20%. This aqueous solution was placed in a 2 liter stainless beaker, and the beaker was used as an electrodeposition bath and as a cathode. A zinc phosphate-treated steel sheet (manufactured by Japan Test Panel Co., Bt # 3004 treatment) was used for the anode, and the temperature was 3 ° C at 30 ° C. The electrodeposition coating was performed for a minute. After electrodeposition coating, the article to be coated was washed with water and dried in a drying oven at 80 ° C for 20 minutes. The test results are shown in Table 2.

Example 2 400 g of a modified resin (A5) having a conjugated diene bond, α, β-unsaturated bond and an acid group containing 1000 ppm of manganese based on the resin solid matter produced in Production Example 11 and triethylamine 21.4
After g was placed in a 2 liter separable flask and stirred for 30 minutes at 50 ° C., 1179 g of deionized water was gradually added and dissolved uniformly to prepare an aqueous solution for electrodeposition having a solid content concentration of about 20%. This aqueous solution was placed in a 2 liter stainless beaker, and the beaker was used as an electrodeposition bath and as a cathode. A zinc phosphate-treated steel sheet (manufactured by Japan Test Panel Co., Bt # 3004 treatment) was used for the anode, and the temperature was 3 ° C at 30 ° C. The electrodeposition coating was performed for a minute. After electrodeposition coating, the article to be coated was washed with water and dried in a drying oven at 80 ° C for 20 minutes. The test results are shown in Table 2.

Example 3 400 g of a modified resin (A6) having a conjugated diene bond, α, β-unsaturated bond and an acid group containing 1000 ppm of cobalt based on the resin solid content produced in Production Example 12 and triethylamine 22.6.
After g was placed in a 2 liter separable flask and stirred for 30 minutes at 50 ° C., 1177 g of deionized water was gradually added and dissolved uniformly to prepare an aqueous solution for electrodeposition having a solid content concentration of about 20%. This aqueous solution was placed in a 2 liter stainless beaker, and the beaker was used as an electrodeposition bath and as a cathode. A zinc phosphate-treated steel sheet (manufactured by Japan Test Panel Co., Bt # 3004 treatment) was used for the anode, and the temperature was 3 ° C at 30 ° C. The electrodeposition coating was performed for a minute. After electrodeposition coating, the article to be coated was washed with water and dried in a drying oven at 80 ° C for 20 minutes. The test results are shown in Table 2.

Comparative Example 1 Includes 2000 ppm of cobalt based on the resin solid content produced in Production Example 8 and has a conjugated diene bond and an acid group, but α, β
-400 g of modified resin (A2) containing no unsaturated bond and 25.8 g of triethylamine were placed in a 2 l separable flask, stirred at 50 ° C for 30 minutes, and then uniformly dissolved while gradually adding 1174 g of deionized water. An aqueous solution for electrodeposition having a concentration of about 20% was prepared. This aqueous solution was put into a 2 liter stainless beaker, and the beaker was used as an electrodeposition bath and as a cathode. The anode was a zinc phosphate treated steel plate (Japan Test Panel Co., Bt
# 3004 treatment) was used and electrodeposition coating was performed at 30 ° C. for 3 minutes. After electrodeposition coating, the article to be coated was washed with water and dried in a drying oven at 80 ° C for 20 minutes. The test results are shown in Table 2.

Comparative Example 2 The resin produced in Production Example 9 contains 2000 ppm of manganese based on the solid content of the resin and has an α, β-unsaturated bond and an acid group,
400 g of a resin composition (A3) containing no conjugated diene bond,
Triethylamine (11.4 g) was placed in a 2-liter separable flask and stirred for 30 minutes at 50 ° C., and then deionized water (1189 g) was gradually added and dissolved uniformly to prepare an aqueous solution for electrodeposition having a solid content concentration of about 20%. This aqueous solution was placed in a 2 liter stainless beaker, and the beaker was used as an electrodeposition bath and as a cathode. A zinc phosphate-treated steel sheet (manufactured by Japan Test Panel Co., Bt # 3004 treatment) was used for the anode, and the temperature was 3 ° C at 30 ° C. The electrodeposition coating was performed for a minute. After electrodeposition coating, the article to be coated was washed with water and dried in a drying oven at 80 ° C for 20 minutes. The test results are shown in Table 2.

Comparative Example 3 In 400 g of modified resin (A4 ′) having a conjugated diene bond, α, β-unsaturated bond and acid group, which was obtained by reacting in the same manner as in Production Example 10 except that cobalt acetylacetonate was not used. Transfer 23.3 g of triethylamine to a 2 liter separable flask and stir at 50 ° C for 30 minutes, then use deionized water.
Dissolve 1177 g uniformly while gradually adding it to a solids concentration of about 2
A 0% aqueous solution for electrodeposition was prepared. This aqueous solution was put into a 2 l stainless beaker, and the beaker was used as an electrodeposition bath and as a cathode, and a zinc phosphate-treated steel plate (Bt # 3004 treated by Nippon Test Panel Co., Ltd.) was used as an anode at 30 ° C for 3 minutes. Electrodeposition coating was performed. After electrodeposition coating, wash the coated object with water and
It was dried in a drying oven at ℃ for 20 minutes. The test results are shown in Table 2.

Claims (3)

(57) [Claims] (A) A drying oil having a number average molecular weight of 500 to 10,000 or a conjugated diene polymer or copolymer is modified, and an acid value per modified product g is 10 to 300 mgK.
Free carboxylic acid group of OH / g, conjugated diene bond is 10 meq or more per 100 g of modified product, and the following formula (Wherein R ₁ and R ₂ are hydrogen atoms or methyl groups), 100 parts by weight of a modified product having an α, β-unsaturated monocarboxylic acid residue of 10 meq or more per 100 g of the modified product, and (B) cobalt. Containing 0.001 to 1.0 part by weight of an organic compound or inorganic compound of one or more metals selected from the group consisting of, manganese, iron, nickel, lead, zinc and chromium in terms of metal, (A) A composition for electrodeposition coating, characterized in that a modified carboxylic acid group of a component is at least partially neutralized with a base and dispersed or dissolved in water. 2. The modified product (A) has a number average molecular weight of 500 to 1
0000 drying oils or conjugated diene polymers or copolymers
To 100 g, 0.05 to 0 of the α, β-unsaturated dicarboxylic acid anhydride is added.
5 mol added, then alcohol with conjugated diene bond and the following formula (Wherein R ₁ and R ₂ are a hydrogen atom or a methyl group, R ₃ is an alkyl group having 2 or more carbon atoms), and α, β-unsaturated monocarboxylic acid hydroxyalkyl ester containing an aliphatic hydroxyl group is represented by The composition for electrodeposition coating composition according to claim 1, which is a modified product obtained by further modification. 3. The modified product (A) has a number average molecular weight of 500 to 1
0000 drying oils or conjugated diene polymers or copolymers
To 100 g, 0.05 to 0 of the α, β-unsaturated dicarboxylic acid anhydride is added.
5 mol was added, followed by conjugated diene bond and the following formula The compound according to claim 1, which is a modified product obtained by reacting an alcohol containing an α, β-unsaturated monocarboxylic acid residue represented by the formula (wherein R ₁ and R ₂ are hydrogen atoms or methyl groups). The composition for electrodeposition paint of.