JPS60219272A - Cathodic electrodeposition paint composition - Google Patents

Abstract

PURPOSE:To provide a cathodic electrodeposition paint compsn. which is low- temperature curable and has excellent corrosion resistace, containing a high- molecular compd. contg. amino groups, a reaction product of a glycidyl compd. with a specified org. acid and a specified manganese compd. CONSTITUTION:A paint compsn. contains 100pts.wt. high-molecular compd. (A) having an MW of 500-5,000 and a carbon-to-carbon double bond content of 50- 500 in terms of iodine value and contg. 30-300mmol of amino group per 100g of the compd., 10-200pts.wt. reaction product (B) obtd. by reacting a glycidyl compd. (1) of formula I (wherein R1, R2 are each H, etc.; n is 0-20), 0-1.80mol (per mol of the glycidyl compd.) of an alpha,beta-unsaturated catboxylic acid (2) of formula II (wherein R3, R4 are each H, etc.) and 2.1-0.30mol (per mol of the glycidyl compd.) of an unsaturated fatty acid (3) having an MW of 100-350 and a carbon-to-carbon conjugated double bond content of 10wt% or above, and 0.005-1.0pt.wt. (in terms of metal) manganese salt of an org. acid or manganese dioxide (C).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention produces a cathode-deposited electrodeposited resin with excellent low-temperature curability, and when electrodeposition coating is performed using this, the resin is deposited on the cathode. This type of cathodically deposited paint overcomes the electrical drawbacks of conventional anodicly deposited electrodeposition paints, which are made water-soluble by neutralizing the entire base of the resin, which has acid groups, namely, exposure to the paint bath. It can completely eliminate the elution of coating metals and the various problems caused by it.

The present inventors conducted research on such cathodic deposition type paints,
First, excellent coating properties were obtained by introducing amino groups into a low polymerization degree synthetic polymer having carbon-carbon double bonds, for example, a high molecular weight compound containing an unsaturated group, such as liquid butadiene, and neutralizing it with acid. He discovered that it was possible to obtain a cathode-deposited electrodeposition paint resin, and filed a patent application (Japanese Patent Laid-Open No. 51-11).
9727, JP-A-52-1476:48, JP-A-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 the coating film could be cured at a relatively low baking temperature by adding a metal dryer such as a water-soluble manganese salt, and filed a patent application (@ Kaisho 53 -1424441° In this case, a large amount of dryer is required, which deteriorates the performance of electrodeposition coating such as throwing power, and causes problems such as roughening of the painted surface. He discovered a method for introducing methacrylic double bonds into the resin and curing it at a relatively low baking temperature (Japanese Patent Application Laid-Open No. 151777/1983). A cathodically deposited electrodeposition coating that cures at low temperatures and has excellent performance is obtained.

However, in recent years, it has been desired to lower the baking temperature in the center from the viewpoint of energy saving, and the inventors of the present invention have conducted various studies and found that it is added for the purpose of improving corrosion resistance. It was discovered that the baking temperature could be lowered by introducing many double bonds with high
We have arrived at the present invention.

Accordingly, an object of the present invention is to provide a cathodically deposited electrodeposition coating material which improves the curability of the resin and has low temperature curability and excellent corrosion resistance.

That is, the present invention provides carbon-carbon double bonds with a molecular weight of 500 to 5.000 and an iodine value of 50 to 500 and 30 per ioog.
10 to 0 parts by weight of a polymer compound having ~300 mmol of amino-11m (B) il + general formula % formula % [In the formula, R,, R, is an aqueous atom or a methyl group at 7'C, 71 is 0 to 20 preferably represents an integer from 1 to 10] A diglycidyl compound represented by (2) the general formula % formula % of 0 to 1.80 mol per molecule of the diglycidylated adduct [wherein R3 and R4 are Molecular weight 100 to 21 to 0.3 mol per molecule of hydrogen atom or methidiglycidyl compound
10 to 200 coulometric parts of reaction products of unsaturated fatty acids containing 10% or more of carbon-carbon conjugated double bonds (C+ -a-like manganese tomb or mammary dioxide: y sword y 0.005 to 1. This is a cathodically deposited electrodeposition coating composition with excellent low temperature curability, containing r as an essential component.

The starting material for the (,41) component of the present invention is 500-5,0
00 molecular weight and 50 to 500 iodine [[1b carbon-
Polymer compounds having carbon double bonds (1) manufactured by conventionally known methods.

That is, using an alkali metal or an organic alkali metal compound as a catalyst, a conjugated diolefin having 4 to 10 carbon atoms alone, or these diolefins together, or an aromatic vinyl monomer in an amount of 50 mol% or less based on the conjugated diolefin, For example, styrene, α-methylstyrene, vinyltoluene or divinylbenzene, and =(0'(:, ~1
A typical manufacturing method is wet IfT anionic polymerization or copolymerization at 00°C. In this case, in order to control the molecular weight and obtain a light-colored low polymer with a low glycerin content, an organic alkali metal compound such as sodium benzyl is used as a catalyst, and an adduct having an alkylaryl group, such as toluene, is chained. A chain transfer polymerization method using a transfer agent (US Pat. No. 3,789,090) or a living polymerization method using a polycyclic aromatic compound such as naphthalene as a total activator and an alkali metal such as sodium as a total catalyst in a tetrahydrofuran solvent (Tokuko Showa) No. 42-17485, No. 43-274
No. 32) Alternatively, use an aromatic hydrocarbon such as toluene or xylene as a bath medium, a dispersion of an alkali metal such as sodium as a catalyst, and control the molecular weight by cooling an ether such as diocypone. Poro law ζ Kosho 32-74
No. 46, No. 38-1245, No. 34-10188 J
etc. are suitable manufacturing methods. It can also be produced by coordination anion 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. 4S-80300) low polymers can also be used.

The component t, 4) of the present invention, that is, the polymer compound having a carbon-carbon double bond with a molecular weight of 500 to 5,000 and an iodine value of 50 to 500 and an amino group of 30 to 300 mmol per Iooy is a conventionally known polymer compound. manufactured by the method.

For example, when maleic anhydride is added to a polymer compound having a carbon-carbon double bond, the general formula [where R, /
U hydrocarbon group having 1 to 20 carbon atoms, R7' and R3'
represents a hydrocarbon group having 1 to 20 carbon atoms in which the hydrogen atom is omitted or a part thereof may be substituted with a hydroxyl group] A method of introducing an amino group by reacting a diamine compound represented by -119727, JP-A-52-1
47638% JP-A-53-8629, JP-A-53-63
4391 or a method of epoxidizing a polymer compound having a carbon-return double bond using a peroxide such as hydrogen peroxide or peracid, and then adding a -class or secondary amine after fc (
JP 53-16048, JP 53-117030)
etc. are known.

Preferably (as an example of the A1 component, a high molecular weight compound having a carbon-carbon double bond with a molecular weight of 500 to 5.000 and an iodine value of ioo to 500 is epoxidized to form a carbon-carbon double bond of 3 to 1
An epoxidized high molecular weight compound containing 2% by weight of oxirane oxygen is prepared, and a part of the epoxy group of the epoxidized high molecular weight compound is expressed by the general formula, where R4' and Rs' each independently represent the number of carbon atoms. 1
~10 hydrocarbon groups, each group may be partially substituted with a hydroxyl group, or may form a ring structure with R, / H, /. [In the formula, R6' and R7' represent a hydrogen atom or a methyl group, and at least one of the remaining epoxy groups is reacted with a basic amine compound represented by the following: is a hydrogen atom] It can be produced by reacting an α,β unsaturated monocarboxylic acid represented by - It is also possible to react an unsaturated fatty acid containing 10% by weight or more of carbon conjugated double bonds i. Furthermore, after adding maleic anhydride to a polymer compound having a carbon-carbon double bond, general 1 to 2 carbon atoms, some of which may be substituted with hydroxyl groups
Method for introducing 0 hydrocarbon groups into the table (JP-A-51-119
727, JP-A-52-147638, JP-A-5A-G6
2a, JP-A-53-63439) can also be used.

The diglycidyl compound of the present invention (l component, that is, (11 general formula % formula % [wherein R,, R, is a hydrogen atom or a methyl group, and n represents an integer from 0 to 20, preferably from 1 to 10] , (2) General formula % of O to 1.80 mol per molecule of the diglydyl compound of (1) above
Formula % [In the formula, R3 and R4 represent a hydrogen atom or a methyl group. ] Corrosion resistance and hardenability are significantly improved by adding a product obtained by reacting an unsaturated fatty acid with a molar molecular weight of 100 to 350 and containing 10% by weight or more of carbon-carbon conjugated double bonds.

The content of component [1] is in the range of 10 to 200 parts by weight, preferably 30 to 100 parts by weight, based on 100 parts by weight of the resin.

If the content of component i) is less than this, the improvement in corrosion resistance will not be sufficient, and if it is more than this, water dispersibility will be deteriorated.

In order to obtain the compound of the above component (B), the compound of the general formula [wherein R
, R is a hydrogen atom or a methyl group, and 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 be prepared by etherifying bisphenol with epichlorohydrin, usually in the presence of an alkali. Such bisphenol compounds include 2,2-bis(4'-hydroxyphenyl), 1,1-pix(4'-hydroxyphenyl)ethane, and 1,1-bis(4'-hydroxyphenyl). phenyl)imbuta7.2.2-bis(4'-human axyphenylonmethane, etc.).In many cases, further reaction of the diglycidyl compound described above with bisphenol etc. and then further reaction of this product with epichlorohydrin results in Diglycidyl compounds with somewhat higher molecular weights were synthesized,
You can use one of these.

The above diglycidyl compound is heated to a temperature of 0 to 200°C, preferably 50 to 150°C, and has the general formula % [wherein R1 and R4 represent a hydrogen atom or a methyl group]. ] Carbon-carbon co-U31 can be produced using α, β unsaturated carboxylic acid represented by 0 to 1.80 mol and a molecular weight of 100 to 350. The α,β unsaturated cargonic acids used here include acrylic acid, methacrylic acid, crotonic acid, cinnamon, etc., and mixtures thereof can also be used. Molecular weight 1
Examples of unsaturated fatty acids containing 00 to 350 and 10% or more of carbon-carbon conjugated double bonds include sorbic acid, Chinese tung oil fatty acid, sunflower oil fatty acid, and dehydrated castor oil fatty acid, as well as soybean oil fatty acid, linseed oil fatty acid, etc. Conjugated fatty acids that are conjugated by isomerizing defenses, etc. can also be used, and purified eleostearic acid and conjugated linoleic acid can also be used. Also, by mixing an unsaturated fatty acid with a large number of conjugated double bonds with an unsaturated fatty acid having 10% or less of carbon-carbon conjugated double bonds, the total number of conjugated double bonds can be reduced to 1.
Mixtures with a concentration of 0 or more can also be used. Among them, dehydrated castor oil is advantageous and preferred because it is easily available industrially.

When carrying out the reaction, 0.01 to 1.0% of a radical polymerization inhibitor such as hydroquinone, methoquinone, A-phenyl/N'ingavir-P-phenylenediamine is added to prevent side reactions. It is preferable to use a suitable catalyst such as tertiary amines or quaternary ammonium salts. The reaction can be carried out in the presence or absence of a solvent, but if a solvent is used, it is inert to the reaction, and solvents that can be used in electrodeposition coatings, such as ethylcerone acetate and MIBK, can be used. It is practically advantageous to use it in an electrodeposition coating without removing the reaction plate and mixing it with component 1A) and component (C) as it is.

(.

In the present invention, it is preferable that the glycidyl compound is partially converted into -0-CB, -CH- groups by reacting with the lugic acid group in the glycidyl compound molecule.

For example, this group can be added to the resin (A
), causing an unfavorable reaction with the basic group possessed by the compound, resulting in an increase in viscosity and impediment to water solubilization.

For example, even if water-solubilization is achieved, the aqueous solution changes over time, resulting in defects such as failure to obtain fixed electrodeposited physical properties or an electrodeposited coating film.

Conventionally, bisphenol-type epoxy resins have been known as resins with excellent corrosion resistance.
No. 23807, Japanese Patent Publication No. 51-158601, attempts have been made to use blocked isocyanate compounds as crosslinking agents. However, such paints require high temperatures of over 200°C in order to obtain the full practical hardness.
Even when curing is possible at a relatively low temperature, there are drawbacks such as only being able to select a baking temperature within a narrow range.

Saranibisphenol type epoxy resin must have a certain degree of monomolecular structure under practical electrodeposition conditions, and as a result, the coating film tends to lack flexibility.

Therefore, according to the present invention, the diglycidyl compound Y-C1
The compound H1) converted to i, -CM-CM, - is used as a component of the cathode-deposited electrodeposition paint, and the resin (
, 4), thereby allowing the resin (
It is truly gratifying that it has been found that the corrosion resistance of 1 can be significantly improved without impairing the excellent curability and film properties of 1.

The <C+ acid component of the present invention, i.e., the manganese salt of iskiic acid, includes water-soluble manganese salts such as manganese formate, manganese acetate, manganese lactate, manganese naphthenate, manganese octylate, and the general formula [wherein R, R8 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; however, R7 and R8 can each have a 6-negative ring structure or a heterocyclic structure containing a 5-membered ring and a 6-membered ring; can contain an unsaturated oro group.

R represents an organic residue having 1 to 20 carbon atoms which may contain an ether bond, an ester bond, and an unsaturated group.

X and X represent a hydrogen atom, an organic residue having 1 to 10 carbon atoms, or a bond, and when XI and X are a bond,
The attached carbons of 1 and 2 can form a two-way bond with each other.
, O, (By adding 15 to 1.0 parts by weight, curing properties are significantly accelerated and a low-temperature curable cathodically deposited electrodeposition coating material is obtained.

Although there is a manganese salt of an organic acid as component (C) of the present invention, it is small, and if the amount is more than 1.0 parts by weight, curability is good, but water dispersibility, corrosion resistance, etc. are deteriorated, so it is not preferable. The preferred range r is 0.01 to 0.5 parts by weight of the metal.

In the present invention, component (A), component (B) and component (C
) In order to water-solubilize or water-disperse a composition consisting of components (A), component < E), and component (C), after premixing component (, −
20 Preferably, it is preferably neutralized with 0.2 to 1.0 molar equivalent of a water-soluble organic acid such as acetic acid, 10 pionic acid, or lactic acid to make it water-soluble.

Compositions of the invention (i, (B) and (C1) dissolved in water
When dispersing, c facilitates dissolution or dispersion,
Ethyl cellosolve, globil cellosolve, which is water-soluble and can dissolve various resin compositions, is used for the purpose of improving the stability of aqueous solutions, improving the fluidity of resins, and improving the smoothness of coating films. Butylceronlube, ethylene glycol dimethyl ether, cyethylene glycol dimethyl ether, diacetone alcohol, 4-methoxy-~100
Preferably, parts by weight are used.

The cathodically deposited electrodeposition coating composition of the present invention may further contain a suitable pigment. For example, iron oxide, lead oxide, strontium amate, car d? One or more pigments such as 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 in advance, a large amount of the pigment is added to a portion of the neutralized component (4+ and dispersed in water or made into an aqueous solution) and mixed.
A pasty master patch can be obtained and this pasty pigment can be added to the composition.

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. In addition, the physical property test of the coating film of Examples and Comparative Examples r
I caught a dJ Is -sao oK and got a 6.

Production example 1 Nisseki polybutadiene B-1. g001 number average molecular weight 18
00,1.2 bond (64%) was epoxidized using peracetic acid to produce epoxidized polybutadiene (El 2 ) having an oxirane oxygen content of 6.5%.

This epoxidized polybutadiene (E,) 1.00OS and ethyl cellosolve 358g and methylethanolamine 75.1.9f: 3A! The mixture was placed in a Senon rubber flask and reacted at iso°C for 6 hours. After reaction, 120℃
Cool to acrylic acid 79.21! , hydroquinone 7.29 and ethyl cellosolve 2'19 were added and reacted at 120° C. for 4 hours to prepare a resin solution (A+)lr of component A of the present invention.

Amine value of this product f 67.5fnrnol / 1
00 El, acid value is 9.9 mmo L/100
I! , and the solid content concentration was 75% by weight.

Production Example 2 Nisseki Polybutadiene B-2ooo was produced into number average molecular silicided polybutadiene (E,).

After charging 333 g of this epoxidized polybutadiene (Exll, 0OQI and ethyl cellosolve) into a 21 autoclave, 62.19 g of dimethylamine was added,
The reaction was carried out at ℃ for 5 hours. After distilling off unreacted amine,
79.3 g of acrylic acid, 7,5 II of hydroquinone and 26.5 g of ethyl cellosolve! y mixture and further reacted at 150°C for 45 minutes to form the components of the present invention (,
A resin solution (l!) of () was prepared. The amine value i188.7 mmol/100&% acid value of this is 10.6
mmol/100g and solids concentration is 75.0% by weight
Met.

Production example 3 Nisseki polybutadiene B-2000 (number average molecular weight 200
0.1.2 bond 65%l 1,000! ! , maleic anhydride 168.9. 10g of xylene, anti-r73C (
2 g of Sumitomo Chemical (product name) was placed in a 21 separable flask fully 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. ! i+
The maleated polyptadiene (M,) was synthesized.

Next, 1,000 g of maleated polybutadiene (M),
Ethyl cellosolve 200.9 was charged into a 2-7 paraple flask equipped with a reflux condenser and heated to 80° C. with stirring. Next, N,N-dimethylamine 1461
1 drop was added. Immediately raise the temperature to 150℃ after the final T.
The reaction was continued at 150°C for an hour. The produced water, ethyl cellosolve and unreacted amine were distilled off under reduced pressure to synthesize imidized polybutadiene having a tertiary amine group. One amine of this imidized polyphtadiene is 132 mmol/100. ! It was i'. This imidized polybutadiene was dissolved in ethyl cellosolve so that the solid content was 75% by weight, and the resin solution (A3) of the components 1 and 4 of the present invention was dissolved.
) was manufactured.

Production Example 4 The following compound obtained by reacting bisphenol A and epichlorohydrin in the presence of a gold alkali decomposition solvent, CH3, is a bisphenol type epoxy resin with an epoxy resin of 500'i. ,000 y-q Dissolved in 338 g of ethylseron lube and dehydrated castor oil (manufactured by Ito Oil Co., Ltd.) 2
81.9. Acrylic acid 72g, hydroquinone 0.5
g and 5 g of N,N-dimethylaminoethanol were added and heated to 100°C to react between 71 groups to form an ethyl cellosolve solution of the epoxy resin-unsaturated orocarboxylic acid adduct (Component IB) of the present invention. Synthesized B+Je.
Kiso 11 mountain 0.2 (mtnol / 1 o O,! /
)Met.

Production Example 5 Bisphenol type epoxy resin with epoxy adhesion of 950i [trade name Epicoat, 1004, manufactured by Yuka Shell Epoxy@] 1. o o o It-<Dissolved in ethyl cellosolve 395.9, eleostearic acid x4? l
Add 38 g of acrylic acid, 0.39 g of hydroquinone and 5 g of N,N-dimethylbenzylamine,
This was an ethyl cellosolve solution of the 4t resin-unsaturated carboxylic acid adduct, which is component [1] of the present invention, and was heated to 0.degree. C. and reacted for 7 hours.

Production example 6 Bisphenol type epoxy resin with epoxy equivalent of 950 [trade name Epicote 1004] 1, o o
o,! Dissolve i' in 385g of butyl cellosolve,
Highly conjugated linoleic acid [trade name] manufactured by Idien Soken Chemical Co., Ltd.] xxt, a, p, acrylic acid 47. ! 0.5 g of N,N-hydroquinone and 5 g of N,N-dimethylaminoethanol were added, heated to 110°C, and reacted for 5 hours to form the epoxy resin-unsaturated carbon component [1] of the present invention. ? Butyl cellosolve solution of acid adduct (B3)
was synthesized.

This solution had an acid value of 5 (mmol/100.9) and an epoxy value of 0.2 (mmol/100 & ).

Production example 7 Bisphenol type epoxy resin with 1500Q per epoxy [trade name Ebiko] 1001:] 1, o o
Dissolve o y in ethyl cellosolve 31211, dehydrated castor oil [manufactured by Ito Ura Oil ■] 1 '41 g, acrylic acid 108I! , hydroquinone 0.2 g and NlN-
Adding 5 g of dimethylaminoethanol and using the same reaction conditions as in Production Example 4, an ethyl cellosolve solution (B4) of the epoxy resin-unsaturated carboxylic acid adduct, component [11] of the present invention, was synthesized. This solution has an acid value s (mmol
/ 1001 lugin], epoxy value 0.3 mmol
/1001).

Production Example 8 Bisphenol type epoxy resin having an epoxy weight of 1d500 [trade name Echt 1001. ? [Made of [I] shell epoxy] 1.000 gi z chinz-h'
Dissolved in 286 g of A-lube, added 144 g of acrylic acid, 10.9 g of hydroquinone, and 5 g of N,N=dimethylaminoethanol, and heated the cocoon to 100° C. for 5 hours to react. An ethyl cellosolve solution 1t13.1 of an epoxy resin-ac 1-nolic acid adduct as a component used in a comparative example was synthesized.

Production example 9 1,000 g of bisphenol type epoxy resin with an epoxy equivalent of 950 [trade name Ebiko 1004, made by Yuka Shell Epoxy ■] was mixed with 358 g of ethyl cellosolve.
Dissolved in acrylic v116 & hydroquinone 10
g and N,N dimethylaminoethanol 5I were added, heated to 100° C. and reacted for 5 hours to obtain an ethylcetate of the epoxy resin-acrylic acid adduct of the components used in the comparative example of the present invention.

Sorp solution [Bn] was synthesized.

Production Example 10 The following compound CH1 CE was obtained by reacting bisphenol A and epichlorohydrin in the presence of an alkali catalyst.

As, epoxy equivalent 955't: Bisphe/-Lutide epoxy 7 resin [trade name Epicote 1004, manufactured by Yuka Shell Epoxy ■] i,' o o o g2 Ethyl cellosolve acetate dissolved in 395.9 M, acrylic acid 37 g , soybean oil fatty acid 144g, hydroquinone 1
2g and 61g of N,N-dimethylamine ethanol were added, heated to 100°C and reacted for 5 hours, and an ethylcerone rub acetate solution (B7 ) was synthesized.

Production example 11 Nisseki polybutadiene B-'100 (number average molecular weight 70
0.1.2 Bond 52% 1. ooo, p, 117.3 g of anhydrous Vine, antigun 3C1ji, and xylene 1 (H?) were charged into a 2E round-armed flask fully equipped with a reflux condenser and reacted at 195°C for 5 hours under a nitrogen stream.Next Then, unreacted maleic anhydride and xylene were distilled off under reduced pressure to synthesize maleated polybutadiene (M) having an acid value of 107 mmol/100.9.

Maleated polybutadiene (#21 500,9) and 148 g of ethyl cellosolve were reacted at 1120°G for 2 hours to open the cast water succinic acid group, and then cooled in a super-temperature trench and gradually added with 100 g of a 2ZSii value% aqueous solution of caustic soda. After neutralization, deionized water was added so that the solid content was 2 sit% to prepare an aqueous solution of maleated polybutadiene.

Next is acetic acid? 7 Guys (AinS04-4.5H2O) 7
After dissolving 4.5.9 in 600 g of water, 60 g of Inglobil alcohol (1.00 g, !F) was added, and 2,192 g of the maleated polybutadiene aqueous solution was gradually added dropwise at room temperature while stirring. 60℃ after gamma painting
After heating for 30 minutes, it was left to stand for 1 hour and it separated into two layers, so I cut off the lower layer and added 1. Add ooog 6
After heating to 0° 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 manganese salt of maleated polybutadiene by double decomposition method.

The manganese salt of this maleated polybutadiene was dissolved in ethyl cellosolve to a solid content of 75% by weight to produce a solution (C8) of an oil-soluble manganese salt of the component (C1) of the present invention (IC+) containing manganese. The amount was 2% by weight.

Example 1 (A,) 400. produced in Production Example 1. li', Production Example 4
After mixing 11115 g of B, 11115 g of butyl cellosolve and 5 g of butyl cellosolve until homogeneous, 6.5 g of acetic acid was added and thoroughly stirred to neutralize. Next, deionized water was gradually added until the solid content was 20%. % aqueous solution was prepared.

4000g of this 20% by weight aqueous solution, carbon blank 4
g, basic lead silicate 2019 and glass beads 2,000
0g was placed in a 51 stainless steel beaker and stirred vigorously for 2 hours in a high-speed rotating mixer, filtered through glass peas, and added deionized water containing 1.29f of manganese acetate to a solid content of 15M%. In addition, an electrodeposition paint fL was prepared.

A carbon electrode was used as an anode using the above electrodeposition paint g, and a phosphoric acid lead treated plate (Japan Test Panel Co., Ltd., Bt 3004) was used.
, O, gx70x150 order) was used as a cathode for anodic deposition type electrodeposition coating. The test results are shown in Table-1.

Comparative Example 1 All procedures were carried out except for using (B,) produced in Production Example 8 instead of (B1) produced in Production Example 4. A corner electrodeposition type electrodeposition coating solution was prepared under exactly the same conditions as in IJ 1, and a test was conducted under the same conditions as in Example 1. The results are shown in Table 1.

Table 1 Test results Note 1) Rubbing test with methyl imbutyl ketone (
50 times per minute Judgment is as follows.

○ Unchanged, scratched area becomes cloudy, × base material negative note 2) Judgment as follows during the maximum rust from the cut part made on the paint film.

◎1 or less, 01-2 Tomo, △2-3W.

X3m or more (5% NaCl 1 water M liquid sugley 1 Example 2 (As) 400Ji 1% produced in Production Example 2 (73t) 240.ii+ produced in Production Example 5 was mixed until homogeneous, then vinegar [8° Oy was added and thoroughly stirred to neutralize.Next, deionized water containing 0.8.9 manganese acetate'i was gradually added to prepare an aqueous solution with a solid content concentration of 25% by weight.This 25% by weight aqueous solution 1. 000 g, carbon black Z51!, basic silicate sharp 251i', and 1.000 g of glass beads were placed in a 3Jl' stainless steel beaker and stirred vigorously for 2 hours with a high-speed rotating mixer. After filtering the glass beads, the solid concentration was determined. Deionized water was added to give a concentration of 18% to prepare an electrodeposition coating solution A14.

Using the above electrodeposition coating liquid, a carbon electrode was used as an anode, and a zinc phosphate treated plate (Japan Test Nononel Co., Ltd., Be2O, 04
, o, 5x70x150B) was used as a cathode, and all cathodic deposition type electrodeposition coating was performed. The test results are shown in Table-2.

Example 3 A cathode-deposited electrodeposition coating solution was prepared under exactly the same conditions as in Example 2, except that Ba) produced in Production Example 6 was used instead of (B, ) produced in Production Example 5. A test was conducted under the same conditions as in Example 2, and the results are shown in Table 2.

Comparative Example 2 In place of (B,) produced in Production Example 5, the cathode-deposited electrodeposition coating solution 'f produced in Production Example 9 was prepared under exactly the same conditions as in Example 112 except for using Bal. A test was conducted under the same conditions as in Example 2, and the results are shown in Table 2.

Comparative Example 3 A cathode-deposited electrodeposition coating liquid was prepared under exactly the same conditions as Example 2, except that (B, ) produced in Production Example 10 was used instead of fC (Bz ) produced in Production Example 5. 4 (31400II produced in Production Example 3, (B4) 150JF produced in Production Example 7, and (C,) 4211 produced in Production Example 11 were mixed until homogeneous, then 8.5 g of acetic acid was added and thoroughly mixed. The mixture was stirred until it became stale. Next, deionized water was gradually added to prepare an aqueous solution having a solid content concentration of 30% by weight.

This 30% by weight aqueous solution 1. Q OOg, carbon black 3g, basic lead silicate 20.9 and glass peas i
, 0OOJ+ were placed in a 31 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 16% to prepare an electrodeposition coating solution.

Using the above electrodeposition coating liquid, a carbon electrode was used as an anode, and a zinc phosphate-treated plate (Japan Test Quenell Co., Ltd., Bt3004.
0.8 x 70 x 150 m) was used as a cathode, and cathodic deposition type electrodeposition coating was performed. The test results are shown in Table-3.

Comparative Example 4 A cathodically deposited electrodeposition paint was prepared under exactly the same conditions as in Example 4, except that (B,] produced in Production Example 8 was used instead of fc (Ba) produced in Production Example 7, and carried out. A test was conducted under the same conditions as in Example 4, and the results are shown in Table 53.

Table 3 Test results Note 1) Rubbing test with mether isoptylctone (
50 times per minute) and judged as follows. ○ Unchanged, Δ The rubbed area becomes cloudy,

◎1+u or less, 01-2ryu, Δ2-3關, X3+n+ or more (5% NaCl water soluble a s yv-) Procedural amendment August 17, 1980 Manabu Shiga, Commissioner of the Japan Patent Office 1, Patent application for indication of the case No. 59-73880 2, Title of the invention: Cathode-deposited electrodeposition coating composition 3, Relationship with the Nagisa case to be amended Patent applicant address: 3-12 Nishi-Shinbashi-chome, Minato-ku, Tokyo (1) Specifications of the present application On page 7, line 9 of the book, "The description of molecular weight 100-300J is corrected to 1 molecular weight 100-350J."

(2) On page 12, line 13, the statement ``Reacting with unsaturated fatty acids'' is corrected to ``Reacting instead of unsaturated fatty acids.''

(3) The description of "diglycidyl compound" on page 14, lines 7-8 is corrected to "diglycidyl compound J."

(4) The description of "diglycidyl ether" in lines 2 to 1 from the bottom of page 16 will be corrected to "diglycidyl ether."

(5) [Propyl cellosolve] on page 24, lines 11-12
The description of ``propyl cellosolve'' has been corrected to ``propyl cellosolve''.

(6) The description of "4-methoxy-4-methylpentanone-2" on page 24, lines 14-15 is corrected to "4-methoxy-4-methyl-2-pentanone."

(7) The description of "reflux condenser" in lines 5 and 12 of page 28 will be corrected to "reflux condenser."

((e) On page 29, line 10, the description of "potash solution, medium" is corrected to "potash catalyst."

(9) “Hydroquinone 0.
5g" is corrected to "Hydroquinone 7,5 #J.

fII ``Hydroquinone 0.2I!'' on page 32, line 10!
" has been corrected to "Hydroquinone 3.2 p j.

Claims (1)

[Scope of Claims] (A carbon-carbon double bond with a molecular weight of 41 soo to 5,000 and an iodine value of 50 to 500 and 30 per 100 g
Polymer compound io having ~300 mmol of ami7 groups
o parts by weight (, Z?) to general formula, where R,,7? , represents a hydrogen atom or a methyl group, and n represents an integer of 0 to 20, preferably 1 to 10.] A diglycidyl compound represented by (2) 0 to 1.80 mol per molecule of the diglycidyl compound of (1) above. Formula % Formula % C In the formula, R8 and R3 represent a hydrogen atom or a methyl group.
Reaction product 1 of unsaturated fatty acids having a molar molecular weight of 100 to 350 and containing 10% by weight or more of carbon-carbon conjugated double bonds
0 to 200 parts by weight (C) Manganese salt of organic acid or manganese dioxide 0
．． 005 to 1.0 parts by weight (in terms of metal content) A cathodic electrodeposition coating composition with excellent low-temperature curability, containing as an essential component.