JPS58198577A - Electrodeposition coating composition which deposits on cathode - Google Patents

Abstract

PURPOSE:To provide the titled compsn. excellent in low-temperature curability, corrosion resistance, etc., prepared by adding clycidyl compd. deriv. and manganese salt of a specified high-molecular weight compd. to a high-molecular weight compd. having C=C bond and amino group. CONSTITUTION:The coating compsn. is prepared by adding 3-100pts.wt. compd. of formula I (where R5 and R6 are H or 1-10C alkyl; n is 0-20; m is 1 or 0; Y is 3-4C alpha,beta-unsatd. monocarboxylic acid; Y' is H or Y) or formula II (where n' is 0-10; R7 is H or 1-10C hydrocarbon) and 0.2-20pts.wt. manganese salt of high-molecular weight compd. having a molecular weight of 300-3,000, an iodine value of 50-500, C=C double bond and sulfonic acid or succinic acid group in 30-300mmol/100g, to 100pts.wt. high-molecular weight compd. having a molecular weight of 500-10,000, an iodine value of 50-500, C=C double bond and amino group in 30-300mmol/100g.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a cathodically deposited electrodeposition coating composition having excellent low temperature curability.

A resin having a salt group consisting of a cationic group forms a cationic resin in water, and when this is used for electrodeposition coating performance, the resin is deposited on the cathode.This type of cathode-deposited layer paint is A resin with acid groups! Essential drawbacks of conventional anodic electrodeposition paints that are neutralized with lr base and made water-soluble: 12+1
It is possible to eliminate water leaching from the object to be coated into the paint bath and various problems caused by it.

The present inventors researched such cathodic deposition type paints,
A cathode that provides excellent chemical properties by introducing an amino group into a high molecular weight compound containing an unsaturated group, such as liquid polybutadiene, and neutralizing it with acid. A patent application was filed for the ability to obtain a resin for precipitation-type electrodeposition paints (Japanese Patent Application Laid-Open No. 1197-1197).
27, JP-A-52-147638, JP-A-53-160
48).

Cathode-deposited electrodeposition coating compositions containing the above-mentioned resins as coating film components are cured mainly by oxidation plating of the amorphous groups contained in the resins, and provide coatings with excellent performance, but they do not take a practical curing time. Requires relatively high baking temperatures to cure. As a result of research on lowering the baking temperature, the present inventors discovered that by adding a metal dryer such as a water-soluble manganese salt, the coating film could be cured at a relatively low baking temperature, and filed a patent application. -142444) 0 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 -surface force (easiness to roughen). He discovered a method of introducing acrylic double bonds into resin and curing it with a relatively low baking rate (Japanese Patent Laid-Open No. 56-151777). It is a cathodically deposited electrodeposition coating that cures at a relatively low temperature and has excellent performance.

From the perspective of energy saving in recent years! ! It is desired to lower the baking temperature, and as a result of various studies, the present inventors have found that carbon-carbon double bonds and sulfone or cono-phosphoric acid resins have carbon-carbon double bonds and sulfonic acid groups. The inventors have discovered that the seizure rate can be further reduced by adding an oil-soluble manganese salt to a polymer compound having a group-containing polymer compound, and have thus arrived at the present invention.

Therefore, the object of the present invention is to provide a polar precipitation type coating material that improves the curability of the above-mentioned carbon-carbon double bond and amine group-containing polymer compound, and provides low-temperature curability and excellent corrosion resistance. be.

500 to 10.0, which is the starting material for component (A) of the present invention.
A polymer compound having a carbon-carbon double bond with a molecular weight of 0.00 and an iodine value of 50 to 500 is produced by a conventionally known method.

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 an aromatic vinyl monomer in an amount of 50 mol or less per these diolefins, or the conjugated diolefin. For example, styrene, α-methylstyrene, vinyltoluene or divinylbenzene, and QC-100℃
A typical manufacturing method is a method in which carbon atoms are brought into competition or entanglement at a temperature of . In this case, in order to control the molecular weight and obtain a light-colored, low-density compound with little gel content, an organic alkali metal compound such as sodium pendyl is used as a catalyst.
Chain transfer method 1 using a compound having an alkylaryl group, such as toluene as a chain transfer agent (US Pat. No. 37890)
90) or the living 1 method (Japanese Patent Publication No. 42-174F15, No. 43-27432) in which a polycyclic aromatic compound such as naphthalene is used as an activator and an alkali metal such as sodium is used as a catalyst in a tetrahydrofuran solvent; An injection method in which an aromatic hydrocarbon such as toluene or xylene is used as a solvent, an alkali metal dispersion such as sodium is used as a catalyst, and an ether such as dioxane is added to control the molecular weight (Japanese Patent Publication No. 32-7446) , No. 38-1245, No. 34-10188) are suitable manufacturing methods.

It is also produced by coordinated anidine injection catalyzed by an acetylacetonate compound of a Group 8 metal such as cobalt or nickel and an alkyl aluminum halide (
(Japanese Patent Publication No. 45-507, 146-80300) Low polymers can also be used.

Component (A) of the present invention, that is, a polymer compound having a molecular weight of 500 to 10,000, an iodine number of 50 to 500, a carbon-carbon double bond, and an amino group of 30 to 300 mmol per 100 g can be prepared by a conventionally known method. Manufactured.

For example, after adding maleic anhydride to a polymer compound having a carbon-carbon double bond, the general formula A method of introducing an amine group by reacting a diamine compound represented by (representing a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group) (
JP-A-51-119727, JP-A-52-147638
, JP-A-53-8629, JP-A-53-63439) or a method of adding a secondary or secondary amine after epoxidizing a polymer compound having a carbon-carbon double bond (JP-A-53-16048, JP-A-53-16048, JP-A-53-11703 (N, etc. are known).

Component (B) of the present invention, that is, the general formula % (wherein R3 and R6 are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an integer of nho to 20, m is 1 or 0
, Yt-J is a residue of an α, β unsaturated monocarboxylic acid having 3 or 4 carbon atoms, and Y′ is a hydrogen atom when m is 0,
When m is 1, it represents Y] or the following general formula (b') ----
--(bwa [in the formula, n' JriO, an integer from 10 to 10, R1H hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and YVi all residues of α, β unsaturated monocarboxylic acid having 3 or 4 carbon atoms) ] Corrosion resistance is significantly improved by adding the compound.

The content of component (H) is in the range of 3 to IQOii parts, preferably 1 to 50 parts by weight, per 100 parts by weight of the resin (A).

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

KFi to obtain the compound of the above component (H), formula % formula % 10 alkyl group, preferably methyl group, n is 0
A glycidyl compound represented by the following formula is used as a raw material. This glycidyl compound can be prepared by etherifying bisphenol with epichlorohydrin, usually in the presence of an alkali. Such bisphenol compounds include 2,2-bis(4'-hydroxyphenyl)propane, 1,1-bis(4'-hydroxyphenyl)1tane, 1. l-bis(4'-hydroxyphenyl)isobutane, and the like. In many cases, by reacting the glycidyl ether of the above-mentioned compound with bisphenol or the like, and then further reacting this product with epichlorohydrin, glycidyl compounds having a somewhat higher molecular weight are synthesized, and these can be used.

Next, the glycidyl compound is reacted with an unsaturated carboxylic acid having 3 or 4 carbon atoms at a temperature of 0 to 200°C, preferably 50 to 150°C. Examples of unsaturated carboxylic acids having 3 or 4 carbon atoms include acrylic acid, methacrylic acid and crotonic acid, and mixtures thereof may also be used.

For the reaction, a suitable catalyst such as tertiary amines or quaternary ammonium salts can be used. Also, in the presence of a solvent,
The reaction can be carried out in the absence of a solvent, but if a solvent is used, please refer to the same book as the solvent used in the step of synthesizing resin (A) [7]. can be used.

When acrylic acid, for example, is used as the unsaturated carboxylic acid, the above reaction is carried out directly according to the following reaction formula.

In the present invention, substantially all of the above glycidyl compound reacts with the unsaturated carboxylic acid to produce Y-CHx-C
It is required to be converted into an HCHt- group (Y has the same meaning as above for H).

When acid is added to bamboo to make it water-soluble, it undergoes an unfavorable reaction with the basic group of the resin (A), causing gelation, resulting in a viscosity that becomes too high and cannot be water-solubilized. For example, even if water solubilization is achieved, the aqueous solution will change over time and will remain at a constant f.
This results in drawbacks such as the inability to obtain s1 adhesion properties or electrodeposition properties.

Conventionally, bisphenol-type epoxy resins have been known as resins with excellent corrosion resistance, and in order to give them crosslinking properties, some of the epoxy groups were left unused, and
23807, Japanese Patent Publication No. 51-15860), attempts have been made to use blocked isocyanate compounds as crosslinking agents. However, such paints require high temperatures such as Fi200°C or higher to obtain practical hardness, and even when they can be cured at relatively low temperatures, they have the disadvantage that only a narrow range of baking temperatures can be selected.

Furthermore, the bisphenol type epoxy resin must have a certain degree of high molecular weight under practical conditions of electric current, and the inevitable Kl! 1ull tends to lack flexibility. Furthermore, when a blocked isocyanate is used in a resin having a carbon-carbon double bond, oxidation during baking tends to be inhibited, making it difficult to obtain a coating film with sufficient performance.

Therefore, according to the present invention, the glycidyl compound Y-C1
, -CH-CH,- as a component of the cathodically deposited electrodeposition paint, the resin, (A
) can be used in combination with resin (A), thereby significantly improving the corrosion resistance of resin (A) without impairing its excellent curability and olfactory properties. It should be serious.

Molecular weight of component (C) 300-a, ooo 50-50
An oil-soluble manganese salt of a polymer compound having a carbon-carbon double bond with an iodine value of 0 and 30 to 300 mmol of sulfonic acid group or succinic acid group per 1002
By adding 20 parts by weight, the curability is significantly accelerated and a low temperature curable cathodically deposited electrodeposition coating material can be obtained.

In general, manganese naphthenate, manganese octenoate, manganese acetylacetonate, etc. are known as oil-soluble manganese salts, but these manganese salts are weak acid manganese salts and can be exchanged with acetic acid as a neutralizing agent in an aqueous solution. A reaction occurs and gradually turns into aqueous manganese salts, which impairs the stability of electrodeposition paints.

In addition, when water-soluble manganese salts are formed, water-soluble manganese salts increase the conductivity of the electrodeposition coating solution, causing rough skin, or water-soluble manganese salts accelerate curing compared to oil-soluble manganese salts. It is not recommended to use manganese salts of weak acids even if they are oil-soluble because their effectiveness is small and curing properties are lowered. Therefore, the resin of component (B) will not harden even if component (A) is present, which may cause a decrease in the performance of the baked coating film, such as solvent resistance.

The manganese salt of oil-soluble sulfonic acid or the manganese salt of succinic acid used in the present invention does not undergo an exchange reaction with acetic acid, a rounding neutralizing agent, which is a platform for extortion, and has an unsaturated group, so the component (A ) or co-cures with component (B) during baking, so it can be used without causing the above-mentioned problems.

Component (C) used in the present invention, i.e. 300 to a, o
The oil-soluble manganese salt of a high molecular weight compound having a carbon-carbon double bond with a molecular weight of 50 to 500 and an iodine number of 30 to 30 mmol per foot and a sulfonic acid group or a succinic acid group has been produced by a conventionally known method. Ru. For example, after sulfonating or maleating the low-acid or co-low-acid combination of conjugated diolefins used as the starting material for component (A) of the present invention, the sodium salt of these acid groups and manganese sulfate, manganese chloride, etc. It is easily produced by the so-called double decomposition method using a salt exchange reaction, or by an acid exchange reaction with a manganese salt of a weak acid such as manganese acetylacetonate, manganese carbonate, or manganese acetate.

The amount of oil-soluble manganese salt added as component (C) of the present invention is 0.
If the amount is less than 2 parts by weight, the effect of promoting curability will be small, and if it is more than 20 parts by weight, curability will be good, but water dispersibility, corrosion resistance, etc. will be deteriorated, which is not preferable. The preferable range is 1 to 10 parts by weight, and the amount of manganese metal is preferably 05 to 0.5 parts by weight.

In the present invention, component (A), component (B) and component (C
) In order to water-solubilize or water-disperse a composition consisting of component (A), component (B) and component (C)? After pre-mixing, 0.1 to 2
．． 0 preferably Vio, 2 to 1.0 molar equivalents of acetic acid,
It is preferable to neutralize with a water-soluble organic acid such as propionic acid or lactic acid to make it water-soluble.

When neutralizing the resin composition (a) or (c) of the present invention and dissolving or dispersing it in water, it is possible to facilitate the dissolution or dispersion, improve the stability of the aqueous solution, improve the fluidity of the resin, and improve the coating properties. For purposes such as improving the smoothness of water-soluble resin compositions, ethyl cellosolve, propyl cellosolve, butyl cellosolve, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diacetone alcohol, 4-methoxy-4-
Organic solvents such as methylpentanone-2 and methyl ethyl ketone were added to each resin composition in an amount of 10 to 100 parts per free weight part.
It is preferable to use a portion of il.

A suitable pigment can be added to the cathodically deposited coating composition of the present invention. For example, iron oxide, lead oxide,
One or more pigments such as strontium chromate, carbon black, titanium dioxide, talc, aluminum silicate, and barium sulfate can be incorporated.

These pigments are that! Although it can be added to the composition of the present invention, in advance, a large amount of pigment is added to a part of the component (Al dispersed or made into an aqueous solution in neutralized water) and mixed to obtain a paste-like masterbatch. This paste-like pigment can be added to the entire composition.

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. The physical properties of the coatings in the Examples and Comparative Examples were tested in accordance with JIS-5400.

Production example 1゜Nisseki Bo 1,1 Butadiene B-2000 (number average molecular weight 2
,000.1,2 bond 651) was epoxidized using peracetic acid to produce epoxidized polybutadiene (E, ) with an oxirane oxygen content of 6.34? Manufactured.

After charging 1.0762 of this epoxidized polybutadiene (E') and ethyl cellosolve 108f%-27-1-toclef, 40ft770 of dimethylamine, 1
The reaction was carried out at 50°C for 5 hours. After distilling off the unreacted amine, a mixture of 95 t of acrylic acid, 8 t of hydroquinone, and 260 t of ethyl cellosolve was added, and the mixture was further reacted at 150°C for 45 minutes to form a resin solution of component (A) of the present invention. The amine value of this product (A,) is 50.
The mmol/1009a value was 5 mmol/100F and the solids concentration was 7s, ot1%.

Production example 2゜Nisseki polybutadiene H-1500 (number average molecular weight 150
0.1.2 bond 63) was epoxidized using peracetic acid to produce epoxidized polybutadiene (E,) having an oxirane oxygen content of 6.5%.

This epoxidized polybutadiene (FJ) 1000f, ethyl cellosolve 368t and jetanolamine were charged into a 105ft3 noseparapure flask and heated to 150°C.
The mixture was allowed to react for 6 hours. After the reaction, the mixture was cooled to 120C, a mixture of acrylic m79f, hydroquinone 7.3f and ethyl cellosolve 26f was added, and the mixture was reacted at 120C for 8 hours to produce a resin solution of component A of the present invention (A, 1).

The amine value of this product is 62 mmol/IOOf.

The acid value is l 2mmol/100? , and the solid content concentration was 751 ■.

Production Example 3 Nisseki Polybutadiene B-2000 (number average molecular weight 200
0,1.2 bonds 65%) 1000f, maleic anhydride t
6sf, xylene 10f1 Antigen 3C (trade name of Sumitomo Chemical) 29 were charged into a 21 separable flask equipped with a reflux condenser and reacted at 190° C. for 5 hours under a nitrogen stream. Next, unreacted maleic anhydride and xylene were distilled off under reduced pressure to synthesize maleated polybutadiene (M,) 5 with a barrier value of 143 mmol/100f.

Butyl Cellosolve 1562 was charged into a 21 separable flask equipped with a reflux condenser and heated to 80° C. with stirring.

Next, dimethylamine propylamine 78F was added dropwise, and then monoethanolamine 23F was added dropwise. Immediately after the addition was completed, the temperature was raised to 150°C and the reaction was continued at 150°C for 4 hours. The produced water, butyl cellosolve and unreacted amine were distilled off under reduced pressure to synthesize imidized polybutadiene having tertiary amine groups and hydroxyl groups. The amine value of this imidized polybutadiene was 89 mmol/100F. The solid content of imidized polybutadiene is so
A resin solution (A3) of the component (A) of the present invention was prepared by dissolving it in ethyl-←Rosolve so that it was completely dissolved.

Production Example 4 The following compound obtained by reacting bisphenol A and epichlorohydrin in the presence of an alkali catalyst was a bisphenol type epoxy resin having an epoxy equivalent of 500 [
Product name Epicote] (manufactured by 101 Ciel Chemical Co., Ltd.) 1.
000f in ethyl cellosolve 227f and acrylic 91371. Hydroquinone 0.2t and N, N
5 of dimethylaminoethanol was added, and the mixture was heated to 100° C. and reacted for 5 hours to synthesize an ethyl cellosolve solution of epoxy 411 II-acrylic acid adduct (B1), which is component (B) of the present invention.

Production Example 5 Bisphenol type epoxy resin with epoxy equivalent of 500 [trade name Epicote 1001, Nonyl Kagaku (&)
] 1.000 t>Dissolved in 288 t of ethyl cellosolve, 64 f of methacrylic acid, 0.0 t of hydroquinone.
Component (B) of the present invention was prepared by adding 5f of 29 and N,N dimethylaminoethanol and under the same reaction conditions as in Production Example 4.
An ethyl cellosolve solution (B) of an epoxy resin-methacrylic acid adduct was synthesized.

Production Example 6 Nisseki Polybutadiene B-700 (number average molecular weight 700.
1.2 bonds 52%)] O (10t, maleic anhydride 1
17.3f, Antigen 3C]? and xylene 10
9 with a reflux condenser installed 2! The mixture was placed in a separable flask and reacted at 195° C. for 5 hours under a nitrogen stream. Next, unreacted maleic anhydride and xylene were distilled off under reduced pressure to synthesize maleated polybutadiene (M,) having an acid value of 107 mmol/100F.

Maleated polybutadiene (M) 500F and ethyl cellosolve 148t were reacted at 120'C for 2 hours to open the succinic anhydride group, and then cooled to room temperature, and gradually added with 100t of an aqueous solution of 22.59 volumes of hydric soda. After addition and neutralization, deionized water was added so that the solid content concentration was 259 volumes to prepare an aqueous solution of maleated polybutadiene.

Next, manganf sulfate (MnSO4-H,04,,) 7
After dissolving in 4.5 f'tr water 6001, 600 t of isopropyl alcohol and 1000 f of benzene were added and the maleated polybutadiene aqueous solution 21 was stirred at room temperature.
92g was gradually added dropwise, and after the completion of the dropping, 60g was heated for 30 minutes and then left to stand for 1 hour.
After adding 1,000 f of deionized water and heating at 60° C. for 30 minutes, electrostatic discharge was performed for 1 hour to remove the lower layer.

The upper layer was taken out and benzene etc. were distilled off under reduced pressure to produce manganese salt of maleated polybutadiene by double decomposition method.

This manganese salt of maleated polybutadiene was dissolved in ethyl cellosolve so that the solid content was 75% by weight to produce a solution (C3) of oil-soluble manganese salt as component (C) of the present invention. The amount of manganese-containing electricity Fi2 in (C1) was -.

Manufacturing example 7 Nisseki Polybutadiene B-1500100of.

Anhydrous maleic acid 11117.3f antigen 3C2f and xylene 10f were charged into a 21 separable flask equipped with a reflux condenser and allowed to react at 195° C. for 5 hours under a nitrogen stream. Next, unreacted maleic anhydride and xylene were distilled off under reduced pressure to give an acid value of 107 mmol/10. Maleated polybutadiene (M,) of Oy was synthesized.

Maleated polybutadiene (M,) 2sOr and ethyl cellosolve 220f were charged into a 11 separable flask equipped with a reflux condenser and a Liebig condenser.
After reacting at 0°C for 2 hours to open the succinic anhydride group,
Aqueous solution of manganese acetate dissolved at 46.4F 175.7
After adding F and heating to 120° C. to distill off water, acetic acid and ethyl cellosolve at normal pressure, the pressure was further reduced and acetic acid and ethyl cellosolve were distilled off to produce a manganese salt of maleated polybutadiene using the silicic acid exchange method.

This manganese salt of maleated polybutadiene was dissolved in ethyl cellosolve so that the solid content was 75% to prepare a solution (C,) of an oil-soluble manganese salt as component (C) of the present invention. The manganese content Fi of (C2) was 3.6111.

Production Example 8 In a 2 t separable flask equipped with a reflux condenser and a dropping funnel, 10 of Nippon Seki Borichtadiene B-700 was collected, and dehydrated dichloroethane 1200117 was added thereto to dissolve it and cooled to 5°C. While keeping the temperature at 5℃,
An SO8/dioxane (1:1) complex synthesized from 1.4 t of dehydrated dioxane and 12.6 f of dehydrated dioxane dissolved in 100 g of dehydrated dichloroethane was added dropwise over 60 minutes under a stream of 9 atom gas. After completion of the dropwise addition, the solution was aged at the same temperature for 30 minutes to synthesize a solution of sulfonated polybutadiene (S). Next, Mn was added to a 2t separable flask.
A solution of (Sl) after ripening was added dropwise over 5 minutes under a nitrogen stream while vigorously stirring CO 0°9.1f and water 18°2fk.

After the dropwise addition was completed, the mixture was heated to 60° C. for 30 minutes to induce hydrolysis. By distilling off the solvent from the reaction solution, a brown semicylindrical manganese salt of sulfonated polybutadiene was produced by acid exchange reaction.

This manganese salt of sulfonated polybutadiene was dissolved in ethyl cellosolve so that the solid content was approximately 75, to produce a solution (C1) of an oil-soluble manganese salt as component (C) of the present invention. The manganese content of (C5) was 2.811.

Example 1 A+400f manufactured in Manufacturing Example 1, B manufactured in Manufacturing Example 4, 10.8.4 f, and 9C manufactured in Manufacturing Example 6
, 45f were mixed until homogeneous, then 6V of acetic acid was added and thoroughly stirred to neutralize. Next, dehydrated water was gradually added to prepare an aqueous solution having a solid content concentration of 20%.

This 20% aqueous solution 2000f, carbon black 49. Basic lead silicate 20f and glass beads 2000
f was placed in a 51 stainless steel beaker and stirred vigorously for 2 hours using a high-speed rotating mixer, and after filtering the glass beads, deionized water was added to give a solid concentration of 151 to prepare an electrodeposition coating solution.

Using the above electrodeposition coating liquid, a carbon electrode was used as an anode, and a zinc phosphate treated plate (Japan Test Panel Co., Ltd., Bt3004.0
．． FIX70x150m) was used as a cathode for cathode deposition type electrodeposition coating. The test results are shown in Table-1.

Comparative Example 1 C+ 'f- produced in Production Example 6 - A cathode-deposited electrodeposition coating liquid was prepared under the same conditions as in Example 1 except that 'f- was not added! i
Tests were conducted under the same conditions as Examples 1 and 1, and the results are shown in Table 1.

Comparative Example 2 A cathode-deposition electrodeposition coating solution was prepared in the same manner as in Example 1, except that 0.9f of manganese acetate was added in place of C1 produced in Production Example 6, under the same conditions as in Example 1. The results are shown in Table 1.

Example 2 A produced in Production Example 2, 400f%11! 9B, 759 produced in Production Example 5, and C216 produced in Production Example 7.
After mixing 7f until homogeneous, 7.4f of vinegar was added and thoroughly stirred to neutralize. Next, deionized water was gradually added to prepare an aqueous solution having a solid content concentration of 25%. This 25-brewing volume - 1000f of aqueous solution, 2.5t of carbon black, 259 basic silica lead and 1000f of gala beads were placed in a 31 stainless steel beaker and heated in a high-speed rotating mixer for 2 hours.
L<kay! After mixing, the glass beads were heated in a furnace, and then deionized water was added so that the solid content concentration was 18% to prepare an electrodeposition coating liquid.

Using the above electrodeposition coating liquid, a carbon electrode was attached as an anode [7. Zinc phosphate treated plate (Japan Test Panel Co., Ltd., 813004,
o, sx'yox150mm)? The cathode and 17# electrode deposition type electrodeposition coating were performed. The test results are shown in Comparative Example 3. C2 produced in Production Example 7 was added (except for 7). All cathodic deposition type electrodeposition coating liquids were prepared under exactly the same conditions as Example 2, and tested under the same conditions as Example 2. Table 2 shows the results.
As shown in [7].

Comparative Example 4 A cathode-deposited electrodeposition coating solution was prepared under the same conditions as in Example 2 except that 0.6% manganese acetate was added to C1 produced in Production Example 7. The test was conducted under the same conditions as above and the results are shown in Table 2.

Example 3 A, 400F produced in Production Example 3, B+ 108.4 f produced in Production Example 4, and Cs produced in Production Example 8
After mixing 30f until homogeneous [7], acetic acid lOf was added and thoroughly stirred to neutralize. Next, deionized water was gradually added to prepare an aqueous solution having a solid content concentration of 30 ['1Ii1.

This 30 @@% aqueous solution 1000F, carbon black 3F, basic lead silicate 20F and glass heats 1000
After stirring vigorously for 2 hours with a high-speed rotating mixer in a FT31 stainless steel beaker, the glass beads were filtered, and deionized water was added to make the solid content S degree 161 to prepare an electrodeposition paint liquid.

17. A zinc phosphate treated plate (Japan Test Panel, flt3004.
0. RX 70 The test results are shown in Table 3.

Comparative Example 5 118 electrodes were precipitated under the same conditions as in Example 2 except that Csf was not added.
#Preparation solution t- was prepared and tested under the same conditions as in Example 3, and the results are shown in Table 3. 1. Comparative Example 6 Manganese acetate was used instead of C3 produced in Production Example 8, and 0.849 A cathode-deposited electrodeposition coating solution was prepared under the same conditions as in Example 3 except for the addition of the following ingredients, and a test was conducted under the same conditions as in Example 3. The results are shown in Table 3.

Claims (1)

[Claims] (A) 500 to 10,000 (7) 50 to 10,000 in molecular weight
Carbon-carbon21 bond with an iodine value of 500 and 100f
1001 parts by weight of a polymer compound having 30 to 300 mmol of amino groups per unit (Bl) General formula % Formula % [In the formula, R and R6 are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, n#-jO to 2゜m is an integer of 1' or 0, Y is a residue of α, β unsaturated monocarboxylic acid having 3 or 4 carbon atoms, and when Y'ijm is 0, it is a hydrogen atom, and when m is 1, it is a hydrogen atom. represents all Y] or a compound represented by the general formula [wherein n' is an integer of 0 to 10, R1 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and Y is α having 3 or 4 carbon atoms] , represents a residue of a β-unsaturated monocarboxylic acid] A compound represented by 3-1oo 11 parts c+ 3ob-a, ooo molecular weight and an iodine value of 50-500 carbon-carbon binary bond and 30 per 100t
1IIIWA precipitation type 1 with excellent low rIAe properties, consisting of 0.2 to 20 parts of a manganese salt of a polymer compound having ~300 mmol of sulfonic acid groups or succinic acid groups
First coating composition.