JPS60229967A - Cathode-deposition electrodeposition paint composition - Google Patents

Abstract

PURPOSE:To provide the titled composition having excellent low-temperature curability and corrosion resistance, and containing a reaction product of a specific component such as epoxidized polymeric compound, etc., a reaction product of a specific component such as a diglycidyl compound, etc., and an organic acid manganese salt, etc. at specific ratios. CONSTITUTION:The objective composition can be prepared by compounding (A) 100pts.(wt.) of a reaction product obtained by the reaction of (a) 100g of a polymeric compound having a molecular weight of 500-5,000 and an iodine value of 50-500, and containing 3-12(wt)% C-C double bond and oxirane oxygen, (b) 30-300m-mol of an amine compound of formula I [R1 and R2 are 1- 20C (OH-substituted) hydrocarbon group], (c) 0-200m-mol of an alpha,beta-unsaturated carboxylic acid of formula II (R3 and R4 are H or methyl) and (d) 200-50m- mol of an unsaturated fatty acid having a molecular weight of 100-350 and containing >=10% conjugated C-C double bond, with (B) 10-200pts. of a reaction product prepared by reacting 1mol of a diglycidyl compound of formula III (R5 and R6 are H or methyl; n is 0-20) with 2mol of an alpha,beta-unsaturated carboxylic acid of formula IV (R7 and R8 are H or methyl) and (C) 0.005-1.0pt. (in terms of metal) of an organic acid manganese salt, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a ridge precipitation type electrical resistance composition having excellent low-temperature curability.

The resin having basic groups of the glaze forms a cationic resin gold in water, and when electrodeposition is performed using this resin, the resin is deposited on the cathode. This peach cathode deposition type paint overcomes the essential drawbacks of conventional anodic deposition type electrodeposition paints, which are water-soluble by neutralizing resins having acid groups with bases, i.e., they do not allow the coated material to enter the paint bath. Metal elution and various problems caused by it can be solved.

The present inventors researched such cathodic deposition type paints,
Before applying the carbon-carbon double box 8, an amine group is introduced into a high molecular weight compound containing an unsaturated group, such as a low degree of polymerization, such as liquid polybutadiene, and the film is neutralized with an acid. He discovered that it was possible to obtain a cathode-deposited paint resin and applied for a patent (Japanese Unexamined Patent Publication No. 51-119
727, JP-A-52-147638, JP-A-53-16
048).

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 water-soluble manganese salt, and filed a patent application (Japanese Patent Application Laid-Open No. 53-142444).

In this case, a large amount of dryer is required, which deteriorates electrodeposition coating performance such as throwing power and causes problems such as f'c, s, and fallen surfaces are likely to become rough. The present inventors also discovered a method of introducing reactive acrylic (methacrylic) double bonds into animal fats and curing them with a relatively low degree of seizure risk.
Demusze [shita (Takekaiki 456-151777)] In this case, when water and manganese salt are added, a cathodically deposited coating material which cures at a relatively slow temperature of 160 DEG C. and exhibits excellent performance can be obtained.

However, in recent years, as a matter of energy conservation, it has become common practice to reduce the concealment of burning, and as a result of our extensive research, the present inventors found that a carbon-carbon conjugated double bond is added to the compound of component (A). The present inventors have discovered that the degree of sintering can be further lowered by introducing the above-mentioned additives.

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.

(A) (1) With a molecular weight of 500 to 5.000,
Polymer compound containing carbon-carbon double bonds with an iodine value of 500 and oxirane oxygen in an amount of 3 to 12% by weight (2) Upper st (1) 3 per 100 f of the polymer compound
0 to 300 mmol of the general formula [wherein R and R7 represent a hydrocarbon having 1 to 20 carbon atoms which may be partially substituted with a hydroxyl group, provided that RIl! :R1 can have a ring structure, and the ring structure can contain an unsaturated group. ] Amine compound (3) The polymer compound 100 of the above (1) is 0 to 21
. 07su2'' general formula % formula % [in the formula, R5 and RaVi represent a hydrogen atom or a methyl group] and (4) a polymer compound 100f of the above formula (1) 100 quintillion parts of a reaction product of an unsaturated fatty acid containing 100 parts by weight of 2°O to 50 mmol of molecules 1 too to 350 carbon-carbon conjugated double bonds (B) general formula [wherein R55R6 is a hydrogen atom or a methyl group, 9 represents an integer of 0 to 20, preferably 1 to 10] and a diglycidyl compound represented by the general formula % formula % of substantially 2 mol per molecule of the diglycidyl compound [in the formula R1 and R6 represents a hydrogen atom or a methyl group. ] Product obtained by reacting α, β unsaturated carboxylic acid represented by 10 to 200 parts by weight (C) Manganese salt of organic acid or manganese dicarboxylate (
This is a cathode-deposited electrodeposition coating composition with excellent low-temperature curability, which contains from 1.0 parts by weight of (as an amount of gold maple) o, oos as an essential component.

500 to 5,000 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 and an iodine number of 50 to 500 is produced by a conventionally known method.

That is, an alkali metal or (iii) a conjugated diolefin having 4 to 10 carbon atoms alone using an organic alkali metal compound as a catalyst;
Alternatively, aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, or divinylbenzene in an amount of 50 molar or less relative to these diolefins or the conjugated diolefin, and gold at 0°C to 100°C
A typical manufacturing method is anionic polymerization or copolymerization at a temperature of . In this case, the molecular weight is controlled 111, r
In order to obtain a light-colored, low-weight supernatant with a low molecular content, a compound such as sodium benzyl is used as a catalyst and a compound having an alkylaryl group, such as toluene, is used as a chain transfer agent. Overlapping method (U.S. Patent No. 3)
789090) or a living polymerization method using a polycyclic aromatic compound such as naphthalene as an activator and an alkali metal such as sodium as a catalyst in a tetrahydrofuran solvent (Japanese Patent Publication No. 42-17485, 43-27432)
or a polymerization method in which the molecular weight is controlled by using an aromatic hydrocarbon such as toluene or xylene as a solvent, a dispersion of an alkali metal such as sodium as a catalyst, and adding an ether such as dioxane. -7446,
No. 38-1245, No. 34-10188) are suitable manufacturing methods.

Mafc, produced by coordination anionic polymerization using an acetylacetonate compound of a group 8 metal such as cobalt or nickel and an alkyl aluminum halognide as a catalyst (Japanese Patent Publication Nos. 45-507 and 46-80300)
Low polymers can also be used.

! (A) IN component of the present invention is obtained by epoxidizing the unsaturated compound using a peroxide such as hydrogen peroxide or peracid by a known method to introduce 3 to 12% by weight of oxirane oxygen groups, and then An amine compound represented by the general formula [wherein R and R1 are the same as above] is reacted in the presence or absence of a solvent in a concealed manner at 50 to 200°C, and then a carbon-carbon conjugated compound with a molecular weight of 100 to 350 The heavy bond is 1O weight t%
It is produced by reacting unsaturated fatty acids containing the above at 100 to 200°C. In this case, an α,β unsaturated carboxylic acid represented by the general formula % (in which Rs and R6 are the same as above) may be reacted together.

Examples of amines used in the reaction are dimethylamine,
Examples include aliphatic amines such as diethylamine, alkanolamines such as methyl ethanolamine and jetanolamine, and cyclic amines such as morpholine and piperidine.

The amount of amine added is epoxidized ^ molecular compound 1 oor
30 to 300 mmol, preferably 50 to 200 mmol.

Carbon-carbon conjugated double bond t10 with molecular weight 100~aOO
Examples of unsaturated fatty acids containing more than % by weight include sorbic acid, Chinese tung oil fatty acid, sunflower oil fatty acid, dehydrated castor oil fatty acid, etc. Also, soybean oil fatty acid, linseed oil fatty acid, etc. are conjugated by isomerization. Conjugated fatty acids can also be used, and purified eleostearic acid and conjugated linoleic acid can also be used. Also, 1
Mixing an unsaturated fatty acid with many conjugated double bonds with an unsaturated fatty acid having 0% by weight or less of carbon-carbon conjugated double bonds,
A mixture in which the total amount of conjugated double bonds is 10% by weight or more can also be used. Among them, dehydrated and mustard oil are advantageous and preferred because they are easily available industrially.

Examples of α,β unsaturated carboxylic acids include acrylic acid and methacrylic acid.

The amount of the unsaturated fatty acid to be added is 50 to 200 mmol, preferably 50 to 150 mmol in terms of carboxylic acid per 100 f of the epoxidized polymer compound. The α,β unsaturated carboxylic acid can be used in amounts up to 200 mmol per toor of epoxidized polymer.

Component (B) of the present invention, that is, general formula R6 [wherein R,, R, are hydrogen atoms or methyl groups, n is 0
represents an integer from 1 to 20, preferably from 1 to 1O] and the glycidyl compound 1
substantially 2 moles per molecule of the general formula C11=C-C-O
Corrosion resistance and hardenability are significantly improved by adding a product obtained by reacting an α,β unsaturated carboxylic acid represented by B [in the formula R7 and RaFi represents a hydrogen atom or a methyl group].

The content of component (B) 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 (/f).

If the content of component CB) is lower than this, the corrosion resistance will be improved.
If l is not sufficient and is greater than this, water dispersibility will deteriorate.

In order to obtain the compound of the above component (B), the general formula [wherein, 8
1%R6 is a hydrogen atom or a methyl group, n is 0 to 20
preferably represents an integer from 1 to 1O] 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'-hydroxyphenylpropane, 1,1-bis(4'-hydroxyphenyl)ethane, 1,1-bis(4'-hydroxyphenyl)inbutane, .2-bis(4'-hydroxyphenyl)methane, etc. In many cases, further reaction of the above diglycidyl ether with bisphenol etc. and then further reaction of this product with epichlorohydrin results in a somewhat higher molecular weight. A diglycidyl compound is synthesized,
You can use these.

The above diglycidyl compound is heated to a temperature of θ to 200°C, preferably 50 to 150°C, and an α,β-unsatonic monocarboxylic acid represented by the general formula %) [wherein R7 and R6 represent a hydrogen atom or a methyl group] Component (B) can be prepared by reacting substantially 2 mol of acid with 1 mol of diglycidyl compound 9J.

α, β unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, fumaric acid and glycidyl (meth)
Equimolar reaction products of acrylate and equimolar reaction products of maleic anhydride and hydroxy (meth)acrylate are used, and mixtures thereof can also be used.

In carrying out the reaction, a radical polymerization inhibitor such as hydroquinone, methoquinone, A-phenyl/A'isopropyl-P-phenylenediamine is added at 0.00% to prevent side reactions. O1~1. It is preferable to add nitrogen and use a suitable catalyst such as tertiary amines or quaternary ammonium salts. In addition, the reaction can be carried out in the presence or absence of a solvent, but if a solvent is used, it must be inert to the reaction. It is practically advantageous to use an appropriate amount of any water-soluble solvent in ethyl acetate cellosolve, mix it with components (, 4) and <C> as it is, without removing it after the reaction, and use it in an electrodeposition coating.

In the present invention, it is preferred that all of the above diglycidyl compounds are α,β unsaturated olomonocarboxylic acids and anti-00H.

When the H 2 group is water-solubilized by adding an acid later, it undergoes an unfavorable reaction with the basic group of the resin CA>, causing celification, resulting in an excessively high viscosity that impedes water-solubilization. Even if hydroxylation occurs, the bathing liquid will become dull over time.
This results in drawbacks such as constant electrodeposition characteristics or failure to obtain an electrodeposited coating film.

Traditionally, bisphenol-type epoxy resins have been known as resins with excellent corrosion resistance.
Attempts have been made to use blocked isocyanate compounds as crosslinking agents. However, such paints require high temperatures of 200°C or higher to obtain practical hardness, and even if they can be cured with low specific yield, they have drawbacks such as being able to select only a narrow baking temperature range. Ta.

Furthermore, the bisphenol type epoxy resin must have a certain degree of high molecular weight under practical electrodeposition conditions, and as a result, the e% and q% inevitably tend to lack flexibility. When a blocked isocyanate is used in an HV4 resin having a carbon-carbon double bond, the baking polymerization during baking tends to be inhibited, making it difficult to obtain a film with sufficient performance.

Therefore, according to the present invention, the compound (Z()H) converted to the sogelicidyl compound 1-C-0-C1-C-0-CH2-C is used as a component of the cathode-deposited electrodeposition paint, and the resin (fiber) ), thereby allowing the resin (,4)
It is truly surprising that it has been found that the corrosion resistance can be significantly improved without sacrificing the excellent hardenability and coating properties of the coating.

Component (C) of the present invention, that is, a manganese salt of an organic acid, is a sphagnum manganese salt such as manganese formate, manganese acetate, manganese lactate, manganese naphthenate, manganese methacylate, and the general formula [wherein R5o and R11 are hydrogen] represents an atom or an alkyl group having 1 to 20 carbon atoms, provided that R3゜ and R11 each represent a 6-membered ring structure or a 5-membered ring structure.
It can have a heterocyclic structure including a membered ring and a 6-membered ring,
The ring structure can contain unsaturated groups.

R52 represents an organic residue having 1 to 20 carbon atoms that may contain an ether bond, an ester bond, and an unsaturated group.

Xl 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 carbons to which l and
By adding 0.05 to 1.0 parts by weight, curing properties are significantly accelerated and a low-temperature curable cathodically deposited electrodeposition coating material can be obtained.

If the amount of organic acid manganese salt or manganese dioxide (component C) of the present invention is less than 0.005 ruts in terms of metal amount, the effect of promoting hardenability will be small;
If the amount exceeds the weight part, the curability is good, but water dispersibility, corrosion resistance, etc. are deteriorated, so it is not preferable. A preferable range is α01 to 0.5 heavy electrical parts in terms of metal content.

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), Components (B) and Components (C), a dust mixture of 0.1 to 0.1 to 2
It is preferable to neutralize it with a water-bathable organic acid such as acetic acid, globionic acid, lactic acid, etc. in an amount of 0.2 to 1.0 molar equivalents to make it water-solubilized.

Compositions (A), (/J) and (C) of the present invention in water @
When dissolving or dispersing, water-based and Ethyl cellosolve, provir selon, butyl selon, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diacetone alcohol, 4-methoxy-4-, which can dissolve each resin composition.
Organic solvents such as methylpentanone-2 and methyl ethyl ketone are added in an amount of 10 to 1,007 parts per 100 parts by weight of each resin composition.
It is preferable to renew the T leaf part 1.

The l-polar deposition type visual coating composition of the present invention may further contain a suitable pigment. For example, iron oxide, lead oxide,
One or more pigments such as strontium chromate, carbon black, titanium dioxide, talc, aluminum silicate, barium sulfate can be included.

These faces 4 and -F can be gradually added to the composition of the present invention as they are, but a large amount of pigment is added to a portion of the jp'W component (A) that has been neutralized and dispersed or liquefied in water in advance. It is also possible to obtain a pasty master patch and add this pasty pigment to the composition.

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

Production Example 1 Polybutadiene B-2000 (number average molecular weight 2oo
o, i, 2 bonds (65) were epoxidized using peracetic acid to produce epoxidized polybutadiene (EI) with an oxirane oxygen content of 6.4%.

This epoxidized polybutadiene l, >1,000? and Sadimethylamine 7092 charged in an ethyl cellosolve 333ff21 autoclave, and heated to 150℃ for 5 minutes.
Time anti-Ll', ': made. After distilling off unreacted amine, acrylic acid 36f', eleostearin + J140F
, hydroquinone 7.52 and ethyl cellosolve 73
．． The mixture of 9 F was saturated and further reacted at 150° C. for 45 minutes to prepare a 1 minute (/f) resin solution (A1) of the present invention. The Amine song of this one is! The acid content was 7.5 mmol/100F, and the solid content was 750 mmol/+00F.

Zeo Lucky Example 2 1Lf+Holybutadiene B-t, 5oO (number average molecular weight 1800.1.2% 64%) was epoxidized using peracetic acid to produce epoxidized polybutadiene with oxirane oxygen content & 5%. .

This epoxidized polybutadiene (E,)t,o.

02 and ethyl cellosolve 358t and methylethanolamine? 5. The mixture was placed in a fi3t separable flask and reacted at 100°C for 6 hours. reaction d, 120
Cool to 18°C and add acrylic acid. OP highly conjugated linoleic acid (part name Hygiene, manufactured by Sokenkaji Co., Ltd.) 2to, or
, hydroquinone 7.2f and ethyl cellosolve 69
．． Process the mixture of 2 f.

The tree of component A of the present invention was reacted at 120°C for 4 hours! A fat solution (A,) was produced.

The amine value of this product was 57.1 otixoot, the acid value was 9.9 r, 1 tnol/l 0 GF, and the solid content concentration was 75% by weight.

Production Example 3 Nisseki Polybutadiene B-2000 (number average molecular weight y 2
000, l, 2 bond 65%) 4ooor, anhydrous maleic t+'l-168f% At 19
The reaction was carried out at 0°C for 5 hours. Next, unreacted maleic anhydride,
The xylene was removed under reduced pressure and the maleated polybutadiene (#, )
f: Synthesized.

Then maleated polybutadiene (M,)t,o.

02, Ethyl Cellosolve 2002 was charged into a 2t Cenosolapuru flask equipped with a reflux condenser and heated to 80° C. with stirring. Next, I'd, IV dimethylamitube 7146f was added. Immediately after the dropwise addition was completed, the temperature was raised to 150°C, and the reaction was continued at 150°C for 5 hours. Using water produced under reduced pressure, ethyl cellosolve, and unreacted amine, an imidized polybutadiene having a tertiary amine group was synthesized. The amine value of this imidized polybutadiene was 132 mmol/xooy. The solid content of this imidized polybutadiene was 75'di''+, il
Resin bath solution (A,) '5c of component (4) used in the comparative example of the present invention, dissolved in ethyl cellosolve to a concentration of
Manufactured.

Production example 4 Nisseki polybutadiene/J-1,800 (number average molecular weight 1
goO (64% of 11,2 bonds) was epoxidized using peracetic acid to produce xyfe-oxygenated polygetadiene (E8) containing 816.4% of oxirane fuzz.

This epoxidized polybutadiene (Em) 1.000F, ethyl cellosolve 3582 and methylethanolamine 75, IF were charged into a 3t separable flask.
The reaction was carried out at 50°C for 6 hours. The reaction was cooled to 120°C and heated to acrylic [79.2F.

Hydroquinone 7, 2 P? -,- and ethyl cellosolve 102 were added and allowed to stand at 120°C for 4 hours.
) was manufactured.

The amine value of this product is 65.4 mmol/L OOf!
.

The acid value was I O, Ommol/1 G Of, and the solid content concentration was 75 deuterium.

Production Example 5 A bisphenol type epoxy resin having an epoxy equivalent of s s 5i [trade name Epicoat 1004 manufactured by Yuka Ciel Epoxy Co., Ltd.] was prepared by reacting bisphenol A with shrimp chlorhydride in the presence of a total alkali catalyst. ) 1.000 t was dissolved in ethyl cellosolve 336.7PK, acrylic acid 79.2F,
Hydroquinone 129 and N,N dimethylaminoethanol were added at 61°C, heated to 100°C, and reacted for 5 hours to form an epoxy resin-acrylic acid adduct of the components used in Examples of the present invention and Comparative t/11. An ethyl cellosolve solution <BI) was synthesized.

Production Example 6 The following compound CH was obtained by reacting bisphenol A and epichlorohydrin in the presence of an alkali catalyst.

As a result, bisphenol type epoxy g fat [trade name Ko Pico] 1001 Yuka Ciel E I x (a) M]t, o o o t having an epoxy equivalent of 485'e was dissolved in 360.6 t of ethyl cellosolve, and acrylic acid 156F
,/"Idloki/71Of and N,fit 52 methylaminoethanol was added, heated to 100°G and reacted for 5 hours, and the epoxy individual fat-acrylic acid adduct of the component used in the comparative example of the present invention was prepared. Ethyl cellosolve solution (lot) τ was synthesized.

Production Example 7 Shiraishi Polybutadiene B-500 (number average molecular weight 500.
1.2 bonds 1%) t, ooor, maleic anhydride 11
7.3F, 77f) i'73G'1 f and xylene 1 (1') were charged into a 2-t double rubble flask equipped with a reflux condenser and reacted at 195°C for 5 hours under a nitrogen stream. The reacted maleic anhydride and xylene were distilled off under reduced pressure to synthesize maleated polybutadiene (M,) having an acid value of 107 mmol/1oOf.

Maleated polybutadiene (&) 500F and ethyl cellosolve 148t were reacted at 120°C for 2 hours to reveal the succinic anhydride group, then cooled to nitrogen temperature, and a 22.5% by weight aqueous solution of sodium hydroxide 1002 was gradually added. After neutralization, deionized water was added so that the solid content concentration was 25% by weight, and the maleated polybutadiene water bath solution was prepared.

Next, manganf sulfate (MnSOt-4,5HIU)
After dissolving 74.5 t in 6001 of water, 600 f of isozorobyl alcohol and 1.000 t of benzene were added, and 2.192 t of the aqueous solution of the above maleated polybutadiene was gradually added dropwise at room temperature while stirring, and the temperature was raised to 60° C. 30
After heating for 1 minute and static electricity for 1 hour, it separated into two layers, so cut the bottom layer, add deionized water L0002, and heat to 60℃ for 30 minutes.
After heating for 1 minute, 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.

This manganese salt of maleated polybutadiene was dissolved in ethyl cellosolve so that the solid content was 75%, and the oil-bathable manganese salt of the component (C゛) of the present invention was dissolved in ga (C+
) Manufactured in 1. The manganese content of (C1) was 2% by weight.

Example 1 (, 4.) 400F manufactured in Production Example 1 and Production Example 5
(B+) 240F and butyl cellosolve 2 manufactured by
After mixing 52 until homogeneous, acetic acid asy was added and thoroughly stirred to neutralize. Next, deionized water was gradually added to prepare an aqueous solution having a solid content of 25% by weight. This 25
Weight% aqueous solution 1,000t1 Carbon Black L5? ,
252 t of basic lead silicate and 1.000 t of glass beads
into a 3t stainless steel beaker and mix with a high-speed rotating mixer.
After stirring vigorously for an hour, after filtering the rasp beads,
Add deionized water so that the solids concentration is III.
An electrodeposition coating solution was prepared.

The above electrodeposition coating liquid was used to make a carbon electrode as an anode, and a zinc phosphate treated plate (Japan Test Panel Co., Ltd., B13004.0) was prepared.
．． Cathode deposition type electrodeposition coating was performed using a 8×70×150 #l11) as a cathode. The test results are shown in Table-1.

Comparative Example 1 A cathode-deposited electrodeposition coating solution was prepared under the same conditions as in Example 1, except that (A,) produced in Production Example 3 was used instead of (, (,) produced in Production Example 1. , 1 A test was conducted under the same conditions as in Example 1, and the results are shown in Table 1.

Table 1 Test results Note 1) Methyl imbutiltone ζ rubbing test (50 times per minute) Judgment is as follows.

O remains unchanged, △ and dark areas become cloudy, and X is exposed.

Note 2) Judgment is made as follows based on the maximum rust width from the cut part made on the paint film.

(Ri 1 #0++ and above, 01~2m, △2~3
Lightning strike, 3m or more (5% NaCl aqueous solution spray).

Note 3) Toyo Baldwin automatic viscoelasticity measuring instrument RH
EOVIBRUN DDV-1-EA type used (measurement conditions) Temperature rising speed 3℃/poison in Frequency 1IHz Example 2 (Δ,) 400F manufactured in Production Example 2, (Bt) 120F produced in Production Example 6, and Production Example 7 (C+
) t9. Because sy was mixed until homogeneous, acetic acid 6.9
2 was added and stirred thoroughly to neutralize. Next, deionized water was gradually added to prepare an aqueous solution having a solid content concentration of 20% by weight.

This 20% by weight aqueous solution 2.00 Or, carbon black 49. Basic lead silicate 20? and Glass Peas 2,0
After putting it in an OOfi5t stainless steel beaker and stirring vigorously for 2 hours with a high-speed rotating mixer, the glass beads were filtered, and deionized water was added so that the solid fraction concentration was 15% by weight and 11% to adjust the electrodeposition coating liquid. .

Using the above electrodeposition coating liquid, a carbon electrode was used as an anode, and a zinc phosphate treated plate (Nippon Test, B13004.
Cathode deposition type fixing coating was performed using 0.8 x 70 x 150 mm as a cathode. The test results are shown in Table-2.

Comparative Example 2 A coating liquid was prepared in the cathode deposition mold 1 under the same conditions as in Example 2 except that (A4) produced in Production Example 4 was used instead of (A, ) produced in Production Example 2. A test was conducted under the same conditions as in Example 2, and the results are shown in Table 2.

Table 2 Test Results Note 1) Rubbing test with methyl isobutyltone (50 times per minute) Judgment as follows.

0 unchanged, △. However, it clouds up, and the cable ends.

Note 2) -14" is determined as follows at maximum rust from the cut part made on the paint film.

◎1 printing or less, ○l~2 chuu, △2~3 korean, ×3 battles or more (5
%NaCl water solution spray).

Note 3) Automatic viscoelasticity measuring instrument R1 manufactured by Toyo Bold Line Co., Ltd.
1 EUVIBRUN DDV-EA type used (measurement conditions) Temperature rising speed 3°C/min Frequency 1xHz Procedural amendment August 17, 1980 Patent section length 1. J1'1tllll': 5 9 - 8
5 1 0 1 No. 2, Name of the invention u%i IL precipitation type 'jjj; Right ji: Oh Hyok-sei 9 No 3 Relation to the Nagisa case Patent applicant residence Ha [Minato-ku, Tokyo 4 Ka 1 - Ding I = + 3 No. 12 Name
(444) Japan A Oil Co., Ltd. (name) and 1 other person Subject of 6 amendments + ti The following two corrections are made to the claims in the specification of the present application.

"(A) (1) 500-5. OOO molecular weight is 50
Polymer compound (2) having a carbon-carbon double bond with an iodine value of ~500 and 3 to 12% by weight of oxirane oxygen The polymer compound of (1) above 100. 30~ per g
300 mmol of the general formula [In the formula, R1 and R1 represent a hydrocarbon having 1 to 20 carbon atoms, a part of which may be substituted with a hydroxyl group; however, R1 and R7 can have a ring structure; The structure may contain unsaturated groups. ] Amine compound (3) Polymer compound of formula (1) 100#Wsu0-2
00 mmol of the general formula CH,,=C-C-OJ'1 [wherein R3 and R4 represent a hydrogen atom or a methyl group. ] α, β unsaturated carboxylic acid represented by (4) an unsaturated carboxylic acid having a molecular weight of 100 to 350 and containing 10% by weight or more of carbon-carbon conjugated double bonds and having a molecular weight of 200 to 50 mmol per 100 g of the polymer compound of formula (1). Reaction product of saturated fatty acid 100 parts by weight CB) A diglycidyl compound represented by the general formula [wherein R, Ro are hydrogen atoms or methyl groups, and n represents an integer from 0 to 20, preferably from 1 to 10]; Substantially 2 moles per molecule of the diglycidyl compound of the general formula [wherein R1 and R3 represent a hydrogen atom or a methyl group. ] 10 to 200 parts by weight of a product obtained by reacting an α,β unsaturated carboxylic acid represented by (C) 0.005 to 1.0 parts by weight of an organic acid manganese salt or manganese dioxide as a metal amount Gold essential component A cathodically deposited electrodeposition coating composition with excellent low-temperature curability.

(2) On page 13, line 13, the statement “conjugated” is corrected to “conjugated”.

(3) The description of "castor oil" on page 14, line 3 is corrected to "castor oil fatty acid."

(4) On page 17, line 1, the word ``make'' is written as ``manufacturing.'' Correct to.

(5) On page 21, line 4, the description of "baking polymerization" is corrected to "oxidative polymerization."

(6) The description of "room temperature" in lines 5 and 13 of page 33 is corrected to "room temperature j.

()) On page 33, line 9, the statement ``adjusted'' was corrected to ``1 adjustment was made.''

(8) [(Mn5O,・4.5H,0
) is corrected to r (Mn504- +, 5JI20) J.

(9) The description of "methyl isobutyltone" in the bottom line of Table 1 on page 36 and the bottom line of Table 2 on page 39 is corrected to ``methyl isobutyl ketone j.

fII　Page 38, line 4, “solid content” was changed to “solid content” Correct to.

a [The description of “adjustment” in lines 6 and 15 of page 38 is corrected to “preparation.”

Claims (1)

[Scope of Claims] (A) (1) 50 with a molecular weight of 5-00 to 5,000
Polymer compound (2) having a carbon-carbon double bond with an iodine value of ~500 and oxirane oxygen in an amount of 3 to 12% by weight
930 to 300 mmol per 1oor of the polymer compound of (1) above (wherein R and R1 represent a hydrocarbon having 1 to 20 carbon atoms, a part of which may be substituted with a hydroxyl group; R1 and R1 can have a ring structure, and the ring structure can contain an unsaturated group. ] Amine compound (3) θ~2 per 1002 of the polymer compound of formula (1)
00 mmol General formula % Formula % [In the formula, R8 and R4 represent a limescale atom or a methyl group. ] α, β unsaturated carganic acid represented by the formula (4) a polymer compound of formula (1) with a molecular weight of 100 to 350 and a carbon-carbon conjugated double bond of 10 to 50 mmol per 1002 parts by weight or more 100 parts by weight of reaction product of unsaturated fatty acids containing (B) diglycidyl represented by the general formula R61 [wherein R3 and R6 are hydrogen atoms or methyl groups, and n represents an integer from 0 to 20, preferably from 1 to 1O] compound and substantially 2 moles per molecule of the diglysidur compound of the general formula % Formula % where R1 and R represent a hydrogen atom or a methyl group. 10 to 200 parts by weight of a product obtained by reacting with phosphoric acid <C> An im-temperature containing 0.005 to 1.0 parts by weight of manganese salt of an organic acid or manganese dioxide as an essential component as a metal amount. A cathodically deposited paint composition with excellent curability.