JPS59133270A - Cathodic electrodeposition paint composition - Google Patents

Abstract

PURPOSE:To provide a cathodic electrodeposition paint compsn. having excellent stability and resistance to corrosion and solvents, by adding a bisphenol type epoxy resin to which an alpha,beta-unsaturated monocarboxylic acid is partially added, to a specified water-dispersible resin. CONSTITUTION:A paint compsn. contains 80-40pts. high-molecular compd. (A) having an MW of 500-10,000 and contg. 50-200mmol of tert-amino groups, 200-2,000mmol of non-conjugated carbon-to-carbon double bonds and 20- 200mmol of alpha,beta-unsaturated monocarboxylate ester groups per 100g of the resin and a compsn. (B) which is made water-soluble or water-dispersible by neutralizing it with an acid, said compsn. consisting of resins of formulas I and II[wherein R is a bivalent org. group of formula III (wherein R1, R2 are each H, a 1-10C alkyl; P is 0, 1-20); X is a functional group of formula IV (wherein R3 is H, methyl); Y is a functional group of formula V; the molar ratio of the X group to the Y group in the mixture is 1.8:0.2-1.2:0.8].

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a negative electrodeposition coating composition having excellent corrosion resistance, solvent resistance and stability.

A resin having a basic group produces a cationic resin in water, and when electrodeposition is performed using this resin, the resin is deposited on the cathode. This type of cathodic deposition type paint is made by neutralizing the resin with acid groups with a base and making it water-soluble. It is possible to eliminate the elution of metals and the various @spots caused by it.

The present inventors have studied such cathodically deposited electrodeposition paints, and have previously discovered that they can be applied to high molecular weight compounds containing unsaturated groups, such as low degree of purity synthetic polymers having carbon-carbon diconstant bonds, such as liquid polybutazene. It was discovered that a pattern resin for cathode-deposited electrocoating paints with excellent overturning properties could be obtained by introducing grade amino groups.
-119727, JP-A-52-147638, pith:
Opening and closing number 53-16048).

The cathodic deposition type fixing paint, Kinukou, which uses the above-mentioned resin as a paint component, cures mainly through the drunkenization of the unsaturated groups contained in the resin and provides a coating film with excellent performance, but the curing time is not practical. Relatively high baking temperature is required for hardening. It is also possible to cure the coating film at a low baking temperature of 1/1 by adding a dryer to the entire width of the water-soluble manganese tower, but in this case, a large amount of dryer is required, and problems such as throwing power etc. 5. Problems such as deterioration of painting performance and easy roughening of the painted surface occur. Furthermore, there were also concerns that performance such as corrosion resistance was not fully satisfied.

In addition, the inventors have also developed a crypt-precipitating method in which a water-dispersible modified epoxy resin in which a secondary amine is added to the water-dispersible resin having a carbon-carbon double bond and a three-part diamino group is added. It was discovered that the material collected by the "Katadenen Paint Department" had excellent corrosion resistance, and a patent application was filed (Japanese Patent Application Laid-Open No. 55-60572, JP-A-55-60851++).

A cathodic deposition type electrodeposition coating composition containing the above #1' fat as a coating component (d has excellent corrosion resistance and stability of the deposited coating liquid, but
Added modified epoxy resin 7'I: Due to poor oxidative polymerizability, there was a drawback that resolvent properties were poor.

1. The present inventors have developed a modification that does not have water dispersibility by adding ゛ to the α and β unsaturated carbons in the water-dispersible resin having a carbon-carbon double bond and a tertiary amine group. He discovered that a cathodically deposited electrodeposition coating composition containing an epoxy resin (d) provides excellent corrosion resistance, solvent resistance, and Matsuoka characteristics, and filed a patent application (Japanese Patent Application No. 1983-69931, Patent, 1982).
-55473, Japanese Patent Application No. 54-117857).

The cathode-deposited electrodeposition paint composition -17/l containing the above dried PV as a paint component cures mainly through oxidative polymerization of the unsaturated groups contained in the dried PV, and strengthens the coating film with poor corrosion resistance. However, there were some problems with the stability of the electrodeposition coating solution.

Therefore, it is an object of the present invention to provide a cathodic deposition coating material which has excellent coating properties such as corrosion resistance and solvent resistance, as well as excellent corrosion resistance and stability of the electrical coating solution.

In order to achieve the above-mentioned object of the present invention, the present inventors have made the conclusion of their research into (A) the above-mentioned carbon-bonded double bond, tertiary amino group, and α/β-unf-z monocarbon. A monopolar deposition type electrical coating composition in which (B) a bisphenol type epoxy resin to which α/β unsaturated monocarboxylic acid is partially added to a water-dispersible resin having an acid ester group has excellent corrosion resistance. The present invention was achieved based on the discovery that the present invention provides 11α physical properties such as solvent resistance and excellent safety of the paint liquid.

That is, the present invention provides: (A) 100 g of resin, 50 mmol to 200 mmol of tertiary amine groups, 200 mmol to 2000 mmol of non-conjugated carbon-carbon double bonds, and 20 mmol of α/β unsaturated monocardic acid ester groups; 80 to 40 parts of a polymer-4 compound having a molecular weight of 500 to 10,000 and having a molecular weight of 500 to 10,000 mmol and [wherein R and general formula R, OB 1'? , 2 (wherein R1 and R2 (1-!: hydrogen atom or alkyl group having 1 to 10 carbon atoms, p represents an integer of 0 to 1 to 20) 2
A valent organic group, A non-functional compound represented by , and the number m of moles of Y group in the mixture and the number n of moles of Y group: n is 1.8:0.2 to 1
．． 2: in the range of 0.8] By neutralizing the composition consisting of the resin 20 to 60s with acid, the composition can be made water-soluble or (d) The water-dispersible composition can be used as an essential component. achieved by.

Component (A) used in the present invention, that is, a resin having a carbon-carbon double bond, a tertiary amino group, and an α-β unsaturated monocarboxylic acid ester group has a rating of 500 to 10.
A polymeric compound having a molecular weight of OOO and a carbon-carbon double bond of 100 to 500 iodine@j is epoxidized to form an epoxidized polymer containing oxirane oxygen of 0.5 to 12 F-i'':%. A molecular weight compound of 1 to 10% is prepared, and a part of the epoxy group of the epoxidized compound has a general formula (wherein R4 and R6 are 1 to 10 carbon atoms each independently).
The hydrocarbon groups of R4, etc. may be partially substituted with a hydroxyl group. , may form a cyclic structure), and then, part or all of the remaining epoxy groups are reacted with the general formula % formula % (wherein R3 is hydrogen atoms do not represent methyl groups).

It is produced by reacting α/β unsaturated monocarboxylic acids represented by:

Polymer V having a carbon-carbon double bond with an iodine value of 100 to 500 and a number average molecular weight of 500 to 10.00'O: Examples of compounds include linseed oil, tung oil, soybean oil, and dehydrated castor oil. Natural oils and fats or natural oil pressure gauges/
So-called stand oils that have been heat-treated to increase their molecular weight, low polymers of conjugated diolefins such as butatsuene, isoprene, and piperylene, low polymerization degree copolymers of two or more of these conjugated diolefins, and Monomers having two or more conjugated diolefins and ethylenically unsaturated bonds, especially aliphatic or monomers such as isobutylene, twinbutylene, styrene, α-methylstyrene, vinyltoluene, and sopinylbenzene. It is a low polymerization degree copolymer with an aromatic vinyl monomer.

A mixture of two or more of these can also be used. These low polymers are produced by conventionally known methods.

In addition, a petroleum fraction with a coal content of 4 to 10 times the temperature of 0 to 100°C using a Friedel-Craft catalyst such as aluminum chloride, boron trifluoride, or a complex thereof.
So-called I7J petroleum (91 fat) having an unsaturated group produced by cationic polymerization in the presence of water, and also a light copolymer of butazoene-isobutylene produced using the same type of catalyst. etc. can also be used.

The molecular weight of the high molecular weight compound as exemplified above is 10,0.
If the molecular weight is greater than 00, the solubility and properties in water may be poor, and if the molecular weight is less than 500, the strength of the coating film will be too small to be used practically.

However, if the iodine value is less than 100, the curing properties will be poor, and if the iodine value is more than 500, the storage stability will be 75=74.
4 (Cannot be put to practical use.

In the present invention, first, an unsaturated high molecular weight compound 1 such as the above-mentioned natural oils or fats or conjugated diolefin low polymers or copolymers is epoxidized, and -
ΣFormula (a") 6 7 (where R6, R, is a water wing atom or a methyl group; X is a hydrogen atom or represents a uqy combination, and when X is a combination, ID
The carbon atom attached to Ra and the +1 carbon atom attached to R7 can both form a part of the main chain).
From the main chain high molecular weight moiety (a') having a molecule Y and an iodine value of 100 to 500, and the F1? An epoxidized high molecular weight compound is prepared.For this epoxidation, a conventionally known method of reacting with 11-acetic acid at a temperature of 0 to 100° C., for example, can be used.

(Japanese Patent Publication No. 33-3239, Publication No. 33-3240, Japanese Patent Publication No. 37-15107) An epoxy group represented by the above general formula (in which R6, R7 and X are the same as above), 0.5 to 12
0 weight is preferably 141.5 to 8.0 weight 4'ti%.

The above epoxy group has an oxirane F content of 0.
If the amount of 5-layer cake is small, the superfat obtained by reacting with a basic amine compound and dissonant carbon vinegar may have few basic groups and water solubility, resulting in poor water dispersibility. (d
The disadvantage is that the amount of reactive carboxylic acid is too small to improve the curing properties.

Also, if the epoxy groups mentioned above are more abundant than the oxirane-79-containing group than the 100-fold group, the number of basic amine groups is the same. The viscosity of the wood chips obtained by reacting with α and β unsaturated monocarboxylic acids is too low to be used for commercial purposes.

The epoxidized polymer compound as described above is then treated with a portion of its epoxy groups, preferably oxirane having an oxygen content of 0.3 to 6.0, more preferably 17i.
The following general formula (in the formula, R4 and 11. are each independently a carbon number of 1 to 10
(Each group may be partially substituted with a hydroxyl group, and R4 and R6 may form a ring structure.) Furthermore, 0.2 fold of the remaining epoxy groups, preferably 1.0 fold of the remaining epoxy groups, is added to the following general formula 0% (wherein R8 represents a hydrogen atom or a methyl group). A resin composition containing a Japanese group, a basic group, a hydroxyl group and an ester group (4) by reacting an α/β unsaturated monocarboxylic acid represented by get.

Examples of secondary amine compounds represented by sulfur are trimethylamine,
Aliphatic secondary amines such as diethylamine, subbutylamine, and dioctylamine, secondary alkanolamines such as soethanolamine, monomethylethanolamine, and dupropanolamine, aromatic secondary amines such as monomethylpentylamine, and morpholamines. It is a secondary amine compound with chemical compounds such as phosphorus and piperidine.

The reaction between the epoxy group and the divalent metal-containing molecular weight material and the secondary amine is carried out at 50 to 200°C, preferably at 100°C.
It is produced at a warm temperature of ~150°C. The above reaction can be carried out in the presence or absence of a solvent. If the viscosity of the epoxy group and double bond gold-containing polymer used in the reaction is high, it is preferable not to use a solvent, but if the viscosity is high, benzene, toluene, xylene, cyclohexane, methyl cellosolve, etc. , ethyl cellosolve, propyl cellosolve, butyl cellosolve, ethyl ether,
Solvents such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether can be used.

When using a solvent, it is economical to use a wood-based solvent such as r,l-ethyl cellosolve, methyl cellosolve, butyl cello lua, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether as a reaction solvent and use it as it is for subsequent water bathing. It's a perfect size.

The alpha/beta-filtering and monocardenic acid used in the present invention are acrylic acid and methacrylic acid, and mixtures thereof can also be used.

The reaction between the monocarboxylic acid and the epoxy group is preferably carried out at a temperature of 50 to 200°C, preferably Nd1oo to 150°C.

The above reaction can also be promoted by adding tertiary amines such as trimethylaminoethanol and quaternary ammonium salts such as tetraethylene pensol chloramed as catalysts.

double bonds of alpha/beta-immiscible monocarboxylic acids (polymerize with each other or copolymerize with double bonds in the main chain high molecular weight compound (a') to form undesirable polymers) In order to prevent this, a polymeric tableting agent such as hydroquinone or BH1' is added to the system in an equivalent amount of Zr.
It is preferable to react.

The amount of epoxy groups in the polymer compound that reacts with the above α/β unsaturated monocarboxylic acid is 7 m
It is usually at least 0.2 detonations, preferably at least 1.0 detonations. Sufficient curing performance cannot be obtained in polymerizations in which the oxirane oxygen content reacted with α/β unsaturated monocarboxylic acid is less than 0.2 fold N ratio.

The component (B) used in the present invention is of the general formula
11; [wherein R is the general formula 2 (in the formula, 77, and R2 is a hydrogen atom or a carbon number of 1 to 1]
0 alkyl, p (represents an integer from 0 to 1 to 20), a divalent specific group; The number of moles of Y group in 1 and the mixture +17)
Ratio of the number of moles of the group: n (cutting 1, 8: 0.2 to 1.2
: in the range of 0.8].

is a mixture, and the ratio man of the number m of moles of Y group and the number n of moles of Y group contained in the whole mixture is 1.8:0.2 ~
It is a mixture in the range of 1.2:0.8.

These usually have an average molecular weight of 300 to 30,000. These are generally α/β unsaturated molecules [300 to 30, represented by the general formula % formula % (Rs is the same as above) per molecule of so-called bisphenol type epoxy resin having epoxy groups at both ends of OOO. Monocarboxylic acid 1.2 mol to 1
．． It is obtained by reacting 8 mol at 50-200°C, preferably 80-150°C. It is preferable to add a salty amine compound every once in a while to promote the reaction. A reaction solvent can be used to lower the viscosity of the reaction system, but water-soluble solvents such as ethyl cellosolve, methyl selonulp, butyl cellosolve, etc. are used as the reaction solvent in the lifting platform where a solvent is used, and used as is for subsequent water solubilization. The method is economical and preferred.

Hydroquinone, BET-
It is preferable to add any polymerization inhibitor per flame and allow the reaction to occur.

The ratio of component (A) and component (B) is (,4) component 80 to 4
0 parts (B) Component 20-60 parts Preferably (,4) Component 6
0 to 50 parts (B) In the range of 40 to 50 parts per g, the corrosion resistance of this one grain is less than the part in the box (B). If the amount is higher, the smoothness of the cold surface becomes poor and it becomes impossible to use as a nutrient.

In the present invention, in order to make component (4) and component (B) water-soluble or water-dispersible (c. Kuke 0.3~0
．． A method of neutralizing with 8 molar equivalents of a water-soluble organic acid such as acetic acid, propionic acid, lactic acid, etc. can be preferably used. When component (B) is blended with component (A), the organic acid used for neutralization and a small amount of water are first added to the blended Tochizukisu composition before it is water-solubilized, and the mixture is made uniform at 50 to 80°C. . Then Tue f:
It is preferable to dissolve the water by cutting the water.

These neutralizations are also usually achieved by simply mixing the acids at room temperature.

In the present invention, a dryer can be added to a composition obtained by dispersing R:min(A, )(B) in water or forming an aqueous solution in this manner.

For the dryer, gold and general salts such as manganese, cobalt, zinc, and lead are used, and water-soluble manganese compounds are especially suitable. Such water-soluble manganese compounds include manganese salts of relatively low-molecular organic acids such as manganese formate, manganese acetate, zolopionic manganese,
Manganese lactate and manganese salts of 'JJt<'+' diacids such as beta manganese, monomanganese, manganese a, and manganese acetylacetonate are used. Addition of manganese compound (doiff+: +
0.01 to 5.0 type bone part, preferably 0.1 to 1.0 as manganese metal per 100 parts of d-acid component A)
A heavy base is used.

Ingredients (, 4) and CB) of the present invention neutralize ir and dissolve or disperse in water, facilitate dissolution or dispersion, improve stability of aqueous solutions, and improve fAa properties of tree manure. However, for the purpose of improving the smoothness of the coating film, water-soluble and dissolving each tree 111H composition such as silylethylselonurp, propyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, diethylene glycol somethyl ether, Organic solvents such as soacetone alcohol, 4-methoxy-4-methylpentanone-2, and methyl ethyl ketone are added in an amount of 10 to 1 per 100 mold parts of each resin composition.
It is preferable to use 00 parts by weight.

The cathodically deposited electrodeposition coating composition of the present invention may further contain a suitable pigment. For example, one or more pigments such as iron oxide, lead oxide, strontium chromate, carbon black, titanium dioxide, talc, aluminum silicate, barium silicate can be incorporated.

It would be a mistake to add these face V='1.1 directly to the composition of the present invention, but is component (A) dissolved in water in advance? A paste-like masterbatch is obtained by adding and mixing a portion of the fl-converted pigment with a multi-pigment, and this paste-like pigment can be added to the composition.

Next, the present invention will be explained more specifically using Examples and Comparative Examples.
F:', I'll clarify. Physical property tests of the coating films of the practical examples and comparative examples were conducted in accordance with J'IS-5400.

Production Example 1 A liquid polygetatsuene having a number average molecular weight of 2000.1,2-bonds of 65% was epoxidized using peracetic acid to produce an oxirane oxygen-containing cello-triple epoxidized polybutatsuene.

Next, 55 g of this epoxidized polybutadiene 100 (1° ethylseron lube 300.9.dimethylamine) was charged into a 21 autoclave, and after reacting at 150°C for 5 hours, the unreacted dimethylamine was distilled off by returning the pressure to vapor pressure. Next, acrylic tit 80 F/ and 0.5 g of hydroquinone were added and reacted at 150°C for 1 hour to produce a component (A), lily fat component (A-1).The solid content concentration was 80%. He was in charge of the county.

This component (A) having a tertiary amine group and an unsaturated group is
It had 100 mmol of tertiary amine groups per 100 g of l'''.

Production Example 2 Liquid polybutadiene with a number average molecular weight of 4 soo and 63% of 1.2 bonds was epoxidized using peracetic acid to produce oxirane [
Epoxidized polybutatsuene with a warm nitrogen content of 65% by weight was produced.

Next, this epoxidized polybutadiene 1000 &.

Ethyl cellosolve 37 (1, 40 g of dimethylamine 2
4. After charging into an autoclave and reacting at 150°C for 5 hours, unreacted dimethylamine was distilled off by returning the pressure to normal pressure, and then 80 g of acrylic acid and 5 hours of hydroquinone
．． 51! r, 1 was added and reacted at 150°C for 1 hour.
A) resin component (A-2) was produced.

This resin ° component [, 4-z) 74 resin 100I Schiff 5
It had millimoles of tertiary amine groups, and the solids concentration was 75%.

Production example 3 Bisphenol type epoxy resin (Mitsui Epoxy Co., Ltd. EboMitsuku R-301) 960.9 (Epoxy 4q
2.0 mol), ethyl cellosolve 343&.

Hydroquinone 9II, acrylic acid 126J9 (1,7
5 mol), and 5 g of dimethylethanolamine at 21
The resin component (B-1) of component (B) was prepared by charging it into a C/J rubble flask and reacting at 110°C for 5 hours.The solid content of this product was 75% by weight, and the residual epoxy group was 17%.
mmol/10'0. ? It was hot.

Production Example 4 Bisphenol-type epoxy resin (Shell Chemical Co., Ltd. Epicoat≠1001) 971 (Engineering, IPxy 412.
0 mol), acrylic acid 108.1 g (1.5 mol)
, hydroquinone 5.4g, ethyl cellosolve 350
, li', trimethylethanolamine 5.3 F wo2
The mixture was charged into a separate flask and reacted at 110°C for 3 hours to produce component (B), the resin component [B-2]. The solid content concentration of this product was 75% by weight, and the residual epoxy group was 33 mmol/100 g.

Production Example 5 Bisphenol-type epoxy resin (Shell Chemical Co., Ltd. Epicote≠101001) 974 epoxy group 20 moles)
, 147.8 g (2.05 moles) of acrylic acid, 358 g of ethyl cellosolve, 5.4 g of hydroquinone and 5.3 g of trimethylethanolamine were placed in a 21st C.J. rubble flask and reacted at 110° C. for 7 hours to give a solid content composition of 75. The acrylic adducted epoxy tree nt = (c -1) with a fluorinated epoxy group of 1 mmol/'100F or less in a heavy ladder is used in a bale i.
contributed.

Example 1 Tree of absorption (A) produced in Production Example 1 1] i = [A −
1) 125, S7, phase part of component (B) produced in Production Example 3 [B-i) soFs Vinegar N, 2.4.9 and 7.2 g of deionized water were uniformly mixed and heated to 60 °C for 1 After cooling for a certain period of time, deionized water was added to prepare an aqueous dispersion having a solid concentration of 20. The average particle size of this dispersion was 50 mμ, which was very small.

This aqueous dispersion contains 1.6 g of carbon black and 4.0 g of lead oxide.
Blend 8g of pigment, then 1.0,! 9 manganese acetate and deionized water were added to make a black electric paint v1. with a solid content concentration of 15. It was created. p II of this electrodeposition coating liquid
The pH was 6.4, and there was no change in pH 1 conductivity even after 20 days of drying at 40°C, and there was no visible pigment aggregation, making it extremely stable.

? j-1: 1. f. The test results for the paint are shown in Table 1.

Example 2 Component (A) tag produced in Production Example 2 [fat [A-2] 1
33.3&, Component (B) resin produced in Production Example 4 [:
B-2:]106. ? ,! 9. 1.89 g of acetic acid and 5.4 g of deionized water were mixed at 80° C. for 1 hour, cooled, and deionized water was added to prepare an aqueous dispersion having a solid content concentration of 20 parts. The average particle size of this dispersion was 45 mμ, which was very small.

This aqueous dispersion contains carbon black O,'l, lead mide 6.
31! , 2.8 g of titania were blended, and then 1.3 g of manganese acetate and deionized water were added to prepare a Daley's electric blue coating phase having a solid content concentration of 15% by weight.

The pH of this electrodeposited solution was 6.3, and there was no change in 'p#, 'igi, or vomiting even after 20 days at 40°C.
Phenomena such as pigment aggregation are also extremely stable.

Compensation: The test results for cooling charges are shown in Table 1.

Ratio Example 1 In place of component (B), an acrylic acid-added epoxy resin [C
Electrodeposition paint was prepared under the same conditions as in Example 1 and 2 except that -1:) was used.

The average particle size of the 20 parts by weight resin dispersion was 400 mμ, which was so great that a precipitate was formed after it was allowed to stand still for one hour.

The electrodeposition paint liquid of 15 layered paint containing Moidaμ'@Tsuki was also heated at 40℃.
After 20 days, flocculation and precipitation occurred.

Table 1 shows the test results for the electrodeposition paint.

Note 1 Calculated from cold production - (1゛, pressure (V), residual constant flow (A-) Note 2 DuPont Ikegami, 500g, %B7, lE 3
A rubbing test with methyl isobutyl ketone (50 times per group) was evaluated as follows.

■・Unchanged, △・The rubbed area is cloudy, ×・Exposure Note 4 Paint 1: R from the cut part applied to the bottom; Judgment as follows with a dog rust cloth (20tt, +) Zinc acid chloride R Buried board B t + 300 4) ◎・Less than 1 plate, 0・1~2 rhymes, △・2~3mπ, ×・3
More than talk (5% NaCl aqueous solution spray)

Claims (1)

[Claims] (A) 100 g of resin, 50 mmol to 200 mmol of tertiary amine group, 200 non-conjugated carbon/carbon double bonds
mmol to 2000 mmol, and 80 to 40 parts of a high molecular weight compound having a molecular weight of 500 to 10,000 having 20 mmol to 200 mmol of α,β unsaturated monocarboxyl ester groups and [wherein R is general formula 2 (in the formula R1 and R2 are hydrogen, atoms, or have 1 to 1 carbon atoms
Example of alkyl 0, p represents an integer from 0 to 1 to 20) 2
'fiHA', X is a functional group represented by the general formula % (in which R3 represents a hydrogen atom or a methyl group), and the number m of moles of Y groups in the mixture is The ratio m:fL of the number n of moles of Y group is 1.8:0.2 to 1.2
:0.8] A self-curing cathodically deposited electrodeposition coating material containing as an essential component a composition that is made water-soluble or water-dispersible by neutralizing the composition. .