JPH01182376A - Method for cationic electro-deposition coating - Google Patents

Abstract

PURPOSE:To obtain a thick cationic electro-deposition coating film curable at a low temperature, by using a water paint containing a resin component consisting of a resin having unsaturated carbonyl group and hydroxyl group and a resin having a group containing a specific aprotic onium salt. CONSTITUTION:The paint used in the title coating process is a water paint containing a resin component consisting of (A) a resin having alpha,beta-unsaturated carbonyl group and a primary or secondary hydroxyl group in the resin and (B) a resin having a group containing an aprotic onium salt of formula I [R1 is hydroxyl group, alkoxy group, eater group, 1-8C hydrocarbon group which may be substituted with halogen atom or H; R2 is H, hydroxyl group or 1-8C hydrocarbon group; -W<+> is group of formula II or formula III (Z is N or P; Y is S; R3, R4 and R5 are 1-14C organic group, etc.)]. A coating object is used as a cathode and is coated with the water paint by cationic electro-deposition coating.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field 1] The present invention relates to a cationic electrodeposition coating method capable of forming a thick electrodeposition coating film that can be cured by heating at a relatively low temperature.

[Prior art] Cationic electrodeposition coatings are widely used for automotive podium brammers, one-coat finishes for various industrial equipment, etc., but generally the electrodeposition coatings are cured at a relatively high temperature of 160°C or higher. It is necessary to heat it to In addition, when incyanate-curing electrocoating paint, which is the most widely used type in this field, is electrocoated, the cured coating may turn yellow, and when a top coat is applied on top of the electrocoat coating, the top coat may bleed. It has drawbacks such as yellowing. Furthermore, recently, corrosion resistance performance,
In order to respond to the increasingly sophisticated requirements for paint finishes,
Electrodeposition coatings that can increase the coating thickness are desired, but with incyanate-curing types that produce desorption products as by-products during curing, the applicable coating thickness is only about 50 microns. However, if it exceeds this amount, there are drawbacks such as abnormalities such as wrinkles on the painted surface and failure to obtain the expected performance due to insufficient curing.

In addition, there are electrodeposition paints that do not produce by-products during curing, such as polybutadiene and unsaturated fatty acid-modified resins, which are cured by oxidation or thermal polymerization, but these have poor coating performance such as corrosion resistance. , a large amount of unsaturated groups remain in the cured coating film, and the polymerization progresses over time, resulting in significant deterioration of the physical properties of the coating film over time. There is a drawback that there is a large difference in hardenability between the inside and the outside, making it easier for abnormalities such as scratches to occur on the surface.

[Problems to be Solved by the Invention] The present inventor has discovered that curing occurs at a relatively low temperature of 140°C or less, and
The purpose of this project is to develop a cationic electrodeposition coating method that provides electrodeposition coatings with good curability and appearance even when the thickness is 1 micron or less, and exhibits excellent coating performance such as water resistance and chemical resistance. I have been conducting intensive research.

[Means for Solving the Problems] As a result, the present inventor has developed a resin containing an α,β-unsaturated carbonyl group and a primary or secondary hydroxyl group, and a resin having a specific aprotic onium salt. By cationically electrodepositing a water-based paint with a resin component, basically no elimination products are generated during curing, and a thick film like that seen in incyanate-curing, oxidation, and thermal polymerization-curing types can be applied. We have achieved a cationic electrodeposition coating method that can achieve the above objectives without causing any problems. That is, the present invention provides (a) a resin containing an α,β-unsaturated carbonyl group and a primary or secondary hydroxyl group in the resin, and (b) an aprotic onium salt-containing group represented by the following general formula (I). -CH-CH2-WΦ OCORs (1) [wherein, R represents a hydrocarbon group having 1 to 8 carbon atoms or a hydrogen atom which may be substituted with a hydroxyl group, an alkoxy group, an ester group, or a halogen atom, R2 represents a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 8 carbon atoms, -W@ is -Z@
-Rs or R3R4 -ye, where Z is a nitrogen atom or a phosphorus atom, and Y is a sulfur atom, R3, R, and R.

are the same or different and represent an organic group having 1 to 14 carbon atoms, and R3 and R4 or R3,R.

and R5 may be taken together to form a heterocyclic group together with the nitrogen atom, phosphorus atom or sulfuric acid atom to which they are bonded. The present invention relates to a cationic electrodeposition coating method, which is characterized in that electrodeposition is carried out using an object as a cathode.

In the resin (a) of the present invention containing an α,β-unsaturated carbonyl group and a primary or secondary hydroxyl group, the α,β-unsaturated carbonyl group has the general formula -C=C-
Examples of 1m groups which can be represented as C- include acryloyl group, methacryloyl group, itaconate group, maleate group, amarate group, crotonate group, cinnamic acid group, acrylamide group, and methacrylamide group.

(a) As a resin, α, β-unsaturated carbonyl group and 1
Any conventionally known resin such as acrylic, polyester, urethane, alkyd, epoxy, or phenol resin may be used as long as the resin has a primary or secondary hydroxyl group, and is not particularly limited. a) The molecular weight of the resin is not particularly limited, but the peak molecular weight measured by gel permeation chromatography (GPC) is preferably about 250 to 100,000, and about 50
About 0 to 20,000 is more preferable.

(L) In the resin, the α,β-unsaturated carbonyl group is
0.1-10 mol per IKg of resin, more preferably 0.1-10 mol per IKg of resin.
It is appropriate that the amount is within the range of 5 to 5 mol, and the primary or secondary hydroxyl group is 0.1 mol or more per 1 kg of resin,
More preferably, the amount is in the range of 0.5 to 10 moles. If the amount of these groups is less than the above-mentioned amount, curability tends to decrease.

C&) The introduction of α, β-unsaturated carbonyl groups into the resin is carried out by a first-order reaction using a functional group that reacts with the functional group in the resin and a compound (resin) having α, β-unsaturated carbonyl groups. For example, (1) addition reaction of carboxyl group and epoxy group (
2) Addition reaction between hydroxyl group and epoxy group (3) Addition reaction between phenolic hydroxyl group and epoxy group (4) Esterification reaction between hydroxyl group and carboxyl group (5) Half-esterification between hydroxyl group and acid anhydride (6) Water # Transesterification reaction between a group and an ester group (7) This can be carried out using an addition reaction between an incyanate group and a hydroxyl group.

The resin (a) in the present invention is a resin containing an α, β-unsaturated carbonyl group and a primary or secondary hydroxyl group,
It is used in water-based paints together with (b) resin, which will be described later, and (a
) resin and (b) resin may be water-solubilized or water-dispersed in a mixed form, and (a) resin itself or (, I
L) It is not necessary to water-solubilize or disperse the resin by neutralizing it with an organic acid, etc. However, from the viewpoint of stability of the electrocoating paint bath and painting workability, (a) 46f resin per Ikg of resin It is preferable to contain about 0.2 to 1.5 moles of tertiary amino group.

(&) The introduction of a tertiary amino group into the resin is, for example, (1)
Addition reaction between epoxy group and secondary amine (2) Addition reaction between epoxy group and tertiary alkanolamine (3) Addition reaction between incyanate group and tertiary alkanolamine (4)
Esterification reaction between a carboxyl group and a tertiary alkanolamine (5) This can be carried out using an addition reaction between an unsaturated group and a secondary amine.

In the present invention, (a) used together with the resin, (b) the resin having an aprotic onium salt-containing group represented by the following general formula (I) [R1 and R2 are as described above] is a quaternary onium salt. It has an ammonium salt, a quaternary phosphonium salt, or a tertiary sulfonium salt, and specific examples of cations in these salts are shown below.

R2R4 R2R4 R3 R2R4 [In each of the above formulas, R2 represents a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 8 carbon atoms, R3, R4, and RS are
The same or different R3 and R4 or R3, R4 and R taken together represent an organic group having 1 to 14 carbon atoms.

The hydrocarbon group having 1 to 8 carbon atoms in R2 in each of the above formulas may form a heterocyclic group together with the nitrogen atom, phosphorus atom, or sulfur atom to which these are bonded. An alkyl group or an alkenyl group is preferable, and R2 is a hydrogen group in addition to a hydrocarbon group having 1 to 8 carbon atoms.
Although it may be a hydroxyl group or a hydroxyl group, a hydroxyl group is particularly preferable from the viewpoint of curability.

Rs, Ra and (/Rs te shows! Carbon a l
The a group of l4 is not particularly limited as long as it does not substantially interfere with the ionization of ammonium bases, phosphonium bases or sulfonium bases,
For example, a hydrocarbon group having 1 to 14 carbon atoms which may contain 4 different atoms such as oxygen atoms in the form of a hydroxyl group or an alkoxy group is generally used.

Examples of such hydrocarbon groups include aliphatic, alicyclic, or aromatic hydrocarbon groups such as alkyl groups, cycloalkyl groups, cycloalkylalkyl groups, aryl groups, and aralkyl groups. The above-mentioned alkyl group may be linear or branched, and preferably has 8 or less carbon atoms, preferably a lower one, such as methyl, ethyl, n- or 1so-propyl, n- Examples include 11so-1SeC- or tert-butyl, pentyl, heptyl, and octyl groups. The cycloalkyl group or cycloalkylalkyl group preferably has 5 to 8 carbon atoms, such as cyclopentyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, and the like. The above aryl groups include phenyl, tolyl, xylyl groups, and the like. Furthermore, a benzyl group is suitable as the aralkyl group.

Preferred examples of hydrocarbon groups containing a different atom, such as an oxygen atom, include hydroxyalkyl) &(
In particular, hydroxy lower alkyl groups), specifically hydroxymethyl, hydroxyethyl, hydroxybutyl, hydroxypentyl, hydroxyheptyl, hydroxyoctyl groups, etc., and alkoxyalkyl groups (especially lower alkoxy lower alkyl groups), specifically methoxymethyl , ethoxymethyl, ethoxyethyl, n-propoxyethyl,
1so-propoxymethyl, n-butoxymethyl,
Examples include 1so-butoxyethyl and tert-butoxyethyl groups.

R2 and R3 or R~2. Examples of -We in the case where R3 and R4 are a heterocyclic group formed together with the nitrogen atom, phosphorus atom or sulfur atom to which they are bonded include those shown below.

The anion in the above onium salt is 0COR.

[In the formula, R1 represents a hydrocarbon group having 1 to 8 carbon atoms or a hydrogen atom which may be substituted with a hydroxyl group, an alkoxy group, an ester group, or a halogen atom.] As the hydrocarbon group of 8, for example, carbon number 1
-8 alkyl group, alkenyl group, cycloalkyl group,
Examples include aliphatic, alicyclic, or aromatic hydrocarbon groups such as cycloalkenyl groups, aryl groups, and aralkyl groups. Among these, alkyl groups and alkenyl groups are preferred, and these groups may be linear or branched, with lower ones being particularly desirable, such as methyl, ethyl, n- or 1so. -propyl, n-, iso
-, sec-, or tert-butyl, pentyl, heptyl, octyl, vinyl, and methyl group-substituted vinyl groups. Preferred examples of the hydroxyl-substituted hydrocarbon group include hydroxyalkyl groups (particularly hydroxy lower alkyl groups), specifically hydroxymethyl, hydroxyethyl, hydroxybutyl, hydroxypentyl, hydroxyheptyl, hydroxyoctyl groups, etc. . Preferred examples of alkoxy-substituted hydrocarbon groups include alkoxyalkyl groups (especially lower alkoxy-lower alkyl groups), specifically methoxymethyl, ethoxymethyl, ethoxyethyl, n-propoxyethyl, 1
so-propoxymethyl, n-butoxymethyl, 1s
Examples include o-butoxyethyl and tert-butoxyethyl groups. Preferred examples of the ester group-substituted hydrocarbon group include a lower alkyloxycarbonylalkyl group, a lower alkyloxycarbonylalkenyl group, specifically methyloxycarbonylmethyl, propyloxycarbonylethyl, ethyloxycarbonylpropyl, methyloxycarbonylbutyl, Examples include methyloxycarbonylbutylnyl and ethyloxycarbonylethylenyl groups. Preferred examples of the halogen-substituted hydrocarbon group include lower halogenated alkyl groups, specifically methyl monochloride, -methyl bromide, -methyl iodide, methyl dichloride, methyl trichloride, - Examples include ethyl chloride group and -butyl chloride group.

Examples of the organic carboxylic acids used to generate the above anions include acetic acid, formic acid, trimethylacetic acid, acrylic acid, methacrylic acid, lactic acid, hydroxyacetic acid, crotonic acid, chloroacetic acid, maleic acid monomethyl ester, and fumaric acid monomethyl ester. Examples include ethyl ester and monomethyl itaconate. Among these, the dissociation constant (pKa
It is preferable that the value (value) is less than lXl0-'. By using onium salts of these organic acids, sufficient performance can be achieved in terms of the curability of the electrodeposition coating and the water resistance of the cured electrodeposition coating.

The introduction of the onium salt into the resin (b) of the present invention can be carried out, for example, according to the method shown in (1) or (ii) below.

(i) After reacting a resin having a halogenated alkyl group with a tertiary amine, phosphine or thioether in a solvent-free or inert organic solvent, the halogen atom is replaced with a hydroxyl group by anion exchange, and then this A method of reacting with an organic acid.

Taking as an example a case where a tertiary amine is used as a compound to be reacted with the resin, the reaction formula is as follows.

R2R4 R,′ R2R.

[In the formula, [F] represents the base portion of the resin, X represents a halogen atom, R2-1R,, R, and R5 are the same as above,
] When using a phosphine instead of a tertiary amine, it is sufficient to replace N with P in the above reaction formula, and also use a tertiary amine.
When a thioether is used instead of a class amine, N may be replaced with S and -R, may be deleted in the above reaction formula.

The reaction between the L resin and the tertiary amine etc. is approximately 100-15
The reaction is carried out under heating at 0° C. and is completed in about 1 to 20 hours.

In order to anion-exchange the above reaction product and react with an organic acid to obtain an onium salt of the organic acid, for example, the reaction product is passed through a bead-type anion exchange resin to replace the halogen with a hydroxyl group. , and then mix this with an organic acid.

(11) A method in which a resin having a 1,2-epoxy group is simultaneously reacted with a tertiary amine, phosphine or 1,000-onythyl, and an organic acid in a solvent-free or inert organic solvent.

Taking as an example a case where a tertiary amine is used as a compound to be reacted with the resin, one reaction formula is shown as follows.

0 R4 0HR4 [In the formula, R, , R3, R4, R, and [F] are the same as above] When phosphine is used instead of tertiary amine and when tertiary
When a thioether is used instead of a class amine, in the above reaction formula, N may be replaced with P, or N may be replaced with S and -R, may be deleted, as in the case of (i) above.

1) The reaction of the above resin, tertiary amine, etc. and organic acid is approximately 4
The reaction is carried out under heating at 0 to 80°C and is completed in about 1 to 20 hours.

- Examples of inert organic solvents used in (i) and (ii) above include ether alcohol solvents such as ethylene glycol monobutyl ether and ethylene glycol monoethyl ether; ether solvents such as dioxane and ethylene glycol diethyl ether; , alcoholic solvents such as ethanol, propatool, butanol,
Examples include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.

In addition, when the resin is an acrylic resin, the onium salt can be introduced into the resin according to the methods (1) and (11) below. Indicates the group.

R1 and we are the same as above, ] It can also be carried out by polymerizing the (meth)acrylic acid ester monomer represented by the following alone or together with a comonomer copolymerizable therewith in accordance with a conventional method.

The resin (b) obtained as described above has a peak molecular weight of 100 to 50,000, more preferably 20,000 by GPC.
It is appropriate that the number be within the range of 0 to 20,000.

Further, the amount of onium base in (b) resin is suitably within the range of 0.01 to 5 mol, more preferably 0.1 to 1 mol, per IKg of the total amount of (a) resin and (b) resin. It is. Further, the resin (b) may contain an α,β-unsaturated carbonyl group, a tertiary amine group, or a hydroxyl group.

The resin (b) obtained as described above has surface-active ability by itself, and can be mixed with the resin (a) and added to the mixture or mixed in water. It may be dissolved and/or dispersed in water, or if the resin contains tertiary amino groups, all or part of it may be neutralized with an organic acid and dissolved in water. Alternatively, each resin may be formed into an aqueous solution or an aqueous dispersion and then mixed; further, one resin may be mixed with an aqueous solution or an aqueous dispersion, and The water-based paint of the present invention, which may be dissolved or dispersed in water, is obtained in this way, but the water-based paint contains coloring pigments, extender pigments, rust-preventing pigments, dyes, pigment dispersion resins, pigment dispersants, and leveling agents. Agents, antifoaming agents, anti-sagging agents, solvents, etc. may be added.

There are no particular restrictions on the solvent as long as it can be used in cationic electrodeposition paints, but examples include alcohols such as impropatol, butanol, monoalkyl ethers of ethylene glycol, monoalkyl ethers of propylene glycol, Monoalkyl ethers of diethylene glycol, monoalkyl ethers of dipropylene glycol, dialkyl ethers of ethylene glycol, dialkyl ethers of diethylene glycol,
Solvents such as cyclic ethers such as dioxane, which have an E-dissolution of 5% or more in water at 25°C, are preferably used in an amount of 0 to 100 parts by weight based on 100 parts by weight of the solid content of the bath. - Alcohols with a solubility in water of less than 5% at 25°C, such as ethylhexyl alcohol and benzyl alcohol, and mono- and di-ethers such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol, such as octoxyethanol, at 25°C. For substances with solubility in water of less than 5%, aromatic, aliphatic, alicyclic hydrocarbons, and ketones, the bath solid content is 10%.
It is preferable to use it in a range of 0 to 20 parts by weight relative to 0 parts by weight.

Also, regarding pigments and additives, if they can be used in normal cationic electrodeposition paints, can they be used? There are no particular restrictions on the type of pigments, but from the viewpoint of bath stability, it is preferable that the amount of pigments is within 50% by weight of the solid content of the aqueous paint of the present invention.

The solid content of the water-based paint obtained as described above can be varied depending on the required coating thickness and coating conditions, but generally the bath has a solid content of 1 to 30%, and cationic electrodeposition is performed using the object to be coated as a cathode. Provided for painting.

As the electrodeposition coating conditions, the conditions generally used in the past can be applied, and a predetermined voltage (usually 10 to 500 ports) is applied between the conductive coating object as a cathode and a counter electrode for a predetermined period of time (usually 30 seconds to 30 seconds). After applying 10 minutes), the object to be coated is removed from the bath and heated to 80°C or higher, preferably 100°C, either as is or after washing with water.
By heating at a temperature of about 120 to 200°C, preferably for at least 5 minutes, and more preferably for about 30 minutes, a good coating film appearance and coating performance can be achieved, which is the objective of the present invention. An excellent electrodeposition coating film can be obtained.

In addition, by adjusting the electrodeposition conditions, it is possible to obtain an electrodeposition coating film with a thickness of about 50 to 100 microns, and even with such a thick film, there are no problems with the coating surface due to abnormalities in the coating surface, poor curing during baking, or cracks. It is possible to obtain a good thick cured electrodeposited coating without yellowing or yellowing.

Electrodeposition coating methods include, in addition to the so-called constant voltage method mentioned above, the so-called slow start method, in which the voltage is started from Ov and gradually increased to a constant voltage, and electrodeposition is performed for a predetermined period of time, and the method in which a constant current is applied instead of applying a constant voltage. Electrodeposition coating can also be suitably carried out by a constant current method in which the current is applied, or by a mode in which these methods are mixed.

In the present invention, the curing reaction mechanism of the electrodeposited coating film by heating is not clear, but the disappearance of unsaturated groups is observed in the change in the infrared absorption spectrum, and this is due to the polymerization of polymerizable unsaturated groups or polymerizable unsaturated groups. This is thought to be due to the addition reaction of active hydrogen such as hydroxyl group to the group.

Furthermore, during this heating, in addition to the curing reaction, Hofmann decomposition of the thirium salt in the resin occurs to improve water resistance.

C action and effect of the invention 1 In the present invention, a specific aprotic onium salt contained in the resin (1) enables water solubilization and water dispersion of the resin, and (2) acts as a catalyst during crosslinking and curing of the film. 8, ■ Hofmann decomposition easily occurs during crosslinking and curing of the coating by heating, and onium salts are no longer included in the cured coating, resulting in a cured electrodeposited coating with excellent performance such as water resistance and chemical resistance. can be obtained.

Furthermore, the present invention makes it possible to obtain an electrodeposited coating film that exhibits excellent curability, good coating appearance, and excellent coating performance even at a thickness of 50 to 100 microns, which could not be obtained using conventional electrodeposition coating methods. can.

L Arashi 1 Examples are given below to further clarify the present invention.

Hereinafter, "part" and "%" refer to "part" and "%" respectively.
``parts by weight'' and ``% by weight''.

Production Example 1 Ethylene glycol monobutyl ether 6 in a flask
0 parts was blended and maintained at 110°C. A mixture of 20 parts of styrene, 10 parts of 2-hydroxyethyl methacrylate, 35 parts of butyl acrylate, 35 parts of glycidyl methacrylate and 3 parts of t-butyl peroxyoctoate was added dropwise into this over a period of 3 hours. It was further aged at 110°C for 7 hours. This was cooled to 50°C, 10.5 parts of jetanolamine was added, and after reaction at 50 to 70°C for 2 hours, acrylic acid 1005 parts hydroquinone 0.0
2 parts and 0.1 part of tetraethylammonium bromide were added, heated to 110°C, and reacted at this temperature for 4 hours.

The obtained resin solution (a-1) has a nonvolatile content of 67%, and this resin (solid content) has an acid value of 0.5, an α,β-unsaturated carbonyl group concentration of 1.2 mol/Kg, and a hydroxyl group concentration. The concentration of 3.tertiary amide 7 group was 0.83 mol/Kg in 4.3 mol/kg, and the peak molecular weight by GPC was about 12,000.

Production Example 2 In a flask were placed 500 parts of Epicoat #152 (novolac phenol type epoxy resin, epoxy equivalent 173, product of Yuka Shell Epoxy Co., Ltd.), 110 parts of dibutylamine, 0.5 part of hydroquinone, and 200 parts of 2-methoxypropanol. After mixing and reacting at 80°C for 2 hours with stirring, 144 parts of acrylic was added and the mixture was heated to 110°C.
The mixture was reacted for 4 hours to obtain a resin solution (a-2) with a solid content of 79%. This resin (solid content) has an acid value of 0.8, an α,β-unsaturated carbonyl group concentration of 2.6 mol/Kg, and a hydroxyl group concentration of 3.
8 mol/Kg, the concentration of 7 tertiary amide groups was 1.2 mol/Kg, and the peak molecular weight by GPC was about 900.

Production Example 3 In a flask, 300 parts of Epicor #1004 (epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent 950), 200 parts of Epicor #1001 (epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent 450) and methyl After blending 200 parts of isobutyl ketone and uniformly dissolving it, 35 parts of jetanolamine was added and reacted at 70°C for 2 hours. Furthermore, 72 parts of acrylic acid and 0.1 part of methoxyhydroquinone were added to this mixture at 120°C.
The reaction was carried out for a period of time to obtain a resin solution (a-3) with a solid content of 74%. This resin (solid content) has an acid value of 1.1, an α,β-unsaturated carbonyl group concentration of 0.74 mol/Kg, and a hydroxyl group concentration of 3.
9 mol/kg, tertiary amine group concentration 0.60 mol/kg, and peak molecular weight by GPC of about 1600.

Production Example 4 500 parts of Epicoat #152 (above) in a flask,
After blending 180 parts of acrylic acid, 0.5 part of tetraethylammonium bromide, 0.05 part of hydroquinone and 150 parts of 2-ethoxybutanol and reacting at 110°C for 4 hours.

Cooled to 50°C. This stuff has jetanolamine 4
1 part was added and reacted at 30°C for 10 hours to obtain a resin solution (a-4) with a solid content of 88%. This resin (solid content) has an acid value of 0.2 and a concentration of α,β-unsaturated carbonyl groups of 3.5 mol/
kg, hydroxyl group C degree 5.0 mol/Kg, tertiary amine group concentration 0.54 mol/Kg, and peak molecular weight determined by GPC of 950.

Production Example 5 900 parts of Epicoat #1OO1 (above) in a flask,
500 parts of methyl isobutyl ketone and 0.01 part of dibutyltin diacetate were blended, uniformly dissolved, and kept at 80°C, and an adduct of inphorone diisocyanate and 2-hydroxyethyl acrylate (1 mol: 1 mol addition) was added. 676 parts of hydroquinone (containing hydroquinone looOppm) were added dropwise over 1 hour, and after the dropwise addition was completed, the mixture was further aged at 80°C for 4 hours. Next, 72 parts of acrylic acid, 0.1 part of tetraethylammonium chloride, and 0.5 part of hydroquinone were added to this, and after reacting at 110°C for 4 hours, the mixture was cooled to 50°C, and 133 parts of diimpropaturamine was added, and the mixture was heated at 30°C. The reaction was carried out for 10 hours to obtain a resin solution (a-5) with a solid content of 78%. This resin (solid content) has an acid value of 0.8 and an α,β-unsaturated carbonyl group concentration of 1.
7 mol/Kg, hydroxyl group concentration 2.2 mol/Kg, tertiary amine group concentration 0.56 mol/Kg, and peak molecular weight by GPC of about 1750.

Production Example 6 Ethylene glycol monobutyl ether 6 in a flask
0 parts was blended and maintained at 100°C. A mixture of 30 parts of methyl methacrylate, 40 parts of butyl acrylate, 20 parts of glycidyl methacrylate, 10 parts of droxyethyl methacrylate and 4 parts of benzoyl peroxide was added dropwise to this solution over a period of 3 hours, and after the completion of the addition, ,100℃
The reaction was carried out for 7 hours. Next, 10.1 parts of acrylic acid and 0.1 parts of tetraethylammonium bromide were added to this material.
Add 5 parts and 0.1 part of methoxyhydroquinone to 11
The reaction was carried out at 0°C for 4 hours, and a resin solution with a solid content of 65% (a
-6) was obtained. This resin (solid content) has an acid value of 0.3, α,
The β-unsaturated carbonyl group concentration was 1.3 mol/Kg, the hydroxyl group concentration was 2.1 mol/Kg, and the peak molecular weight by GPC was about 17,000.

Production Example 7 After blending 900 parts of Epicote #1001 (above) and 200 parts of 2-ethoxybutanol in a flask and uniformly dissolving the mixture, 91.6 parts of β-thiodiglycol,
'144 parts of acrylic acid and 0.5 parts of hydroquinone were added and reacted at 70°C for 5 hours to obtain a resin solution (b-1) with a solid content of 85%. This resin (solid content) had a tertiary sulfonium salt concentration of 0.66 mol/Kg and a peak molecular weight of about 1100 by GPC.

Production Example 8 1 part of 2-ethylhexyl glycidyl ether in a flask
86 parts, dimethylaminoethanol 89 parts and lactic acid 9 parts
0.1 part was blended and the reaction was carried out at 70°C for 1.5 hours.
A resin liquid (b-2) was obtained. This resin had a quaternary ammonium salt concentration of 2.7 mol/Kg and a peak molecular weight of 395 by GPC.

Production Example 9 119 parts of N-methyldiethanolamine in a flask,
Blending 46 parts of formic acid and 72 parts of butylene oxide,
The reaction was carried out at 40°C for 2 hours to obtain a resin liquid (b-3). This resin has a quaternary ammonium salt concentration of 4.2 mol/K.
The peak molecular weight was 235 by g and GPC.

Production Example 10 101 parts of triethylamine, 60 parts of acetic acid and 72 parts of butylene oxide were mixed in a flask and reacted at 40°C for 7 hours to obtain a resin liquid (b-4). This resin is the fourth
The ammonium salt concentration was 4.3 mol/Kg, and the peak molecular weight by GPC was 230.

Production Example 11 In a flask, 500 parts of Epicote #152 (above), 208 parts of acrylic acid, 183 parts of 1,000 osyglycol, and 2
- 200 parts of ethoxyethanol was blended and the reaction was carried out at 70°C for 6 hours with stirring to obtain a resin solution (b-5) with a solid content of 81.5%. This resin (solid content) had a tertiary sulfonium salt C degree of 1.7 mol/Kg, an α,β-unsaturated carbonyl group concentration of 1.6 mol/Kg, and a peak molecular weight of 900 by GPC.

Production Example 12 90% ethylene glycol diethyl ether in a flask
17.4 parts of dimethylaminoethanol, 20 parts of styrene, 37.6 parts of n-butyl methacrylate, 25 parts of glycidyl methacrylate, and 5 parts of azobisisovaleronitrile. The mixture was added dropwise over a period of 3 hours, and then maintained at 80°C for an additional 1 hour. Then add 7zobisisovaleronitrile to this
．． A solution prepared by dissolving 5 parts of ethylene glycol diethyl ether in 10 parts of ethylene glycol diethyl ether was added dropwise over 1 hour, and the solution was further heated at 80°C for 5 parts.
After aging for a time, 12.5 parts of acrylic fi, 0.1 part of tetraethylammonium chloride and 0.05 part of hydroquinone were added, and the mixture was reacted at 100°C for 5 hours, and then cooled to 50°C. To this was added 3.6 parts of butylene oxide and 3 parts of acetic acid, and the reaction was carried out at 50°C for 8 hours to obtain a resin solution (b-6) with a solid content of 57%.

This resin (solid content) had an acid value of 0.7, an α, β-unsaturated carbonyl group concentration of 1.5 mol/Kg, a quaternary ammonium salt concentration of 0.42 mol/Kg, and a peak molecular weight of 20,000 by GPC. Ta.

Production Example 13 900 parts of Epicoat #1001 (above) in a flask,
300 parts of 2-methoxypropanol, 525 parts of triphenylphosphine, and 120 ffl of acetic acid were mixed together and reacted at 80°C for 7 hours to obtain a resin solution (b-7) containing 84% solid paper.
) was obtained. This resin (solid content) had an acid value of 0.9, a quaternary phosphoniurium salt concentration of 1.3 mol/Kg, and a peak molecular weight of 1,600 by GPC.

Example 1 100 parts of the resin solution (a-1) obtained in Production Example 1, 20 parts of rutile titanium dihydride, 10 parts of talc and 1 part of benzyl alcohol were mixed, and the mixture was milled in a tube gauge using a pebble ball mill. It took 244 hours for zero dispersion, in which dispersion was carried out until the whelks reached 7 to 1 OIL. This dispersion, 10 parts of the resin solution (b-2) obtained in Production Example 8, and 2.0 parts of acetic acid.
The mixture with 5 parts of
A stable aqueous paint dispersion was obtained by adding slowly to 475 parts of deionized water while stirring at 00 rpm.

This aqueous paint dispersion was used as an electrodeposition bath at a bath temperature of 28±1°C.
A zinc phosphate-treated steel plate was used as the object to be coated, and click-on electrodeposition was performed under conditions of electrodeposition at 200V for 3 minutes.

The electrodeposited plate was then washed with water and then baked and cured at 120°C for 20 minutes. The performance of the obtained cured coated plate is shown in Table 2.

Examples 2 to 8 and Comparative Example 1.2 In the same manner as in Example 1, aqueous paint dispersions were prepared using the formulations shown in Table 1. Then, cationic electrodeposition coating and baking were performed in the same manner as in Example 1 under the conditions shown in Table 2. The performance of the obtained cured coated plate is shown in Table 2.

Comparative Example 3 72% Polyamide Modified Epoxy Isocyanate Curing Type Cation Electrodeposition Coating Cation (Nirecrone $9200 Clear Kansai Pain L [manufactured by]) 100 parts of carbon black 0
．． After adding 5 parts of talc, 5 parts of talc, and 1 part of benzyl alcohol and dispersing in a ball mill for 36 hours, 106.5 parts of the dispersion was mixed with 409 parts of deionized water and 1 part of acetic acid, which were stirred with a high-speed disper (800-1000 rpm). 5 parts to obtain an aqueous paint dispersion.

Electrodeposition coating and baking were carried out in the same manner as in Example 1 except that the aqueous paint dispersion was used as an electrodeposition bath and the electrodeposition conditions were 250V for 3 minutes to obtain a cured coated plate. The performance of the obtained cured coated plate is shown in Table 2.

Comparative Example 4 A cured coated plate was obtained in the same manner as in Comparative Example 3 except that the electrodeposition coating was performed at 350 V for 6 minutes. The performance of the obtained cured coated plate is shown in Table 2.

The tests in Table 2 were conducted according to the following method.

(Tree 1) Impact resistance: JIS K5400-1979
6.13.3B method, 0 weight 500g, carried out in an atmosphere of 20°C,! Using the diameter of the tip of the core in inches, both the 0 facing (concave portion) and the backing (convex portion) were evaluated with a maximum height of 50 cm, which is the maximum height without coating damage.

(Thursday 2) Adhesion: JIS K5400-1979 6
．． 15s, make 100 l mm x 1 am (F) gongs on the paint film, stick adhesive cellophane tape on the surface, and calculate the number of gongs remaining on the painted surface after rapidly peeling it off. Described.

(Wood 3) Boiling water resistance: After the coated plate was immersed in boiling water for 1 hour, the coated plate was left to stand for 24 hours, and the same test as in the above (Wood 2) adhesion was conducted on the coated plate.

(Tree 4) Tsuruto spray resistance: Make cross-cut scratches on the coating film with a knife to reach the base material, and then
A salt spray test was conducted using No. 22371, and the time at which the maximum blistering width or creep width on one side of the crosscut reached 3cm was recorded.

(*5) Pour the test paint into a cylindrical container made of stainless steel and keep it at 28±1°C to 27c+s from the bottom, and stir evenly. Next, a 15x300x0.4+e■ inner plate was attached to the inside of a stainless steel pipe with an inner diameter of 1611 mφ, a thickness of 1 mti, and a height of 300 ram, and the pipe was placed vertically in a stainless steel cylindrical container, 20 m from the bottom.
Install at a distance of m. Change the voltage from O to painting voltage 2 in 10 seconds
Increase the voltage to 00V. (At this time, adjust the rising speed so that the current does not exceed IOA.) After 3 minutes of energization, turn off the switch, wash the inner plate and pipe with water, and then bake dry the inner plate. The height to the tip of the inner plate where the paint adhered was measured and this value was displayed. The larger this value is, the better the throwing power is.

(Zero 6) Gel fraction: The free coating film was immersed in A7Ton at about 57° C. (under reflux) for 4 hours to perform extraction.

(Thursday 7) Bath stability: Bath paint stirred at 30℃ for 2 months
When i is filtered through a wire mesh of 400 mesh, the filtration residue is 1
The weight after drying at 20"C for 1 hour is expressed in (g/l bath paint).

Claims (1)

[Claims] (1) (a) α,β-unsaturated carbonyl group and 1
A resin containing a class or secondary hydroxyl group and (b) an aprotic onium salt-containing group represented by the following general formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, R_1 is 1 or more carbon atoms which may be substituted with hydroxyl group, alkoxy group, ester group or halogen atom
8 hydrocarbon group or hydrogen atom. R_2 represents a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 8 carbon atoms, -W^
■There are ▲mathematical formulas, chemical formulas, tables, etc.▼ or ▲mathematical formulas,
There are chemical formulas, tables, etc. Showing ▼. Here, Z is a nitrogen atom or a phosphorus atom, Y is a sulfur atom, R_3, R_4
and R_5 are the same or different and represent an organic group having 1 to 14 carbon atoms, and R_3 and R_4 or R_3,
R_4 and R_5 may be taken together to form a heterocyclic group together with the nitrogen atom, phosphorus atom or sulfur atom to which they are bonded. ] A cationic electrodeposition coating method characterized by electrodeposition coating using a water-based paint containing a resin having the following as a resin component, with the object to be coated serving as a cathode.