JPH07258586A - Cationic electrodeposition coating composition - Google Patents

Abstract

PURPOSE:To provide a cationic electrodeposition coating composition to which both low-temperature curability and high corrosion resistance are imparted without using any lead compound. CONSTITUTION:The composition contains a base resin containing cationic groups, a blocked isocyanate curing agent and a deblocking catalyst for the blocked isocyanate curing agent. The deblocking catalyst contains at least one metal compound selected from the group consisting of an organotin compound, organic acid salts of cobalt, nickel and zinc and a diketone metal complex.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an electrodeposition coating composition, and more particularly to a cationic electrodeposition coating composition.

[0002]

BACKGROUND OF THE INVENTION Cationic electrodeposition coating compositions generally contain a base resin containing a cationic group, a blocked isocyanate curing agent, and a dissociation catalyst for the blocked isocyanate curing agent. Here, the dissociation catalyst is a component for dissociating the block portion of the blocked isocyanate-based curing agent and promoting regeneration of the isocyanate group.

By the way, this kind of cationic electrodeposition coating composition is mainly used as a primer for automobile bodies and parts, and is required to have a coating film forming ability capable of forming a coating film having high corrosion resistance. In order to realize such coating film forming ability, a general cationic electrodeposition coating composition further contains a basic lead pigment as a rust preventive pigment. However, lead-based pigments are being avoided from the viewpoint of preventing environmental pollution. Therefore, the cationic electrodeposition coating composition is required to have a coating film forming ability capable of achieving the same corrosion resistance as that obtained when a lead-based compound is used instead of a lead-based compound.

On the other hand, the cationic electrodeposition coating composition is also required to have low-temperature curability. This is to reduce the energy cost required for electrodeposition coating by setting the bath temperature at the time of electrodeposition coating low.

As a cationic electrodeposition coating composition for simultaneously fulfilling the above requirements, a specific epoxy-polyamine resin containing polyamide as a modifier, a blocked isocyanate curing agent, a benzoate organic tin compound, and bismuth. A compound containing a base compound or a zirconium compound has been proposed (JP-A-5-311099).

[0006]

The above-mentioned conventional cationic electrodeposition coating composition is capable of forming a coating film having good corrosion resistance and good low-temperature curability even though it does not contain a lead compound. However, since it is necessary to use an expensive material such as a bismuth compound or a zirconium compound, the cost is high. Further, since the bismuth-based compound and the zirconium-based compound are difficult to mix uniformly in the paint by themselves, they impair the handleability of the cationic electrodeposition paint.

An object of the present invention is to use lead-free compounds,
It is to realize low temperature curability and high corrosion resistance at the same time and at low cost.

The cationic electrodeposition coating composition of the present invention contains a base resin containing a cationic group, a blocked isocyanate curing agent, and a dissociation catalyst for the blocked isocyanate curing agent. Here, the dissociation catalyst contains an organotin compound and at least one metal compound selected from the group consisting of cobalt, nickel or zinc organic acid salts and diketone metal complexes.

Here, the organic tin compound is, for example, at least one organic tin compound selected from the group of organic tin compounds represented by the following general formulas (1) and (2). Also,
The organic acid salt is, for example, an organic acid metal salt represented by the following general formula (3).

[0010]

[Chemical 4]

[0011]

[Chemical 5]

In the general formulas (1) and (2), R ¹ and R ³ are each an alkyl group or an aryl group having 1 to 12 carbon atoms. R ² is a hydrogen atom or an alkyl group, alkenyl group, aralkyl group, cycloalkyl group, alkoxyalkyl group or aryl group having 1 to 21 carbon atoms. X and Y are OCOR ² , OH, halogen, O1 / 2 or S1 / 2. Z is O, S
Alternatively, it is a divalent carboxylic acid residue. p is 0 or 1
Is an integer.

[0013]

[Chemical 6]

In the general formula (3), R ⁴ is a hydrogen atom, or an alkyl group having 1 to 21 carbon atoms, an alkenyl group, an aralkyl group, a cycloalkyl group, an alkoxyalkyl group or an aryl group. M is cobalt, nickel or zinc. q is an integer of 0 or 1. ********

Base Resin The base resin used in the present invention is not particularly limited as long as it is usually used for cationic electrodeposition coating.
Specific base resins for cationic electrodeposition coatings include, for example, those obtained by copolymerizing or graft-polymerizing an amino group-containing monomer, those obtained by adding an amine to an epoxy group-containing polymer, and those obtained by onium chloride of an epoxy group-containing polymer,
Examples thereof include a reaction product of a dicarboxylic acid and a polyamine, a maleated polymer to which an amine has been added, and an isocyanate-containing polymer to which an amine has been added.

Preferred as the base resin used in the present invention are amino group-containing resins. Specifically, an amino-epoxy having a primary or secondary hydroxyl group and a primary, secondary or tertiary amino group and having an amino value of 30 to 150 and an average molecular weight of 200 to 20,000. resin,
Amino-poly (meth) acrylate resins and amino-polyurethane resins. The number of hydroxyl groups and the number of amino groups contained in this type of base resin may be one or two or more. When the amino value is less than 30, it becomes difficult to obtain a stable emulsion. On the other hand, if it exceeds 150, E
D Workability may be a problem. A more preferable range of amino value is 45 to 120.

The most preferable base resin used in the present invention is a modified epoxy resin containing an oxazolidone ring in the molecule. The modified epoxy resin can be obtained by dealcoholizing a bisurethane compound reacted with a diisocyanate compound or a heterourethane compound reacted with another active hydrogen compound with an epoxy resin. When such a base resin containing an oxazolidone ring is used, it becomes difficult for the coating film to become thin due to the heat loss.

Curing Agent The blocked isocyanate curing agent used in the present invention is a general blocked isocyanate curing agent, that is,
A blocking agent is added to the isocyanate group contained in the polyisocyanate compound. Since the curing agent usually has three or more functional groups, the number of blocked isocyanate groups contained in the blocked isocyanate curing agent used in the present invention is also preferably three or more.

Examples of the above-mentioned polyisocyanate compound include alkylene diisocyanates such as trimethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylene diisocyanate and hexamethylene diisocyanate, bis (isocyanatomethyl) cyclohexane, cyclopentane diisocyanate, cyclohexane diisocyanate and isophorone diisocyanate. Aromatic diisocyanates such as cycloalkylene-based diisocyanates, tolylene diisocyanates, phenylene diisocyanates, diphenylmethane diisocyanates, diphenyl ether diisocyanates, xylylene diisocyanates, diisocyanates Aromatic aliphatic diisocyanates such as diethylbenzene, triphenylmethane triisocyanates , Tri isocyanatobenzene, triisocyanate such as triisocyanate toluene, tetraisocyanates, polymerization polyisocyanates such as dimers or trimers of tolylene diisocyanate, ethylene glycol to the various polyisocyanate compounds such as diphenyl dimethyl methane tetra isocyanates,
Examples thereof include terminal isocyanate-containing compounds obtained by reacting low molecular weight active hydrogen-containing organic compounds such as propylene glycol, diethylene glycol, trimethylolpropane, hydrogenated bisphenol A, hexanetriol, glycerin, pentaerythritol, castor oil, and triethanolamine. To be

On the other hand, as the blocking agent, phenols, lactams, alcohols, amino alcohols, amines or imides, active methylene-containing compounds such as diethyl malonate, methyl acetoacetate and ethyl acetoacetate, oximes, Examples thereof include mercaptans, acid amides, imidazoles, ureas, carbamates and sulfites.

Examples of the phenols include phenol, cresol, xylenol, t-butylphenol, p-nonylphenol, p-tert-octylphenol, hydroxybenzoic acid and the like. Examples of lactams include ε-caprolactam, γ-butyrolactam, δ-valerolactam, β-propiolactam and the like.

The alcohols include methanol, ethanol, propanol, isopropanol, butanol, amyl alcohol, hexyl alcohol, 2-ethylhexanol, heptyl alcohol, octyl alcohol, cyclohexanol, benzyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether. Ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether,
Ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, propylene glycol Examples include mono-2-ethylhexyl ether and the like.

Examples of amino alcohols include dimethylethanolamine, dimethylpropanolamine, dimethylisopropanolamine, dimethylbutanolamine,
Diethyl ethanolamine, 2- [2- (dimethylamino) ethoxy] ethanol, 2- (2- [2- (dimethylamino) ethoxy] ethoxy) ethanol, 1- [2
-(Dimethylamino) ethoxy] -2-propanol,
Examples include 1- (1- [1- (dimethylamino) -2-propoxy] -2-propoxy) -2-propanol and the like. Examples of amines or imides include diphenylamine, xylidine, carbazole, dibutylamine, succinimide, phthalimide and the like. Examples of the oximes include formamidoxime, acetoxime, acetaldoxime, cyclohexaneoxime, methylethylketoxime, diacetylmonooxime, and benzophenone oxime.

Next, preferred examples of the blocked isocyanate-based curing agent used in the present invention are listed and specifically described.

[Blocked Isocyanate Hardener I Containing Aromatic Isocyanurate Ring] By using this kind of hardener, it is possible to suppress loss on heating without impairing general coating film characteristics such as corrosion resistance and smoothness. . Here, the aromatic isocyanurate ring generally means a cyclic structure formed by polymerization of three molecules of aromatic isocyanate. Specifically, it refers to a cyclic structure represented by the following structural formula (4).

[0026]

[Chemical 7]

In the formula, -A- is a residue derived from aromatic hydrocarbon. The number of aromatic isocyanurate rings contained in one blocked isocyanate-based curing agent molecule is preferably 1 to 5, and more preferably 2 or 3.
It is an individual. When the number of aromatic isocyanurate rings is 6 or more, the viscosity of the curing agent becomes high, which may reduce the workability of the electrodeposition coating composition.

In such a blocked isocyanate curing agent containing an aromatic isocyanurate ring, it is preferable that at least one of the blocked isocyanate groups has an isocyanate group blocked with a glycol ether as an active hydrogen compound. Of course, all of the blocked isocyanate groups may be isocyanate groups blocked with glycol ether. Here, the above-mentioned glycol ether is preferably
For example, it is represented by the following general formula (5).

[0029]

[Chemical 8]

In the formula, Ra is an alkyl group having 4 to 12 carbon atoms (preferably 6 to 8 carbon atoms), Rb is a hydrogen atom or a methyl group, and n is an integer of 1 to 4. Here, when the carbon number of Ra is less than 4, the smoothness of the coating film may be impaired. On the contrary, when the carbon number of Ra exceeds 12, there is a possibility that the curing reactivity may decrease and the heating loss may increase.

Specific examples of the above glycol ether include ethylene glycol compounds and propylene glycol compounds. Examples of the ethylene glycol compound include ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, and diethylene glycol mono-2-ethylhexyl ether.

On the other hand, as the propylene glycol-based compound, propylene glycol monobutyl ether, propylene glycol monohexyl ether, propylene glycol mono-2-ethylhexyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monohexyl ether, dipropylene glycol mono- 2-Ethylhexyl ether can be exemplified.

Among the specific examples of the above-mentioned ethylene glycol type compound and propylene glycol type compound, particularly preferable ones are ethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether and propylene glycol mono-2-.
Ethylhexyl ether and dipropylene glycol mono-2-ethylhexyl ether.

As the glycol ether for blocking the isocyanate group, in addition to the glycol ether represented by the above general formula (5), the above general formula (5)
Ra, Rb and n in may be an alkyl group having 1 to 3 carbon atoms, a hydrogen atom or a methyl group, and an integer of 1 to 4 respectively. Specific examples of such glycol ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether.

The above-mentioned glycol ether has Ra and R so as to have a carbon number of 6 to 15 in consideration of suppression of heat loss and the glass transition temperature (described later) of the curing agent itself.
Most preferably, b and n are set.

Of the above-mentioned blocked isocyanate groups,
Except for the glycol ether-blocked isocyanate groups, the above-mentioned general blocking agents other than glycol ethers are blocked isocyanate groups.

The above-mentioned curing agent containing an aromatic isocyanurate ring is particularly preferably one having a structure in which the blocked isocyanate group portion satisfies the following conditions. At least 20 of all blocked isocyanate groups
Equivalent% is an isocyanate group blocked by the glycol ether represented by the above general formula (5). If this equivalent% is less than 20 equivalent%, the smoothness of the coating film may be deteriorated. In addition to the above conditions, blocked isocyanate groups other than those blocked by the glycol ether represented by the general formula (5) have the general formula RcOH (Rc may contain a hydroxyl group, and have 1 to 10 carbon atoms). An hydrocarbon represented by the formula: Rd (OCH ₂ CH
Re) mOH (Rd is an alkyl group having 1 to 3 carbon atoms, Rd
e is a hydrogen atom or a methyl group, m is an integer of 1 to 4) and at least one active hydrogen compound selected from the group consisting of glycol ethers, active methylene compounds, oxime compounds, amino alcohols, imidazoles and lactams It must be a blocked isocyanate group.

The glass transition temperature of the isocyanurate ring-containing curing agent is preferably 40 ° C. or lower. Glass transition temperature is 4
If it exceeds 0 ° C, the flowability at the time of heating may deteriorate, and the smoothness of the coating film may deteriorate. The glass transition temperature depends on the type and amount of the blocking agent used for blocking the isocyanate group, and can be achieved by appropriately adjusting these. The glass transition temperature can be determined by analogy with a calibration curve obtained from the measurement result of the model compound by a differential thermal analyzer, but it is preferably finally determined by directly measuring the cured product.

In the isocyanurate ring-containing curing agent,
The ratio of the total weight of the blocked portions of each blocked isocyanate group to the molecular weight of the compound constituting the curing agent is preferably 10 to 55%. Here, the blocking portion means a portion derived from a blocking agent that blocks an isocyanate group, in other words, a portion corresponding to a blocking agent obtained by removing active hydrogen from the blocking agent before blocking.
If this ratio is less than 10%, the smoothness of the coating film may be impaired. On the other hand, if it exceeds 55%, it is difficult to obtain the effect of suppressing the heating loss.

Next, an example of the above-mentioned isocyanurate ring-containing curing agent will be shown. This curing agent is represented by the following general formula (6) when represented by a structural formula.

[0041]

[Chemical 9]

In the formula, each of A ^{1 to} A ¹¹ is

[0043]

[Chemical 10]

It is a structural portion derived from an aromatic diisocyanate compound selected from the group consisting of: In addition, A ^{1 to} A ¹¹
May all be the same or different from each other. R ^{5 to} R ¹¹ are each a residue obtained by removing active hydrogen from the blocking agent, and at least one is a residue obtained by removing active hydrogen from the above glycol ether. Further, f, g, h and i are 0 or 1 respectively.

The isocyanurate ring-containing curing agent is generally obtained by blocking a polyisocyanate compound obtained by trimerizing an aromatic diisocyanate compound with a blocking agent. Examples of the aromatic isocyanate compound include tolylene diisocyanate and phenylene diisocyanate.

Examples of the polyisocyanate compound used in this production method include those represented by the following general formula (7).

[0047]

[Chemical 11]

In the formula, l is 0 to 4, preferably 1 to 2. The polyisocyanate compound is a monomer component,
That is, an aromatic isocyanate compound such as tolylene diisocyanate or phenylene diisocyanate may be contained as the residual monomer component that remains without trimerization. However, if the proportion of this type of residual monomer in the polyisocyanate compound exceeds 50% by weight, the desired curing agent may not be obtained.

When the above polyisocyanate compound is blocked, a blocking agent is reacted with the above polyisocyanate compound. Here, when 2 or more types of blocking agents are made to react, you may add 2 or more types of blocking agents to a polyisocyanate compound at once, and may make it react, and to add to a polyisocyanate compound for every blocking agent. You may make it react. However, when using two or more types of blocking agents having different reactivities, the blocking agent having higher reactivity is reacted with the polyisocyanate compound before the blocking agent having lower reactivity is used. Is preferred. The preferred glass transition temperature of the curing agent and the preferred proportion of the blocking portion can be achieved by selecting or adjusting the type and amount of the blocking agent, respectively.

[Blocked Isocyanate Curing Agent II Containing Isocyanurate Ring and Blocked Isocyanate Group of Both Aromatic Isocyanate Group and Aliphatic Isocyanate Group] When a curing agent of this kind is used, in the case of the above-mentioned curing agent I, Similarly, the loss on heating can be suppressed without impairing general coating film characteristics such as corrosion resistance and smoothness.

This curing agent is composed of a compound having an isocyanurate ring and a plurality of blocked isocyanate groups, and the plurality of isocyanate groups contains both an aromatic isocyanate group and an aliphatic isocyanate group. There is. Here, the aromatic isocyanate group,
An isocyanate group directly bonded to an aromatic ring is referred to. An aliphatic isocyanate group is an isocyanate group bonded to an aliphatic hydrocarbon chain.

The isocyanurate ring contained in this curing agent may be either an aromatic isocyanurate ring or an aliphatic isocyanurate ring. Here, the aromatic isocyanurate ring is as described in the curing agent I. The aliphatic isocyanurate ring generally means a cyclic structure formed by polymerization of 3 molecules of an aliphatic isocyanate compound.

The part derived from the blocking agent in the plurality of blocked isocyanate groups contained in this curing agent is not particularly limited. Generally, blocked isocyanate groups are
The dissociation temperature varies depending on the type of blocking agent.
If it is blocked by a blocking agent that easily dissociates, it can be cured at a low temperature, but it may have poor storage stability. On the other hand, if blocked with a blocking agent that does not easily dissociate, the storage stability is excellent, but the curability at low temperatures may be poor. Examples of the blocking agent that easily dissociates include oximes, active methylene-containing compounds and phenols, and examples of the blocking agent that hardly dissociate include alcohols, lactams and amino alcohols.

Generally, aromatic isocyanate groups are more reactive than aliphatic isocyanate groups. Therefore, in consideration of the compatibility between the low temperature curability and the storage stability, the aromatic isocyanate group is preferably blocked with a blocking agent selected from the group consisting of alcohols, lactams and amino alcohols. On the other hand, the aliphatic isocyanate group is preferably blocked with a blocking agent selected from the group consisting of oximes, active methylene-containing compounds and phenols.

This kind of curing agent II is a general method in which a polyisocyanate compound containing an isocyanurate ring and both aromatic and aliphatic isocyanate groups is prepared and the polyisocyanate compound is reacted with a blocking agent. Can be manufactured by. The above-mentioned polyisocyanate compound can be obtained by synthesizing a target product by general organic synthesis or by purchasing a commercial product. Examples of commercially available products include Tronate-XTHT manufactured by Rhone-Poulin, which is a complex isocyanurate compound of hexamethylene diisocyanate and tolylene diisocyanate.

The aromatic isocyanate group is blocked with a blocking agent selected from the group consisting of alcohols, lactams and amino alcohols, and the aliphatic isocyanate group is oxime-containing, active methylene-containing compound. And when blocked with a blocking agent selected from the group consisting of phenols, first, at least one blocking agent selected from the group consisting of alcohols, lactams and amino alcohols (blocking agent X ) Is reacted with a polyisocyanate compound, and then at least one blocking agent (blocking agent Y) selected from the group consisting of oximes, active methylene-containing compounds and phenols is preferably reacted. It is considered that after such a manufacturing process, the blocking agent X first blocks the aromatic isocyanate group, and then the blocking agent Y blocks the aliphatic isocyanate group to obtain the curing agent. .

The blocking agent X is 1 to 1 with respect to the aromatic isocyanate group in the polyisocyanate compound.
It is preferable to use 1 equivalent. On the other hand, blocking agent Y
Is preferably used in an amount of 1 to 1.1 equivalents based on the aliphatic isocyanate group in the polyisocyanate compound. When the above range is set, both low temperature curability and storage stability can be achieved. The curing agent obtained through the above manufacturing process can be represented by, for example, the following general formula (8).

[0058]

[Chemical 12]

In the formula, R ¹² is a residue obtained by removing active hydrogen from at least one blocking agent selected from the group consisting of alcohols, lactams and amino alcohols. R ¹³ is a residue obtained by removing active hydrogen from at least one blocking agent selected from the group consisting of oximes, active methylene-containing compounds and phenols. n shows 0-4.

[Curing Agent III Containing Two Types of Block Isocyanate Compounds Having Different Glass Transition Temperatures] By using this type of curing agent, it is possible to reduce the influence of a change in electrodeposition bath temperature on the film thickness. This curing agent contains two types of blocked isocyanate compounds, namely, blocked isocyanate compound A and blocked isocyanate compound B. Blocked isocyanate compounds A and B
Is not particularly limited as long as it satisfies the following relationship.

Two kinds of blocked isocyanate compound A
And B must have different glass transition temperatures. As the blocked isocyanate compound A, one having a glass transition temperature higher than that of the blocked isocyanate compound B is used. The difference in glass transition temperature between the blocked isocyanate compound A and the blocked isocyanate compound B is at least 25 ° C., preferably 25
~ 60 ° C. When the difference in glass transition temperature is less than 25 ° C., the film thickness of the coating film by electrodeposition coating is easily affected by the change in electrodeposition bath temperature. If the difference in glass transition temperature exceeds 60 ° C., the function as a curing agent may not be sufficiently exhibited. The glass transition temperature mentioned here is a value measured by a differential thermal analyzer.

The glass transition temperature of each blocked isocyanate compound is preferably 10 to 40 ° C. for the blocked isocyanate compound A and −20 to 0 ° C. for the blocked isocyanate compound B. Outside these ranges,
It may adversely affect the general physical properties of the electrodeposition coating film.

The difference in solubility parameter between the blocked isocyanate compound A and the blocked isocyanate compound B is preferably 0.1 to 3.0, more preferably 0.6 to 1.5. Outside this range, the change in bath temperature during electrodeposition coating has a large effect on the film thickness. The solubility parameter between the two blocked isocyanate compounds does not matter. That is, the solubility parameter of the blocked isocyanate compound A may be larger or smaller than that of the blocked isocyanate compound B.

The solubility parameter of each blocked isocyanate compound is not particularly limited. However, the blocked isocyanate compound A is preferably 9.5 to 11.5, and the blocked isocyanate compound B is preferably 11.6 to 13.5. In addition, the solubility parameter (SP) is the Journal of Applies.
d Polymer Science, 12, 2359
(1968), K. W. SUH and J.
M. It is determined by the following formula (1) according to CORBETT.

[0065]

[Equation 1]

In the formula, Vml is the volume of the low SP solvent at the cloud point,
Vmh is the cloud volume of the high SP solvent, δml is the solubility parameter of the low SP solvent, and δmh is the solubility parameter of the high SP solvent.

As the blocked isocyanate compounds A and B, various compounds can be used as long as they are prepared by blocking a general polyisocyanate compound with a general blocking agent. As the polyisocyanate compound, both an aromatic polyisocyanate compound and an aliphatic polyisocyanate compound can be used. Therefore,
As the combination of the blocked isocyanate compounds A and B, for example, the following four combinations are possible.

1. A: Aromatic blocked isocyanate compound B: Aliphatic blocked isocyanate compound 2. A: Aromatic blocked isocyanate compound B: Aromatic blocked isocyanate compound 3. A: Aliphatic blocked isocyanate compound B: Aliphatic blocked isocyanate compound 4. A: Aliphatic Block Isocyanate Compound B: Aromatic Block Isocyanate Compound Among the above combinations, from the viewpoint of design flexibility, 1. Is preferred.

The mixing ratio of the blocked isocyanate compound A to the blocked isocyanate compound B is preferably 15/85 to 40/60 in terms of weight ratio (A / B). If it is out of this range, the film thickness of the coating film tends to be affected by the change in the temperature of the electrodeposition bath.

In consideration of suppression of heat loss, it is preferable that one or both of the blocked isocyanate compound A and the blocked isocyanate compound B contain an isocyanurate ring as in the above curing agents I and II. The above-mentioned curing agent III is obtained by mixing the above-mentioned blocked isocyanate compounds A and B by any method.

[0071]Dissociation catalyst  The dissociation catalyst used in the composition of the present invention is an organotin compound.
And cobalt, nickel or zinc organic acid salts and di-
At least one selected from the group consisting of ketone metal complexes
And metal compounds of.

[Regarding Organic Tin Compound] The organic tin compound used in the present invention is, for example, at least one selected from the group of organic tin compounds represented by the following general formulas (1) and (2).

[0073]

[Chemical 13]

[0074]

[Chemical 14]

In the general formulas (1) and (2), R ¹
And R ³ are each an alkyl group or an aryl group having 1 to 12 carbon atoms. Specific examples include a methyl group, a butyl group, an octyl group, a lauryl group, and a phenyl group. Of these, a butyl group and an octyl group are particularly preferable.

R ² is a hydrogen atom or has 1 to 2 carbon atoms.
It is one alkyl group, alkenyl group, aralkyl group, cycloalkyl group, alkoxyalkyl group or aryl group. Specific examples thereof include residues of octylic acid and 2-ethylhexyl acid.

X and Y are OCOR ² , OH, halogen, O1 / 2 or S1 / 2. Where OCOR
² is a carboxylic acid residue having ² to 22 carbon atoms, which has the above-described R ² group. Specifically, formic acid, acetic acid, caproic acid, octylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, neopentanoic acid, neoheptanoic acid, neodecanoic acid, acrylic acid, crotonic acid,
Isocrotonic acid, undecylenic acid, oleic acid, erucic acid, sorbic acid, linoleic acid, linolenic acid, phenylacetic acid, phenylbutyric acid, phenylpropionic acid, cyclopentanecarboxylic acid, acetoacetic acid, benzoic acid, methoxybenzoic acid, tert-butylbenzoic acid Examples thereof include acid and hydroxybenzoic acid. Of these, acetic acid, octylic acid, lauric acid and benzoic acid are particularly preferable. Further, examples of the halogen include chlorine, bromine, fluorine, iodine and astatine, and among these, chlorine is particularly preferable.

Z is O (oxygen atom), S (sulfur atom) or a divalent carboxylic acid residue. Here, the divalent carboxylic acid residue is a residue of a divalent aliphatic carboxylic acid or aromatic carboxylic acid such as adipic acid, maleic acid or phthalic acid, or a sulfur-containing divalent fatty acid such as thiodipropionic acid. Residues of group carboxylic acids are mentioned. p is an integer of 0 or 1.

Formulas represented by the above general formulas (1) and (2)
Specific examples of the organic tin compound include monomethyl tin triformic acid.
Salt, monomethyltin triacetate, monomethyltin trioctyl
Phosphate, monomethyltin trilaurate, monomethyltin
Tristearate, monomethyltin triacrylate,
Monomethyltin tricrotonate, monomethyltin triole
Inoate, monomethyltin trierucate, monomethyltin
Sorbate, monomethyltin trilinoleate, monomer
Chill tin trisphenyl acetate, monomethyl tin trisphe
Nylpropionate, monomethyltin trisacetoacetic acid
Salt, monomethyltin tribenzoate, monobutyltin trivine
Acid salt, monobutyltin tricaproate, monobutyltin salt
Lyoctylate, monobutyltin trilaurate, mono
Butyltin trimyristate, monobutyltin tripalmi
Titanate, monobutyltin tristearate, monobutyrate
Rutin tribehenate, monobutyltin triacrylate,
Monobutyltin tricrotonate, Monobutyltin triiso
Crotonate, monobutyltin triundecylenate, molybdenum
Nobutyltin trioleate, Monobutyltin trierca
Acid salt, monobutyltin trisorbate, monobutyltin salt
Linolenate, monobutyltin trilinolenate, mono
Butyltin trisphenylacetate, monobutyltin trisulfate
Phenyl butyrate, monobutyltin trisphenylpropion
Acid salt, monobutyltin triscyclopentanecarboxylic acid
Salt, monobutyltin trisacetoacetate, monobutyltin
Libenzoate, monobutyltin trismethoxybenzoic acid
Salt, monooctyl tin triacetate, monooctyl tin trio
Cutylate, monooctyltin trilaurate, monoo
Octyl tin tristearate, monooctyl tin tribehe
Phosphate, monooctyltin triacrylate, monooctyl
Rutin trioleate, monooctyltin trierucate
Salt, monooctyltin trisorbate, monooctyltin
Trilinoleate, monooctyltin trisphenylacetic acid
Salt, monooctyltin trisphenylpropionate, molybdenum
Nooctyltin trisacetoacetate, Monooctyltin triacetate
Benzoate, monolauryl tin triacetate, monolauryl
Tin trioctylate, monolauryl tin trilaurate
Salt, monolauryl tin tristearate, monolauryl
Tin triacrylate, monolauryl tin trioleate
Salt, monolauryltin trisphenylbutyrate, monolauri
Rutin tribenzoate, monophenyl tin triacetate, mono
Phenyltin trioctylate, monophenyltin trilaurate
Phosphate, monophenyltin tricrotonate, monophe
Nyl tin trioleate, monophenyl tin trispheny
Acetate, monophenyltin trisphenylpropionic acid
Salt, monophenyltin tribenzoate, monomethyltin divine
Acid salt / monohydroxide, monomethyltin monoacetic acid
Salt / dihydroxide, monomethyltin dicaproic acid
Salt / monohydroxide, monomethyltin dioctyl
Acid salt / monohydroxide, monomethyltin dilaurate
Phosphate / monohydroxide, monomethyltin dibenzoate
Perfume salt / monohydroxide, monobutyltin diacetate
Salt / monohydroxide, monobutyltin monoacetate
・ Dihydrooxide, monobutyltin dioctylate
・ Monohydroxide, monobutyltin monooctyl
Acid salt / dihydroxide, monobutyltin dilaurine
Acid salt / monohydroxide, monobutyltin monolaurate
Phosphate / dihydroxide, monobutyltin diac
Phosphate / monohydroxide, monobutyltin mono
Oleate / dihydroxide, monobutyltin vinyl
Sphenylacetate / monohydroxide, monobutyrate
Rutin dibenzoate / monohydroxide, monobutyrate
Rutin monobenzoate / dihydrooxide, monooctane
Chilltin diacetate / monohydroxide, monooctyl
Rutin monoacetate / dihydroxide, monooctyl
Tin dioctylate / monohydroxide, monooctane
Cyltin dioctylate / monohydroxide, mono
Octyltin monooctylate / dihydrooxide,
Monooctyltin dilaurate / monohydroxai
De, monooctyltin monolaurate / dihydrooxy
Side, monooctyltin dicrotonate / monohydro
Oxide, monooctyltin dierucate monohydrate
Rooxide, monooctyltin dilinolenate / monoha
Idrooxide, monooctyltin bisphenyl butyrate
・ Monohydroxide, monooctyltin biscyclo
Pentanecarboxylate / monohydroxide, mono
Octyl tin dibenzoate / monohydroxide, mono
Octyl tin monobenzoate / dihydrooxide, moth
Nooctyltin bismethoxybenzoate / monohydroo
Cide, monolauryl tin diformate, monohydro oki
Side, monolauryl tin diacetate / monohydroxa
Id, monolauryl tin monolaurate / dihydro
Quiside, monolauryl tin dimyristate / mono high
Drooxide, monolauric acid dipalmitate
Nohydrox oxide, monolauryl tin monostearin
Acid salt / dihydroxide, monolauryl tin dibehen
Acid salt / monohydroxide, monolauryl tin diiso
Crotonate / monohydroxide, monolauryl
Tin diundecylenate / monohydroxide, mono
Lauryl tin disorbate / monohydroxide,
Monolauryl tin dilinoleate / monohydroxai
De, monolauryl tin monophenyl propionate, diha
Idrooxide, monolauryl tin bisacetoacetate
Monohydroxide, monolauryl tin dibenzoate
・ Monohydroxide, monolauryl tin monomethoxide
Cibenzoate / dihydroxide, monophenyltin
Monoacetate / dihydroxide, monophenyltin di
Octylate / monohydroxide, monophenyl
Tin dilaurate / monohydroxide, monofe
Nyltin dioleate / monohydroxide, mono
Phenyltin monoacetoacetate / dihydrooxide,
Monophenyltin dibenzoate / monohydroxai
De, monomethyltin diacetate / monochloride, monomethyi
Rutin monoacetate / dichloride, monomethyltin dioctyl
Phosphate / monochloride, monomethyltin monooctylic acid
Salt / dichloride, monomethyltin dilaurate / mono
Chloride, Monomethyltin diacrylate, Monochrome
Id, monomethyltin dioleate / monochloride,
Monomethyltin bisphenylpropionate monochlora
B, monomethyltin dibenzoate / monochloride, mono
Butyltin diacetate / monochloride, monobutyltin mono
Acetate / dichloride, monobutyltin monocaproate
・ Dichloride, monobutyltin dioctylate ・ Monoc
Loride, monobutyltin monooctylate / dichlorate
, Monobutyltin dilaurate / monochloride,
Nobutyltin monolaurate dichloride, monobutyrate
Rutin monobehenate / dichloride, monobutyltin mono
Crotonate / dichloride, monobutyltin dierucic acid
Salt / monochloride, monobutyltin bisphenylacetate
・ Monolide, monobutyltin bisacetoacetate
Nochloride, monobutyltin monobenzoic acid / dichlore
De, monobutyltin monomethoxybenzoate / dichlorate
De, monooctyltin diacetate / monochloride, monoo
Octyl tin monoacetate / dichloride, monooctyl tin di
Octylate monochloride, monooctyl tin monoo
Cutylate / dichloride, monooctyltin dilaurin
Acid chloride / monochloride, monooctyltin monolauric acid
Salt, dichloride, monooctyl tin distearate
Monochloride, monooctyltin dilanedecylenate ・
Monochloride, monooctyltin dioleate mono
Chloride, monooctyltin bisacetoacetate / monoc
Loride, monooctyl tin dibenzoate, monochlori
De, monooctyl tin monobenzoate / dichloride, molybdenum
Nolauryl tin monoacetate / dichloride, monolauryl
Tin monooctylate dichloride, monolauryl tin di
Laurate / monochloride, monolauryl tin dimilli
Statin salt / monochloride, monolauryl tin diisoc
Rotonate monochloride, monolauryl tin monophe
Nyl butyrate / dichloride, monolauryl tin dibenzoate
Salt / monochloride, monolauryl tin monobenzoate
Dichloride, monophenyltin diformate, Monochrome
De, monophenyl tin monoacetate / dichloride, monof
Phenyl tin dioctylate monochloride, monophenyl
Rutin dilaurate monochloride, monophenyl tin
Dipalmitate / monochloride, monophenyltin di
Sorbate monochloride, monophenyl tin bis-a
Cetoacetate / monochloride, monophenyltin monometh
Xybenzoate dichloride, monomethyltin diacetate
・ Oxide (1/2), monomethyltin monoacetate
Cide, monomethyltin dicaproate / oxide
(1/2), monomethyltin dioctylate oxide
(1/2), monomethyltin dilaurate / oxide
(1/2), monomethyltin dibehenate / oxide
(1/2), monomethyltin diacrylate / oxide
(1/2), monomethyltin bisacetoacetate / Oxai
(1/2), monomethyltin dibenzoate / oxide
(1/2), monomethyltin diacetate / oxide (1 /
2), monobutyltin diacetate / oxide (1/2),
Monobutyltin monoacetate / oxide, monobutyltin di
Octylate / oxide (1/2), monobutyltin molybdenum
Noctylate oxide, monobutyltin dilaurine
Acid salt / oxide (1/2), monobutyltin monolauri
Phosphate / oxide, monobutyltin distearate /
Oxide, monobutyltin dicrotonate / oxide
(1/2), monobutyltin bisphenylacetate / oxa
Id (1/2), Monobutyltin dibenzoate / Oxai
Dode, monobutyltin monobenzoate / oxide, monobu
Chilltin bismethoxybenzoate oxide (1 /
2), monooctyltin diacetate / oxide (1 /
2), monooctyltin monoacetate / oxide, monoo
Octyl tin dioctylate oxide (1/2), mono
Octyl tin monooctylate / oxide, monooctyl
Rutin dilaurate oxide (1/2), monooctane
Chill tin dilaurate / oxide (1/2), Monoo
Octyl tin monolaurate / oxide, monooctyl
Tin dimyristate / oxide (1/2), monooctane
Chilltin dicrotonate / oxide (1/2), Monoo
Octyl tin bisphenyl butyrate / oxide (1/2),
Monooctyltin dibenzoate / oxide (1/2),
Monooctyltin monobenzoate / oxide, monooctyl
Chilltin bismethoxybenzoate oxide (1 /
2), monolauryl tin diacetate / oxide (1 /
2), monolauryl tin dicaproate oxide (1
/ 2), monolauryl tin dioctylate oxide
(1/2), monolauryl tin monolaurate / oxa
Id, monolauryl tin dipalmitate / oxide
(1/2), monolauryl tin diisocrotonate / Oki
Side (1/2), monolauryl tin dibenzoate / Oki
Side (1/2), monomethyltin diacetate / Sulfie
(1/2), monomethyltin dioctylate / sulfa
Id (1/2), monomethyltin dilaurate / sulf
(1/2), monomethyltin dilaurate / monkey
Fido (1/2), monomethyltin dibenzoate / monkey
Fide (1/2), monobutyltin diacetate / sulfa
Id (1/2), monobutyltin monoacetate / Sulfie
, Monobutyltin dioctylate / sulfide (1 /
2), monobutyltin monooctylate sulfide,
Monobutyltin dilaurate / sulfide (1 /
2), monobutyltin monolaurate / sulfide,
Monobutyltin dibenzoate / sulfide (1/2),
Monobutyltin monobenzoate / sulfide, monooctane
Chill tin diacetate / sulfide (1/2), monooctyl
Rutin monoacetate / sulfide, monooctyltin dioc
Citrate / sulfide (1/2), monooctyl tin molybdenum
Nooctyl acid salt / Sulfide, Monooctyl tin dilaur
Phosphate / sulfide (1/2), monooctyl tin molybdenum
Nolaurate / sulfide, monooctyltin dibenzoate
Aromatic salt / sulfide (1/2), monooctyl tin mono
Benzoate / Sulfide, Monomethyltin monoacetate /
Monohydroxide monochloride, monobutyl
Tin monooctylate / monohydroxide / oxa
Id (1/2), monooctyltin monolaurate, molybdenum
No Hydroxide Sulfide (1/2), Mono
Lauryl tin monobenzoate / monochloride / hydro
Oxide, monophenyltin monooctylate / monoc
Loride sulfide (1/2), monophenyl tin molybdenum
Nolaurate, oxide (1/2), sulfite
De, dimethyltin diformate / dimethyltin diacetate, dimethy
Rutin dioctylate, dimethyltin distearate, ditin
Methyltin dineopentanate, dimethyltin diacrylic acid
Salt, dimethyltin bisphenylacetate, dimethyltin bis-a
Cetoacetate, dimethyltin bismethoxybenzoate, dib
Cyltin diacetate, dibutyltin dioctylate, dibutyl
Tin dilaurate, dibutyl tin dibehenate, dibutyl
Tin dineodecanoate, dibutyltin dicrotonate, dibu
Chilltin bisphenyl butyrate, dibutyltin bisacetoacetic acid
Salt, dibutyltin dibenzoate, dibutyltin bister compound
Libutyl benzoate, dioctyl tin diacetate, dioc
Chill tin dioctylate, dioctyl tin dilaurate,
Dioctyl tin dimyristate, dioctyl tin dineoate
Butanoate, dioctyltin diisocrotonate, dioctane
Chill tin dioctylate, dioctyl tin dibenzoate, di
Octyl tin bishydroxybenzoate, dilauryl tin di
Acetate, dilauryl tin dicaproate, dilauryl tin di
Octylate, dilauryltin dipalmitate, dilaurate
Ryl tin distearate, dilauryl tin diisocroton
Acid salt, dilauryltin dierucate, dilauryltin dibenzoate
Perfume salt, diphenyltin diformate, diphenyltin dilauri
Phosphate, diphenyltin diundecylenate, diphenyl
Tin dilinolenate, diphenyl tin dicyclopentanecar
Bonate, diphenyltin bismethoxybenzoate, bis
(Dimethyltin monoacetate) oxide, bis (dimethyl)
Tin monooctylate) oxide, bis (dimethyltin molybdate)
Nolaurate oxide, bis (dimethyltin monoa)
(Crylate) oxide, bis (dimethyltin monophenyl)
Acetate, bis (dimethyltin monocyclope)
(Tantan carboxylate) oxide, bis (dimethyltin molybdate)
Noacetoacetic acid salt) oxide, bis (dimethyltinmonoacetate)
Benzoate) oxide, bis (dibutyltin monoacetate)
Oxide, bis (dibutyltin monocaproate) oki
Side, bis (dibutyltin monooctylate) oxai
Bis (dibutyltin monolaurate) oxide,
Bis (dibutyltin monomyristate) oxade, bi
Sus (dibutyltin monopalmitate) oxide, bis
(Dibutyltin monostearate) oxide, bis
(Dibutyltin mononeodecanoate) oxide, bis
(Dibutyltin monooleate) Oxide, Bis (di)
Butyltin monophenyl butyrate) oxide, bis (dib)
Chilltin monobenzoate) oxide, bis (dibutyltin)
Mono-tert-butyl benzoate) oxide, bis
(Dioctyltin monoformate) oxide, bis (dioctyl)
Cyltin monoacetate) oxide, bis (dioctyltin molybdenum)
Nooctylate oxide, bis (dioctyltin mono)
Laurate oxide, bis (dioctyltin monos)
Thearate oxide, bis (dioctyltin monone)
Odecanoate oxide, bis (dioctyl tin monoc)
Rotonate oxide, bis (dioctyltin monolino)
Oxalate) oxide, bis (dioctyltin monophenyl)
Rupropionate) oxide, bis (dioctyltin molybdenum)
Benzoate) oxide, bis (dioctyltin) monomer
Toxybenzoate oxide, bis (dioctyltin molybdenum)
Nohydroxybenzoate) oxide, bis (dilauri)
Rutin monocaproate) oxide, bis (dilauryl)
Tin monooctylate) oxide, bis (dilauryl tin)
Monolaurate oxide, bis (dilauryltin molybdate)
Noisocrotonate oxide, bis (dilauryl tin)
Monolinolenic acid salt) oxide, bis (dilauryltin molybdenum)
Benzoate oxide, bis (diphenyltin monolayer)
Urate oxide, bis (diphenyltin monoun)
Decylenate) oxide, bis (diphenyltinmonoe)
Lukaate oxide, bis (diphenyltin monosorbi)
Acid salt) oxide, bis (diphenyltin monomethoxy)
Benzoate oxide, bis (dimethyltin monoformic acid)
Salt) sulfide, bis (dimethyltin monoacetate) monkey
Fido, bis (dimethyltin monooctylate) sulf
Guide, bis (dimethyltin monolaurate) sulfa
Id, bis (dibutyltin monoacrylate) sulphide
De, bis (dimethyltin monooleate) sulphide
De, bis (dimethyltin monophenylacetate) sulphide
De, bis (dimethyltin monocyclopentanecarboxylic acid
Salt) Sulfide, bis (dimethyltin monobenzoate)
Sulfide, bis (dibutyltin monoacetate) sulf
Aid, bis (dibutyltin monocaproate) sulfa
Id, bis (dibutyltin monooctylate) sulphide
De, bis (dibutyltin monolaurate) sulphide
De, bis (dibutyltin monomyristate) sulphide
De, bis (dibutyltin monopalmitate) sulphide
De, bis (dibutyltin monostearate) sulphide
Bis (dibutyltin monobehenate) sulfide,
Bis (dibutyltin monotonate) sulfide, Bi
Su (dibutyltin monoisocrotonate) sulfide,
Bis (dibutyltin monoundecylenate) sulphide
Bis (dibutyltin monoerucate) sulfide,
Bis (dibutyltin monosorbate) sulfide, Bi
Su (dibutyltin monophenylbutyrate) sulfide, Bi
Sus (dibutyltin monobenzoate) sulfide, bis
(Dioctyltin monoacetate) sulfide, bis (geo
Octyltin monooctylate sulfide, bis (geo)
Cutyltin monolaurate sulfide, bis (geo)
Cutyltin monolinoleate) sulfide, bis (geo)
Octyl tin monolinolenate) sulfide, bis (geo)
Octyltin monophenylpropionate) sulfide,
Bis (dioctyltin monoacetoacetate) sulfide,
Bis (dioctyl tin monobenzoate) sulfide, Bi
Su (dioctyltin monomethoxybenzoate) sulphide
De, bis (dilauryl tin monoacetate) sulfide, bi
Su (dilauryl tin monooctylate) sulfide, Bi
Su (dilauryl tin monolaurate) sulfide, Bi
Su (dilauryl tin monobenzoate) sulfide, bis
(Diphenyltin monoacetate) sulfide, bis (diph
Phenyltin monooctylate) sulfide, bis (diff
Phenyl tin monolaurate sulfide, bis (geo)
Cutyltin monobenzoate) sulfide, bis (dimethy)
Rutin monoformate adipate, bis (dimethyltin mono)
Acetate) adipate, bis (dimethyltin monooctyl)
Acid salt) adipate, bis (dimethyltin monolauric acid)
Salt) adipate, bis (dimethyltin monoacrylic acid)
Salt) adipate, bis (dimethyltin monooleate)
Salt) adipate, bis (dimethyltin monophenylacetic acid)
Salt) adipate, bis (dimethyltin monobenzoate)
Adipate, bis (dibutyltin monoacetate) adipate
Acid salt, bis (dibutyltin monocaproate) adipic acid
Salt, bis (dibutyltin monooctylate) adipic acid
Salt, bis (dibutyltin monolaurate) adipic acid
Salt, bis (dibutyltin monostearate) adipic acid
Salt, bis (dibutyltin monoacrylate) adipic acid
Salt, bis (dibutyltin monooleate) adipic acid
Salt, bis (dibutyltin monolinoleate) adipic acid
Salt, bis (dibutyltin monophenylacetate) adipic acid
Salt, bis (dibutyltin monobenzoate) adipate,
Bis (dioctyltin monoacetate) adipate, bis
(Dioctyltin monocaproate) adipate, bis
(Dioctyltin monooctylate) adipate, bis
(Dioctyltin monolaurate) adipate, bis
(Dioctyltin monobehenate) adipate, bis
(Dioctyltin monochlorotonate) adipate, bis
(Dioctyltin monoisocrotonate) adipate,
Bis (dioctyltin monophenylbutyrate) adipic acid
Salt, bis (dioctyltin monobenzoate) adipic acid
Salt, bis (dioctyltin monomethoxybenzoate) horse mackerel
Pinate, bis (dilauryltin monoacetate) adipic acid
Salt, bis (dilauryltin monooctylate) adipic acid
Salt, bis (dilauryltin monolaurate) adipic acid
Salt, bis (dilauryltin monomyristate) adipine
Acid salt, bis (dilauryltin monopalmitate) adip
Phosphate, bis (dilauryltin monobehenate) adipine
Acid salt, bis (dilauryltin monoacrylate) adipine
Acid salt, bis (dilauryltin monooleate) adipine
Acid salt, bis (dilauryltin monoerucate) adipic acid
Salt, bis (dilauryltin monophenylacetate) adipine
Acid salt, bis (dilauryltin monoacetoacetate) adipine
Acid salt, bis (dilauryltin monobenzoate) adipic acid
Salt, bis (dilauryltin monooctylate) adipic acid
Salt, bis (diphenyltin monolaurate) adipic acid
Salt, bis (diphenyltin monobenzoate) adipic acid
Salt, bis (dimethyltin monoacetate) maleate, bis
(Dimethyltin monooctylate) maleate, bis
(Dimethyltin monolaurate) maleate, bis
(Dimethyltin monostearate) Maleate, bis
(Dimethyltin monoundecylenate) Maleate, Bi
Su (dimethyltin monoerucate) maleate, bis
(Dimethyltin monosorbate) maleate, bis
(Dimethyltin monolinolenate) maleate, bis
(Dimethyltin monophenylpropionate) Maleic acid
Salt, bis (dimethyltin monoacetoacetate) maleic acid
Salt, bis (dimethyltin monobenzoate) maleate,
Bis (dibutyltin monoformate) maleate, bis (dibutyltin)
Butyltin monoacetate) maleate, bis (dibutyltin)
Monooctylate maleate, bis (dibutyltin molybdate)
Nolaurate maleate, bis (dibutyltin mono)
Laurate maleate, bis (dibutyltin monobe)
(Henate) Maleate, Bis (dibutyltin monoacrylate)
Phosphate) Maleate, Bis (dibutyltin monoolein)
Acid salt) maleate, bis (dibutyltin monophenyl vinegar)
Acid salt) maleate, bis (dibutyltin monoacetoacetic acid)
Salt) maleate, bis (dibutyltin monobenzoate)
Maleate, bis (dibutyltin monomethoxybenzoic acid)
Salt) maleate, bis (dioctyltin monoacetate)
Leanate, bis (dioctyltin monocaproate)
Leanate, bis (dioctyltin monooctylate)
Leanate, bis (dioctyltin monolaurate)
Leanate, bis (dioctyltin monomyristate)
Maleate, bis (dioctyltin monopalmitic acid)
Salt) Maleate, Bis (dioctyltin monochlorotonate)
Salt) maleate, bis (dioctyltin monoisocroto)
Acid salt) maleate, bis (dioctyltin monolinole)
Acid salt) maleate, bis (dioctyltin monopheni)
Phosphate) Maleate, Bis (dioctyltin monocyclo)
Pentane dicarboxylate) maleate, bis (dioctane)
Chill tin monobenzoate maleate, bis (dioctyl)
Rutin monomethoxybenzoate) maleate, bis (di)
Octyl tin monomethoxybenzoate) maleate, bi
Su (dilauryl tin monoacetate) maleate, bis (di
Lauryl tin monooctylate) maleate, bis (di)
Lauryl tin monolaurate) maleate, bis (di)
Lauryl tin monolinoleate) maleate, bis (di)
Lauryl tin monophenyl propionate) Maleic acid
Salt, bis (dilauryltin monobenzoate) maleic acid
Salt, bis (dioctyltin monomethoxybenzoate) male
Inoate, bis (diphenyltin monoacetate) maleic acid
Salt, bis (diphenyltin monooctylate) maleic acid
Salt, bis (diphenyltin monolaurate) maleic acid
Salt, bis (diphenyltin monosorbate) maleic acid
Salt, bis (diphenyltin monobenzoate) maleic acid
Salt, bis (diphenyltin monomethoxybenzoate) male
Inoate, bis (dimethyltin monoformate) phthalate,
Bis (dimethyltin monoacetate) phthalate, bis (dim
Chilltin monooctylate) phthalate, bis (dimethyl)
Tin monolaurate phthalate, bis (dimethyltin molybdate)
Nostearate phthalate, bis (dimethyltin mono)
Undecylenate) phthalate, bis (dimethyltin mono)
Benzoate phthalate, bis (dimethyltin monomethoxide)
Cibenzoate phthalate, bis (dibutyltin monoacetic acid)
Salt) phthalate, bis (dibutyltin monocaproate)
Phthalate, bis (dibutyltin monooctylate) lid
Phosphate, bis (dibutyltin monolaurate) phthalate
Salt, bis (dibutyltin monoacrylate) phthalate,
Bis (dibutyltin monooleate) phthalate, bis
(Dibutyltin monophenylate) phthalate, bis (dibutyltin)
Butyltin monobenzoate phthalate, bis (dioctyl)
Rutin monoacetate) phthalate, bis (dioctyltin mono)
Octylate phthalate, bis (dioctyltin monora
Urilate) phthalate, bis (dioctyltin monomilli)
Stinto) phthalate, bis (dioctyltin monosol)
Phosphate, bis (dioctyltin monopheni)
Lupropionate) phthalate, bis (dioctyltin molybdenum)
Noacetoacetate) phthalate, bis (dioctyltin mono)
Benzoate phthalate, bis (dioctyltin monomethoate)
Xybenzoate phthalate, bis (dilauryltin mono)
Acetate) phthalate, bis (dilauryltin monooctyl)
Phthalate, bis (dilauryltin monolaurate)
Salt) phthalate, bis (dilauryl tin monobenzoate)
Phthalate, bis (diphenyltin monoacetate) phthalate
Salt, bis (diphenyltin monooctylate) phthalic acid
Salt, bis (diphenyltin monolaurate) phthalic acid
Salt, bis (diphenyltin monobenzoate) phthalate,
Bis (dimethyltin monoformate) thiodipropionate,
Bis (dimethyltin monoacetate) thiodipropionate,
Bis (dimethyltin monooctylate) thiodipropion
Acid salt, bis (dimethyltin monolaurate) thiodipro
Pionate, bis (dimethyltin monotonate) thio
Dipropionate, Bis (dimethyltin monophenylpro)
Thiodipropionate, bis (dimethyltin)
Monocyclopentanecarboxylate) Thiodipropionic acid
Salt, bis (dimethyltin monoacetoacetate) thiodipropy
Onate, bis (dimethyltin monobenzoate) thiodip
Ropionate, bis (dibutyltin monoacetate) thiodip
Ropionate, bis (dibutyltin monocaproate)
Odipropionate, bis (dibutyltin monooctyl acid)
Salt) thiodipropionate, bis (dibutyltin monolaurate)
Phosphate) thiodipropionate, bis (dibutyltin molybdenum)
Nopalmitate) thiodipropionate, bis (dib)
Tyltin monoisocrotonate) thiodipropionate,
Bis (dibutyltin monophenylbutyrate) thiodipropio
Phosphate, bis (dibutyltin monobenzoate) thiodipro
Pionate, bis (dioctyltin monoacetate) thiodip
Ropionate, bis (dioctyltin monooctylate)
Thiodipropionate, bis (dioctyltin monolaurate
Thiodipropionate, bis (dioctyltin molybdate)
Noerucate) Thiodipropionate, Bis (diocty)
Rutin monoacetoacetate) thiodipropionate, bis
(Dioctyltin monobenzoate) Thiodipropionic acid
Salt, bis (dioctyltin monomethoxybenzoate) thio
Dipropionate, Bis (dilauryltin monoacetate) Thi
Odipropionate, bis (dilauryltin monooctyl
Acid salt) thiodipropionate, bis (dilauryltin mono)
Laurate) thiodipropionate, bis (dilauri)
Rutin monolinoleate) thiodipropionate, bis
(Dilauryltin monophenylacetate) Thiodipropion
Acid salt, bis (dilauryltin monobenzoate) thiodipro
Pionate, bis (dilauryltin monoacetate) thiodip
Ropionate, bis (diphenyltin monooctylate)
Thiodipropionate, bis (diphenyltin monolauri
Acid salt) thiodipropionate, bis (diphenyltin molybdate)
Nolinolenate) thiodipropionate, bis (dife
Nyltin monobenzoate) thiodipropionate, etc.
To be

Among the above examples, preferred are monobutyltin triacetate, monobutyltin trioctylate, monobutyltin trilaurate, monobutyltin tribenzoate, monooctyltin triacetate, monooctyltin trioctylate, Monooctyltin trilaurate, monooctyltin tribenzoate, monobutyltin diacetate / monohydroxide, monobutyltin monoacetate / dihydrooxide, monobutyltin dioctylate / monohydrooxide, monobutyltin monooctylate Salt / dihydrooxide, monobutyltin dilaurate / monohydroxide, monobutyltin monolaurate / dihydrooxide, monobutyltin dibenzoate /
Monohydroxide, monobutyltin monobenzoate / dihydrooxide, monooctyltin diacetate / monohydroxide, monooctyltin monoacetate / dihydrooxide, monooctyltin dioctylate
Monohydroxide, monooctyltin dilaurate / monohydroxide, monooctyltin monolaurate / dihydrooxide, monooctyltin dibenzoate / monohydroxide, monooctyltin monobenzoate / dihydrooxide, monobutyl Tin diacetate / monochloride, monobutyltin monoacetate / dichloride, monobutyltin dioctylate / monochloride, monobutyltin monooctylate / dichloride, monobutyltin dilaurate / monochloride, monobutyltin monolaurate / dichloride , Monobutyltin dibenzoate monochloride, monobutyltin monobenzoic acid dichloride, monooctyltin diacetate monochloride, monooctyltin monoacetate dichloride, monooctyltin geode Tylate / monochloride, monooctyltin dilaurate / monochloride, monooctyltin monolaurate / dichloride, monooctyltin dibenzoate / monochloride, monooctyltin monobenzoate / dichloride, monobutyltin dichloride Acetate / oxide (1/2), monobutyltin monoacetate / oxide, monobutyltin dioctylate / oxide (1 /
2), monobutyltin monooctylate / oxide, monobutyltin dilaurate / oxide (1/2), monobutyltin monolaurate / oxide, monobutyltin dibenzoate / oxide (1/2), monobutyltin mono Benzoate / oxide, monooctyltin diacetate / oxide (1/2), monooctyltin monoacetate /
Oxide, monooctyltin dioctylate / oxide (1/2), monooctyltin monooctylate / oxide, monooctyltin dilaurate / oxide (1/2), monooctyltin monolaurate / oxide, mono Octyl tin dibenzoate oxide (1 /
2), monooctyltin monobenzoate / oxide, monobutyltin diacetate / sulfide (1/2), monobutyltin monoacetate / sulfide, monobutyltin dioctylate / sulfide (1/2), monobutyltin mono Octylate / Sulfide, Monobutyltin dilaurate / Sulfide (1/2), Monobutyltin monolaurate / Sulfide, Monobutyltin dibenzoate /
Sulfide (1/2), monobutyltin monobenzoate / sulfide, monooctyltin diacetate / sulfide (1/2), monooctyltin monoacetate / sulfide, monooctyltin dioctylate / sulfide (1)
/ 2), monooctyltin monooctylate sulfide, monooctyltin dilaurate sulfide (1
/ 2), monooctyltin monolaurate sulfide, monooctyltin dibenzoate sulfide (1 /
2), monooctyltin monobenzoate / sulfide,
Dibutyltin diacetate, dibutyltin dioctylate, dibutyltin dilaurate, dibutyltin dibenzoate, dioctyltin diacetate, dioctyltin dioctylate, dioctyltin dilaurate, dioctyltin dibenzoate,
Bis (dibutyltin monoacetate) oxide, bis (dibutyltin monooctylate) oxide, bis (dibutyltin monolaurate) oxide, bis (dibutyltin monobenzoate) oxide, bis (dioctyltin monoacetate) Oxide, bis (dioctyltin monooctylate) oxide, bis (dioctyltin monolaurate) oxide, bis (dioctyltin monobenzoate)
Oxide, bis (dibutyltin monoacetate) sulfide, bis (dibutyltin monooctylate) sulfide, bis (dibutyltin monolaurate) sulfide, bis (dibutyltin monobenzoate) sulfide,
These are bis (dioctyltin monoacetate) sulfide, bis (dioctyltin monooctylate) sulfide, bis (dioctyltin monolaurate) sulfide, and bis (dioctyltin monobenzoate) sulfide.

Particularly preferred are bis (dibutyltin monoacetate) oxide, bis (dibutyltin monooctylate) oxide, bis (dibutyltin monolaurate) oxide, bis (dibutyltin monobenzoate) oxide. , Bis (dioctyltin monoacetate) oxide, bis (dioctyltin monooctylate) oxide, bis (dioctyltin monolaurate) oxide, and bis (dioctyltin monobenzoate) oxide. Two or more kinds of the above-mentioned organotin compounds may be used in combination.

[Regarding Organic Acid Salt] The organic acid salt used in the present invention is, for example, an organic acid metal salt represented by the following general formula (3).

[0083]

[Chemical 15]

In the general formula (3), R ⁴ has the same meaning as R ^{2 in} the general formulas (1) and (2). Also,
M represents cobalt, nickel or zinc. Of these, inexpensive zinc is particularly preferable. Furthermore, q is 0
Alternatively, it is an integer of 1.

Specific examples of the organotin compound represented by the general formula (3) include cobalt diformate, cobalt diacetate, cobalt dicaproate, cobalt dioctylate, cobalt dilaurate and cobalt dichloride. Myristic acid salt, cobalt dipalmitic acid salt, cobalt distearic acid salt, cobalt dibehenic acid salt, cobalt dineopentanic acid salt, cobalt diacrylic acid salt, cobalt dicrotonic acid salt, cobalt diisocrotonic acid salt, cobalt diundecylene Acid salt, cobalt dioleate, cobalt dierucate, cobalt disorbate, cobalt dilinoleate, cobalt dilinolenate, cobalt bisphenyl acetate, cobalt bisphenyl butyrate, cobalt bisphenyl propionate Salt, cobalt biscyclopentanecarboxylate, co Ruthobisacetoacetate, cobalt dibenzoate, cobalt bismethoxybenzoate, cobalt bis-tert-butyl benzoate, nickel diformate, nickel diacetate, nickel dicaproate, nickel dioctylate, nickel dilaurate, nickel Dimyristate, nickel dipalmitate, nickel distearate, nickel dibehenate, nickel dineoheptanate, nickel diacrylate, nickel dicrotonate, nickel diisocrotonate, nickel di Undecylenate, nickel dioleate,
Nickel dierucate, nickel disorbate, nickel dilinoleate, nickel dilinolenate, nickel bisphenyl acetate, nickel bisphenyl butyrate,
Nickel bisphenyl propionate, nickel biscyclopentanecarboxylate, nickel bisacetoacetate, nickel dibenzoate, nickel bismethoxybenzoate, nickel bishydroxybenzoate, zinc diformate, zinc diacetate, Zinc dicaproate, zinc dioctylate, zinc dilaurate, zinc dimyristate, zinc dipalmitate, zinc distearate, zinc dibehenate, zinc dineodecanoate, zinc diacrylate, zinc dicrotonate Salt, zinc diisocrotonate, zinc diundecylenate, zinc dioleate, zinc dierucate, zinc disorbate, zinc dilinoleate, zinc dilinolenate, zinc bisphenylacetate,
Zinc bisphenyl butyrate, Zinc bisphenylpropionate, Zinc biscyclopentanecarboxylate, Zinc bisacetoacetate, Zinc dibenzoate, Zinc bismethoxybenzoate, Zinc bis-tert-butylbenzoate, Zinc bishydroxybenzoate Acid salt, bis (cobalt monoformate) oxide, bis (cobalt monoacetate) oxide, bis (cobalt monooctylate) oxide, bis (cobalt monolaurate) oxide, bis (cobalt monomyristate) oxide, Bis (cobalt monobehenate) oxide, bis (cobalt monoacrylate) oxide, bis (cobalt monotonate) oxide, bis (cobalt monoundecylenate) oxide, bis (cobalt monooleate) oxide, Screw( Baltic mono sorbate) oxide, bis (cobalt monophenyl acetate) oxide,
Bis (cobalt monophenylpropionate) oxide, bis (cobalt monocyclopentanecarboxylate)
Oxide, bis (cobalt monoacetoacetate) oxide, bis (cobalt monobenzoate) oxide, bis (cobalt monomethoxybenzoate) oxide, bis (nickel monoacetate) oxide, bis (nickel monocaproate) Oxide, bis (nickel monooctylate) oxide, bis (nickel monolaurate) oxide, bis (nickel monopalmitate) oxide, bis (nickel monostearate)
Oxide, bis (nickel monoacrylate) oxide, bis (nickel monoisocrotonate) oxide, bis (nickel monooleate) oxide, bis (nickel monoerucate) oxide, bis (nickel monolinoleate) ) Oxide, bis (nickel monolinolenate) oxide, bis (nickel monophenyl butyrate) oxide, bis (nickel monoacetoacetate) oxide, bis (nickel monobenzoate) oxide, bis (nickel monomethoxybenzoic acid) Salt) oxide, bis (zinc monoformate) oxide, bis (zinc monoacetate) oxide, bis (zinc monocaproate) oxide, bis (zinc monooctylate) oxide, bis (zinc monolaurate) oxide,
Bis (zinc monomyristate) oxide, bis (zinc monopalmitate) oxide, bis (zinc monostearate) oxide, bis (zinc monobehenate) oxide, bis (zinc mononeodecanoate) oxide, bis (Zinc monoacrylate) oxide, bis (zinc monotonate) oxide, bis (zinc monoisocrotonate) oxide, bis (zinc monoundecylenate) oxide, bis (zinc monooleate) oxide, Bis (zinc monoerucate) oxide, bis (zinc monosorbate) oxide, bis (zinc monolinoleate) oxide, bis (zinc monolinolenate) oxide, bis (zinc monophenylacetate) oxide, bis (Zinc monophenyl butyrate) Oxide, bis (zinc Roh phenylpropionic Sanshioshio)
Oxide, bis (zinc monocyclopentanecarboxylate) oxide, bis (zinc monoacetoacetate) oxide, bis (zinc monobenzoate) oxide, bis (zinc monomethoxybenzoate) oxide, bis (zinc monotertiary) Butylbenzoate) oxide and the like.

Of the above examples, the preferable one is
Cobalt diformate, cobalt dioctylate, cobalt dilaurate, cobalt dibenzoate, nickel diacetate, nickel dioctylate, nickel dilaurate, nickel dibenzoate, zinc diacetate, zinc dioctylate, Zinc dilaurate, zinc dibenzoate, bis (cobalt monoacetate) oxide, bis (cobalt monooctylate) oxide, bis (cobalt monolaurate) oxide, bis (cobalt monobenzoate) oxide, bis (Nickel monoacetate) oxide, bis (nickel monooctylate) oxide, bis (nickel monolaurate) oxide, bis (nickel monobenzoate) oxide, bis (zinc monoacetate) oxide, bis (zinc mono) Octylate) oxide, bis (sub) Monolaurin salt) oxide, bis (zinc mono benzoate) oxide.

Particularly preferred are bis (cobalt monoacetate) oxide, bis (cobalt monooctylate) oxide, bis (cobalt monolaurate) oxide, bis (cobalt benzoate) oxide and bis (nickel mono). Acetate) oxide, bis (nickel monooctylate) oxide, bis (nickel monolaurate) oxide, bis (nickel monobenzoate) oxide, bis (zinc monoacetate) oxide, bis (zinc monooctylate) ) Oxide, bis (zinc monolaurate) oxide, and bis (zinc monobenzoate) oxide.

[Diketone Metal Complex] The diketone metal complex used in the present invention is a complex compound composed of a diketone having two carbonyl groups in the molecule and cobalt, nickel or zinc.

The above-mentioned diketone is not particularly limited, and examples thereof include β-diketones represented by the following general formula (9).

[0090]

[Chemical 16]

In the formula, R ¹⁴ is a hydrogen atom, an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group,
R ¹⁵ CO- or an R ¹⁶ CO-. R ¹⁵ and R
¹⁶ represents a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, an alkoxyaryl group, an alkylaryl group, and an arylalkyl group, respectively. In addition, R ¹⁵
And R ¹⁶ may be the same as or different from each other. Further, R ¹⁵ and R ¹⁶ may form a cyclic structure between them.

Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, secondary butyl group, tertiary butyl group, acyl group, neopentyl group, isoamyl group, hexyl group and isohexyl group. , Heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, decyl group, isodecyl group, lauryl group, tridecyl group, carbon number 12 to 1
Examples thereof include a mixed alkyl group of 5, a stearyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclododecyl group, and a 4-methylcyclohexyl group.

Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the cycloalkyl group include a cyclooctyl group and an alkoxyaryl group. Examples of the alkoxyaryl group include a methoxyphenyl group, a propoxyphenyl group and a butoxyphenyl group.

Examples of the arylalkyl group include benzyl group, β-phenylethyl group, γ-phenylpropyl group and β-phenylpropyl group. Examples of the alkylaryl group include a tolyl group, a xylyl group, an ethylphenyl group, a butylphenyl group, a tert-butylphenyl group, an octylphenyl group, an isooctylphenyl group, a third octylphenyl group, a nonylphenyl group and a dinonylphenyl group. , 2,4-di-tert-butylphenyl group and the like.

Specific examples of the above β-diketone include dehydroacetic acid, dehydropropionyl acetic acid, dehydrobenzoyl acetic acid, cyclohexane-1,3-dione, dimedone, 2,2'-methylenebiscyclohexane-1,3-.
Dione, 2-benzylcyclohexane-1,3-dione, acetyltetralone, palmitoyltetralone, stearoyltetralone, benzoyltetralone, 2-acetylcyclohexanone, 2-benzoylcyclohexanone, 2-acetyl-cyclohexane-1,3-dione , Benzoyl-p-chlorobenzoylmethane, bis (4-methylbenzoyl) methane, bis (2-hydroxybenzoyl) methane, benzoylacetylmethane, tribenzoylmethane, diacetylbenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, lauroyl. Benzoylmethane, dibenzoylmethane, 4-methoxybenzoylbenzoylmethane, bis (4-methoxybenzoyl) methane, bis (4
-Chlorobenzoyl) methane, bis (3,4-methylenedioxybenzoyl) methane, benzoyl acetyl
Octyl methane, benzoyl acetyl phenyl methane, stearoyl 4-methoxy benzoyl methane, bis (4-tertiary butyl benzoyl) methane, benzoyl
Acetyl ethyl methane, benzoyl trifluor
Acetyl methane, diacetyl methane, butanoyl acetyl methane, heptanoyl acetyl methane, triacetyl methane, distearoyl methane, stearoyl acetyl methane, palmitoyl acetyl methane, lauroyl acetyl methane, benzoyl formyl methane,
Acetyl formyl methyl methane, benzoyl phenyl acetyl methane, bis (cyclohexanoyl) methane, bis (cyclohexanoyl) methane, dipivaloyl methane is mentioned.

Specific examples of the diketone compound of the above-mentioned diketone used in the present invention include cobalt stearoyl benzoyl methane, cobalt benzoyl methane,
Cobalt diacetyl methane, cobalt butanoyl acetyl methane, nickel stearoyl benzoyl methane, nickel dibenzoyl methane, nickel diacetyl methane, nickel butanoyl acetyl methane, zinc stearoyl benzoyl methane, zinc dibenzoyl methane, zinc diacetyl methane, zinc Butanoyl acetyl methane is mentioned.

The dissociation catalyst used in the present invention is, for example, at least one organotin compound (a) selected from the organotin compound group represented by the above general formula (1) or (2).
And at least one selected from the group consisting of the organic acid metal salt represented by the above general formula (3) and the diketone metal complex.
And a seed metal compound (b). That is, the dissociation catalyst uses the organotin compound (a) and the metal compound (b) together.

Here, the blending ratio (a: b) of the organotin compound (a) and the metal compound (b) is 9: 1 by weight.
1: 9 is preferable. If the blending ratio is outside this range, the low temperature curability of the composition of the present invention may be reduced. It is more preferable to set the blending ratio so that the addition amount of the organotin compound (a) is smaller than the addition amount of the metal compound (b). In this case, the catalytic effect at low temperature is enhanced, and the coating film appearance including smoothness of the coating film is improved. From such a viewpoint, the most preferable mixing ratio (a: b) of the organotin compound (a) and the metal compound (b) is 1: 1 to 2: 8.

Mixing ratio The cationic electrodeposition coating composition of the present invention contains the above-mentioned base resin in an amount of 50 parts by weight or more, preferably 60 parts by weight or more. When the ratio of the base resin is less than 50 parts by weight, it is difficult to obtain the desired corrosion resistance. On the other hand, the upper limit of the ratio of the base resin contained in the composition is 90 parts by weight, preferably 80 parts by weight. If it exceeds 90 parts by weight, a sufficient cured coating film may not be obtained in some cases.

The proportion of the blocked isocyanate curing agent is 10 parts by weight or more, preferably 20 parts by weight or more. If the proportion is less than 10 parts by weight, a sufficient cured coating film may not be obtained. On the other hand, the upper limit of the proportion of the blocked isocyanate curing agent is 50 parts by weight or less, preferably 40 parts by weight or less. If it exceeds 50 parts by weight, the desired corrosion resistance is difficult to obtain.

Further, the proportion of the dissociation catalyst is 0.01% by weight or more, preferably 0.5% by weight or more of the solid content of the base resin. If the proportion is less than 0.01% by weight, the desired low temperature curability and high corrosion resistance may not be achieved at the same time. On the other hand, the upper limit of the proportion of the dissociation catalyst is 5.0% by weight or less, preferably 3% by weight or less, of the solid content of the base resin. If it exceeds 5.0% by weight, cracks and pinholes are likely to occur in the electrodeposition coating film, which may impair the smoothness of the coating film.

The composition of the present invention may contain a pigment, a resin for dispersing the pigment and a solvent, if necessary, in addition to the essential components of the above technique. As the pigment, the pigment-dispersing resin, and the solvent, those commonly used for cationic electrodeposition coatings can be used.

The composition of the present invention is obtained by uniformly mixing the above-mentioned essential components and, if necessary, other components. The dissociation catalyst used in the present invention can be uniformly dispersed in the base resin without using a dispersing resin or the like. Therefore, the composition of the present invention is easy to prepare.

[0104]

EXAMPLES Production Example 1 (Production of base resin) A three-necked flask equipped with a reflux condenser, a thermometer, a stirrer and a dropping funnel was prepared. In this flask,
A mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate in a ratio of 8: 2 54
Parts by weight, 136 parts by weight of methyl isobutyl ketone, and 0.5 parts by weight of dibutyltin dilaurate were added and stirred, and then 11 parts by weight of methanol was further added dropwise from the dropping funnel over 30 minutes. The temperature in the flask was maintained at 60 ° C. to react for 30 minutes, and then 54 parts by weight of ethylene glycol mono-2-ethylhexyl ether was added dropwise from the dropping funnel over 1 hour. 60 to 65
The reaction was continued while maintaining the temperature at 0 ° C., and the reaction was terminated when the absorption spectrum of the isocyanate group disappeared in the infrared absorption spectrum.

Next, 285 parts by weight of an epoxy resin having an epoxy equivalent of 475 and 380 parts by weight of an epoxy resin having an epoxy equivalent of 950, which were respectively synthesized from bisphenol F and epichlorohydrin, were added to the flask and uniformly mixed. Then, the flask was heated to 120 ° C., 0.62 parts by weight of benzyldimethylamine was added, and the reaction was carried out while distilling off by-produced methanol using a decanter.
As a result, an oxazolidone ring-containing epoxy resin having an epoxy equivalent of 1120 was obtained.

Next, the flask was cooled, to which 29 parts by weight of diethanolamine and 2 parts of N-methylethanolamine 2 were added.
2 parts by weight and 33 parts by weight of a ketiminized product of aminoethanolamine (79% methyl isobutyl ketone solution) were added and reacted at 110 ° C. for 2 hours. After the reaction, the base resin was obtained by diluting with methyl isobutyl ketone until the nonvolatile content became 80%.

Production Example 2 (Production of Blocked Isocyanate Curing Agent) A three-necked flask equipped with a reflux condenser, a thermometer and a stirrer was prepared. Trimer hexamethylene diisocyanate and methyl ethyl ketoxime were added to the flask and the trimer hexamethylene diisocyanate was blocked with methyl ethyl ketoxime. The obtained blocked isocyanate is treated with a mixed solvent containing methyl isobutyl ketone and butanol in a ratio of 95: 5,
A blocked isocyanate curing agent having a solid content of 95% was obtained.

Production Example 3 (Production of Pigment Dispersion Paste) Pigment dispersion resin (modified epoxy resin containing tertiary sulfonium salt manufactured by Nippon Paint Co., Ltd .: base amount 75 meq / 10)
0 g, solid content 60% by weight) 120.0 parts by weight, 4.0 parts by weight of carbon black, 26.0 parts by weight of kaolin, 140.0 parts by weight of titanium dioxide and 30.0 parts by weight of aluminum phosphomolybdate are added to a sand mill. Was pulverized and dispersed. 33.3 parts by weight of ion-exchanged water was added thereto to adjust the nonvolatile content to 60%.

Examples 1 to 10 and Comparative Examples 1 to 140 140 parts by weight of the base resin obtained in Production Example 1 (as solid content), 60 parts by weight of the blocked isocyanate curing agent obtained in Production Example 2 (solid content) (Converted), the dissociation catalyst shown in Table 1 and 3.15 parts by weight of acetic acid were mixed to obtain a coating dispersion.
Deionized water was added to this with stirring, and the nonvolatile content was 30
Adjusted to be%. 115 parts by weight of the pigment dispersion paste (nonvolatile matter 60) obtained in Production Example 3 was added to this paint dispersion.
%), 783 parts by weight of deionized water, 10 parts by weight of 2-ethylhexyl cellosolve, and a surface control material were added to obtain a cationic electrodeposition coating composition having a nonvolatile content of 20%.

[0110]

[Table 1]

Test Using cold rolled untreated steel plate as a cathode, the dry film pressure was 20 μm.
The electrodeposition paints obtained in Examples 1 to 10 and Comparative Examples 1 to 4 were respectively electrodeposited so that Then, the coating film was cured under the baking conditions shown in Table 2. The obtained coating film was examined for curability, corrosion resistance, impact resistance, and plane smoothness. The results are shown in Table 2. The test method is as follows.

(Curability) The coating film was rubbed 50 times with gauze dipped in methyl isobutyl ketone, and the curing property was judged by the surface condition of the coating film. The evaluation criteria are as follows. ◯: The coating film is not scratched. Δ: The coating film is slightly scratched. X: The coating film is significantly scratched.

(Corrosion resistance) A cut reaching the substrate was put into a coating film using a knife, and a salt water immersion test was conducted using 5% saline at 55 ° C. The occurrence of peeling and blister of the coating film was evaluated according to the following criteria. It was examined peeling one side maximum peel width from the cut portion (mm). ◯: less than 3 mm. Δ: 3 mm or more and less than 6 mm. X: 6 mm or more. The blister number was examined in the range of 15 cm × 7 cm blister. ○: Very few. Δ: Little. X: Many.

(Impact resistance) The DuPont type (1 / 2φ, 500 g) of JIS-K5400 was carried out, and the height (cm) at which cracking or peeling did not occur was examined. (Plane smoothness) The appearance (degree of waviness) of the coating film was visually evaluated. ◯: Good. Δ: Slightly defective.

[0115]

[Table 2]

[0116]

Since the cationic electrodeposition coating composition of the present invention uses the above-mentioned dissociation catalyst, the low temperature curability and the corrosion resistance of the coating film can be simultaneously achieved at low cost.

Claims (12)

[Claims] 1. A base resin containing a cationic group, a blocked isocyanate curing agent, and a dissociation catalyst for the blocked isocyanate curing agent, wherein the dissociation catalyst comprises an organotin compound and cobalt, nickel or zinc. A cationic electrodeposition coating composition containing at least one metal compound selected from the group consisting of organic acid salts and diketone metal complexes. 2. The organotin compound has the following general formula (1):
The cationic electrodeposition coating composition according to claim 1, which is at least one kind of organic tin compound selected from the group of organic tin compounds represented by (2) and (2). [Chemical 1] [Chemical 2] (In the general formulas (1) and (2), R ¹ and R ³ : an alkyl group or an aryl group each having 1 to 12 carbon atoms R ² : a hydrogen atom, or an alkyl group having 1 to 21 carbon atoms, Alkenyl group, aralkyl group, cycloalkyl group,
Alkoxyalkyl group or aryl group X and Y: OCOR ² , OH, halogen, O1 / 2 or S1 / 2 Z: O, S or divalent carboxylic acid residue p: an integer of 0 or 1. ) 3. The cationic electrodeposition coating composition according to claim 1, wherein the organic acid salt is an organic acid metal salt represented by the following general formula (3). [Chemical 3] (In the general formula (3), R ^{4 is a} hydrogen atom, or an alkyl group having 1 to 21 carbon atoms, an alkenyl group, an aralkyl group, a cycloalkyl group,
Alkoxyalkyl group or aryl group M: cobalt, nickel or zinc q: an integer of 0 or 1. ) 4. The cationic electrodeposition coating composition according to claim 1, 2 or 3, wherein the base resin is an amino group-containing resin. 5. The cationic electrodeposition coating composition according to claim 1, wherein the base resin is an oxazolidone ring-containing epoxy resin. 6. The blocked isocyanate curing agent is
4. An isocyanurate ring, comprising: 1, 2, 3,
The cationic electrodeposition coating composition according to 4 or 5. 7. The blocked isocyanate curing agent is
The cationic electrodeposition coating composition according to claim 6, which contains an isocyanate group blocked by a glycol ether. 8. The blocked isocyanate curing agent comprises:
The cationic electrodeposition coating composition according to claim 6, comprising both a blocked aliphatic isocyanate group and a blocked aromatic isocyanate group. 9. The blocked isocyanate curing agent is
The cationic electrodeposition coating composition according to claim 1, which is a mixture of two types of blocked isocyanate curing agents having different glass transition temperatures. 10. The dissociation catalyst comprises a: b = 9: 1 to the organotin compound (a) and the metal compound (b).
A weight ratio of 1: 9 is included, Claims 1, 2, 3, 4,
The cationic electrodeposition coating composition according to 5, 6, 7, 8 or 9. 11. The dissociation catalyst contains a larger amount of the metal compound (b) than the organotin compound (a), as described in any one of claims 1 to 3. 9. The cationic electrodeposition coating composition according to item 9. 12. The base resin and the blocked isocyanate curing agent are contained in an amount of 90 to 50 parts by weight and 1 respectively.
0 to 50 parts by weight, and 0.01 to 5.0% by weight of the solid content of the base resin in the dissociation catalyst.
The cationic electrodeposition coating composition according to 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11.