JP3493829B2 - Curable base coat coating composition, coating film forming method, and coated article - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel curable base coat coating composition, a method for forming a coating film using the same, and a coated article.

[0002]

2. Description of the Related Art As a method for forming a coating film on the outer surface of an automobile body, a clear coat is applied by a wet-on-wet method on a base coat containing a coloring pigment and / or a bright pigment, and is simultaneously baked and cured. The method of forming a two-coat, one-bake coating film is a known technique. Conventionally,
As a coating material used in this coating film forming method, a polyol / melamine system, which is a main resin of polyol for both base coat and clear coat and is cured with an amino resin, is a general material and widely known in the industrial coating field as a known technique. It is used. However, in recent years in North America, the damage on the surface of the clear coat of this polyol / melamine-based coating material due to acid rain has increased dramatically. This phenomenon occurs due to hydrolysis of the ether bond, which is a crosslinked structure formed by the polyol / melamine-based paint, by acid rain. Therefore, this phenomenon is an essential defect of this polyol / melamine based coating.

In order to solve this problem, the present applicant has already proposed a novel curing technique in which an epoxy group-containing resin is cured with a chemically blocked acid type curing agent (JP-A-4-218561). Japanese Patent Laid-Open No. 4-22
7763, JP-A-5-320529, etc.). When applying this curing technology to clear coat,
The clear coat has essentially no chemical bond such as ether bond or amino bond which is easily hydrolyzed by an acid in its cross-linked coating film structure, and therefore not only has excellent acid rain resistance, but also stain resistance or weather resistance. In addition, since the main resin does not contain a hydrogen-bonding functional group such as a carboxyl group or a hydroxyl group, it is very advantageous for making the clear coat paint a high solid. However, when this clear coat is applied to a conventional polyol / melamine base coat by a wet-on-wet method and cured, the coating performance under normal use environment can be achieved, but under extremely harsh environment, For example, the coating film performance after immersion in boiling water or immersion in a mixed solvent of ethanol and unleaded gasoline has many inadequate points. In this way, a thermosetting base coat paint capable of sufficiently exhibiting the excellent properties of the novel thermosetting clear coat paint, which is composed of a combination of a chemically blocked acid type curing agent and a resin containing an epoxy group, No method of coating formation and coated articles have hitherto been found. In addition, when a conventional polyol / melamine clear coat is applied and cured by a wet-on-wet method with two coats and one bake, the coating performance in normal use environment can be achieved, but when the car is running at high speed The pebbles that bounced up,
There were many points of insufficient chipping resistance to improve the chipping phenomenon in which the coating film applied to the outer surface of an automobile was damaged and peeled off due to high-speed collision.
Conventionally, the chipping resistance has not been studied by improving the base coat, but the chipping resistance has been improved by adding a flat pigment or a urethane resin to the intermediate coating composition. However, the addition of the flat pigment causes an increase in the peeled area, the addition of the urethane resin causes a decrease in the compatibility, and a consequent decrease in the appearance. Such a problem of peeling in the chipping resistance is caused by the curable clear.
This is due to the fact that when the coat is crosslinked, the number of active sites for adhesion with the conventional polyol / melamine base coat is small.
A curable base coat paint, a method for forming a coating film, and a coated article capable of sufficiently exhibiting the excellent properties of the curable clear coat paint have not been found until now. Further, as the conventionally known thermosetting base coat composition, a carboxyl group-containing acrylic polymer and an epoxy group-containing curing agent are essential components, and if necessary, polyol, melamine, block isocyanurate and acid / epoxy curing catalyst. There is a thermosetting base coat composition containing (JP-A-6-248234, JP-A-6-248230). However, since this composition contains a carboxyl group-containing acrylic polymer, it has the drawback of poor stability. In addition, other conventionally known thermosetting base coat compositions include (1) an epoxy group-containing compound or polymer and (2) at least one functional group such as a carboxyl group or a hydroxyl group that reacts with an epoxy group. There is a thermosetting base coat composition containing the compound or polymer as an essential component (JP-A-60-248261). However, since the compound of the component (2) always reacts with the epoxy group of the component (1), the pot life is short and the water resistance is poor. In addition, low molecular weight polyepoxide, low molecular weight hydroxyl group-containing polyfunctional substance,
Thermosetting base coat composition containing acid anhydride curing agent and onium salt curing catalyst (JP-A-63-84674, JP-A-63-84673), hydroxyl group- and carboxyl group-containing resin, alicyclic group Thermosetting base coat composition containing a polyepoxide curing agent and a curing catalyst (JP-A-4-170485, JP-A-4-1265).
63), an acrylic resin having a hydroxyl group and a carboxyl group, a carboxyl group-containing acrylic resin, and a thermosetting base coat composition containing an acrylic resin having a hydroxyl group and an epoxy group (JP-A-6-128446). Has been. However, these are all of the acid / epoxy group reaction type, similar to the above, and have the shortcomings of short pot life and poor water resistance.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made for the purpose of providing a curable base coat coating composition which can sufficiently exhibit the excellent properties of a curable clear coat coating. Another object of the present invention is to provide a coating film forming method by a combination of a curable base coat coating composition and the above curable clear coat coating, and a coated article obtained by the method.

[0005]

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that when the clear coat is thermally crosslinked, a conventional polyol / melamine base coat is formed. As a result of further intensive research, focusing on the fact that there are few active sites for attachment, (1)
A resin component comprising a polymer of an ethylenically unsaturated monomer having a specific epoxy equivalent, a specific hydroxyl value, a specific glass transition temperature and a specific weight average molecular weight, and (2) one molecule of a functional group capable of reacting with a hydroxyl group. A curing agent having two or more inside,
(3) A Lewis acid catalyst, and (4) a curable base coat coating composition containing a coloring pigment and / or a bright pigment ensure an active point of adhesion to a curable clear coating coating and have excellent coating performance. Based on this finding, the present invention has been completed.

That is, the present invention provides (1) an epoxy equivalent of 500 to 3000 , a hydroxyl value of 20 to 200, a glass transition temperature of −30 to 80 ° C., and a weight average molecular weight of 300.
Resin component not having a carboxyl group consisting of a polymer of ethylenically unsaturated monomer in the range of 0 to 150,000, (2) Curing consisting of only a curing agent having two or more functional groups capable of reacting with a hydroxyl group in one molecule agents, (3) a Lewis acid catalyst, and (4) Ri <br/> consists coloring pigment and / or luster pigments, mixing ratio of the curing agent (2), a resin component of (1)
Relative to 100 parts by weight, there is provided a curable base coating composition comprising 10 to 100 parts by weight der Rukoto.

The present invention also provides a step of coating the surface of an object to be coated with the curable base coat coating composition, further comprising a chemically blocked acid type curing agent and a resin containing an epoxy group on the base coat. The present invention provides a method for forming a coating film, which comprises a step of applying a curable clear coat coating composition consisting of a combination of the above in a wet on wet manner. The present invention also includes a step of coating the curable base coat coating composition on the surface of an article to be coated,
Further, a curable clear coat comprising a polyol / melamine system and / or a polyisocyanate compound or a block thereof as a curing agent, in which a polyol is the main resin on this base coat and is cured with an amino resin. It is intended to provide a method for forming a coating film, which comprises a step of applying a coating composition in a wet-on-wet manner. Furthermore, the present invention provides a coated article coated by the above coating film forming method. Hereinafter, the present invention will be described in detail.

A resin component having no carboxyl group, which is a polymer of an ethylenically unsaturated monomer as the component (1) used in the curable base coat coating composition of the present invention (hereinafter, simply referred to as the ethylenic monomer as the component (1)). Saturated monomer
It is called a resin component composed of a polymer of. ) Is an epoxy equivalent of 500 to 3000 , preferably 700 to 3000 .
It has an epoxy group of. The resin component having no carboxyl group, which is a polymer of the ethylenically unsaturated monomer, acts as a chemical attachment point with the curable clear coat coating composition. When the epoxy equivalent of the resin component composed of the polymer of the ethylenically unsaturated monomer exceeds 3000 , the chemical attachment point is insufficient and the desired coating film performance cannot be obtained. On the other hand, when the epoxy equivalent is less than 500, the addition reaction between the epoxy groups is likely to occur and the coating film performance is deteriorated.

Further, the resin component comprising the polymer of the ethylenically unsaturated monomer as the component (1) has a hydroxyl value of 2
It has 0 to 200, preferably 20 to 100 hydroxyl groups. The hydroxyl group of the resin component composed of the polymer of the ethylenically unsaturated monomer reacts with the curing agent of the component (2) to form a crosslinked structure and secures the coating performance of the base coat. When the hydroxyl value of the resin component composed of the polymer of the ethylenically unsaturated monomer exceeds 200, curing proceeds excessively, the base coat coating becomes brittle, and desired coating performance cannot be obtained. On the other hand, when the hydroxyl value is less than 20 , curing does not proceed sufficiently and desired coating performance cannot be obtained.

To impart an epoxy group to the resin component composed of the polymer of the ethylenically unsaturated monomer, for example, an ethylenically unsaturated monomer having an epoxy group is copolymerized with another ethylenically unsaturated monomer. Can be done by. Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl acrylate, β-methylglycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and allyl. Glycidyl ether, methallyl glycidyl ether, N
-Glycidyl acrylic acid amide, vinyl sulfonic acid glycidyl, and the like. These ethylenically unsaturated monomers having an epoxy group may be used alone or in combination of two or more.

Further, in order to impart a hydroxyl group to the resin component comprising the polymer of the ethylenically unsaturated monomer, it is carried out, for example, by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another unsaturated monomer. be able to.
Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate and 4
-Hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, N-methylolacrylic acid amide and their ε-caprolactone adducts and the like can be mentioned. These ethylenically unsaturated monomers having a hydroxyl group may be used alone or in combination of two or more.

The above-mentioned other ethylenically unsaturated monomer is
Generally, a monomer having a non-reactive functional group is shown, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-
Butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, phenyl acrylate, phenyl methacrylate, benzyl acrylate, benzyl Methacrylate, tetracyclododecyl acrylate, tetracyclododecyl methacrylate, norbornyl acrylate, etc., or styrene, α-methylstyrene,
Vinyl toluene, fumaric acid dialkyl ester, itaconic acid dialkyl ester, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate and the like can be mentioned. Can be used accordingly. In the case of copolymerizing an ethylenically unsaturated monomer having an epoxy group with another ethylenically unsaturated monomer, an ethylenically unsaturated monomer having a hydroxyl group can also be used as another ethylenically unsaturated monomer, When copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another ethylenically unsaturated monomer, an ethylenically unsaturated monomer having an epoxy group can be used as the other ethylenically unsaturated monomer. These other ethylenically unsaturated monomers may be used alone or in combination of two or more.

The resin component comprising the polymer of the ethylenically unsaturated monomer as the component (1) has a glass transition temperature of −
30-80 degreeC, Preferably it is -20-80 degreeC, Especially preferably, it is -20-50 degreeC. When the glass transition temperature of the resin component comprising the polymer of the ethylenically unsaturated monomer is less than -30 ° C, sufficient coating film hardness cannot be obtained, and when it exceeds 80 ° C, the coating film becomes brittle and mechanical. Strength decreases. Here, the glass transition temperature is a numerical value calculated from the FOX equation shown below.

## EQU1 ## 1 / Tg = Σ (mi / Tgi) (In the formula, Tg means the glass transition temperature of the resin component composed of the polymer of the ethylenically unsaturated monomer, and mi is the weight fraction of the monomer i component. And Tgi means the glass transition temperature of the homopolymer of the monomer i component.)

Further, the resin component comprising the polymer of the ethylenically unsaturated monomer as the component (1) has a weight average molecular weight in the range of 3,000 to 150,000, preferably 50.
The range is from 00 to 100,000. The weight average molecular weight of the resin component composed of a polymer of an ethylenically unsaturated monomer is 3
If it is less than 000, crosslinking of the coating film does not proceed sufficiently, desired coating film performance cannot be obtained, and the weight average molecular weight is 15
If it exceeds 0000, it is difficult to apply the resin because the resin itself has a high viscosity. Here, the weight average molecular weight refers to a polystyrene equivalent weight average molecular weight measured by gel permeation chromatography.

The resin component composed of the polymer of the ethylenically unsaturated monomer is an ethylenically unsaturated monomer having the above epoxy group, an ethylenically unsaturated monomer having a hydroxyl group, and other ethylenically unsaturated monomer as required. Can be easily synthesized by radical copolymerization, and as the copolymerization method, known methods such as solution polymerization, dispersion polymerization, suspension polymerization and emulsion polymerization are used. Further, the resin component composed of the polymer of the ethylenically unsaturated monomer as the component (1) has an epoxy equivalent, a hydroxyl value, a glass transition temperature, and a weight average molecular weight as long as they are within the range of claim 1. It is also possible to use a mixture of a plurality of monomer polymers. The resin component comprising the polymer of the ethylenically unsaturated monomer as the component (1) may be used alone or in combination of two or more.

As the functional group of the curing agent having two or more functional groups capable of reacting with the hydroxyl group of the component (2) used in the present invention in one molecule, for example, a methylol group, an alkoxyalkyl group, an alkoxysilane group, Examples thereof include an alkoxyamide group, an isocyanate group, a carbamate group, an adiponitrile group, an ester group, a lactone ring and an acid anhydride ring. The curing agent has two or more of these functional groups in one molecule, preferably 2 to 50, and particularly preferably 2 to 6.
Specific examples of the curing agent include aminoplast resins and polyisocyanate compounds.

The aminoplast resin is a compound containing an amino group or an amide group, for example, melamine, benzoguanamine, urea, dicyandiamide, glycolurea and the like, and alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, n-butyl alcohol and isobutyl alcohol. The resin obtained by dehydration condensation with formaldehyde in the presence of On the other hand, as the polyisocyanate compound, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, aliphatic and alicyclic diisocyanate compounds such as 4,4′-diisocyanatoethyldicyclohexylmethane and their nurates, burettes, Examples thereof include adducts, and blocked isocyanates obtained by chemically blocking the isocyanate group of the above compounds with active methylene, oxime, lactam, alcohol, phenol and the like. (2)
As the curing agent as a component, one kind may be used alone, or two or more kinds may be used in combination.

The mixing ratio of the curing agent with respect to the ethylenic 100 parts by weight of the resin component comprising a polymer of unsaturated monomers, 10 to 100 parts by weight. In particular, when the curing agent is an aminoplast resin, the mixing ratio of the resin component composed of the polymer of the ethylenically unsaturated monomer and the aminoplast resin is usually 80:20 on the basis of resin solid content.
To 50:50, preferably 70:30 to 6
The range is 0:40. When the curing agent is an isocyanate compound, the mixing ratio of the resin component made of a polymer of the ethylenically unsaturated monomer and the isocyanate compound is usually 1: 0 on the basis of hydroxyl group and isocyanate group.
It is in the range of 7 to 0.7: 1, preferably 1: 0.85.
The range is from 0.85: 1.

Examples of the component (3) Lewis acid catalyst used in the present invention include boron trifluoride, aluminum trichloride, ferrous titanium chloride, ferric chloride, ferrous chloride and ferric chloride. Metal halides such as zinc chloride, zinc bromide, stannous chloride, stannic chloride, stannous bromide, stannic bromide, trialkylboron, trialkylaluminum, dialkylaluminum halides, monoalkylhalogens Aluminum chloride, tetraalkyltin, aluminum acetylacetonate, iron acetylacetonate, zirconium acetylacetonate, dibutyltin acetylacetonate, dibutyltin dilaurate, dioctyltin ester malate, magnesium naphthenate, calcium naphthenate, manganese naphthenate, naphthenic acid iron, Putian cobalt, copper naphthenate, zinc naphthenate, zirconium naphthenate, lead naphthenate, calcium octylate, manganese octylate,
Iron octylate, cobalt octylate, zinc octylate,
Examples thereof include organometallic compounds such as zirconium octylate, tin octylate, lead octylate, zinc laurate, magnesium stearate, aluminum stearate, calcium stearate, cobalt stearate, zinc stearate, and lead stearate. Among these Lewis acids, zinc compounds are preferable, and zinc chloride, zinc naphthenate, and zinc octylate are particularly preferable. These Lewis acid catalysts may be used alone or in combination of two or more. This Lewis acid catalyst acts as a reaction catalyst between an epoxy group in a resin composed of a polymer of an ethylenically unsaturated monomer of a base coat coating composition and a clear coat coating composition and a curing catalyst in the base coat coating composition, The compounding ratio thereof is usually 0.1 with respect to the resin solid content in the base coat coating composition.
It is from 05 to 3% by weight, preferably from 0.1 to 2% by weight.

Among the coloring pigments and / or bright pigments of the component (4) used in the present invention, the coloring pigments include, for example, titanium oxide, zinc oxide, yellow iron oxide, red iron oxide, carbon black and the like. Inorganic pigments, phthalocyanine blue, thren blue, phthalocyanine green, insoluble azo, soluble azo, perylene, quinacridone red,
Examples include organic pigments such as thioindigo red, dioxazine violet, anthrapyrimidine yellow, quinophthalone yellow, and benzidine yellow. Examples of bright pigments include aluminum flakes, nickel flakes, pearl mica, colored pearl mica, micro titanium oxide, and micro graphite. These coloring pigments and / or bright pigments may be used alone or in combination of two or more. The mixing ratio of the coloring pigment and / or the luster pigment of the component (4) is usually 0.5 to 200 parts by weight, preferably 2 to 100 parts by weight with respect to 100 parts by weight of the resin solid content.

In the curable base coat coating composition of the present invention, various resins such as acrylic resin, polyester resin, cellulose acetate butyrate, etc., which are added to the usual solvent type coating in a complementary manner, polyethylene wax, polyamide wax, internal Rheology modifiers such as cross-linked resin particles, extenders such as talc, kaolin, bentonite, and hydrophobic silica, ultraviolet absorbers, light stabilizers, anti-yellowing agents, leveling agents, anti-armpitting agents, and other paint additives. If necessary, one or more can be added.

The curable base coat coating composition of the present invention can be used as a solution type coating. The solvent used is not particularly limited as long as it can dissolve the Lewis acid catalyst, but n-hexane, n-
Aliphatic hydrocarbons such as heptane and n-octane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chloroform and carbon tetrachloride,
Alcohols such as methanol, ethanol, isopropanol and butanol, ethers such as dibutyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate, n-propyl acetate and n-butyl acetate. And the like, which are usually used as a coating solvent. Moreover, you may use what mixed the soluble amount of water to these solvents, and used them as a solvent. These solvents may be used alone or in combination of two or more.

The curable base coat coating composition of the present invention comprises coating a curable base coat coating composition on the surface of an object to be coated, and further containing a chemically blocked acid type curing agent and an epoxy group on the base coat. Wet a curable clear coat coating composition consisting of a combination with a resin
It is particularly effective when used as the curable base coat coating composition in the coating film forming method of coating on wet. The curable clear coat coating composition,
A chemically blocked acid type curing agent is included as the component (A). The chemically blocked acid type curing agent is
The functional group of the acid type curing agent is chemically bonded to the blocking agent to block the functional group, and specific examples thereof include ester derivatives, acid amide derivatives, hydrazide derivatives, oxime derivatives, and alkoxy. Examples include chemically blocked acid type curing agents such as ester derivatives and thioalkoxy ester derivatives.

Suitable compounds of the chemically blocked acid type curing agent of the component (A) include those represented by the general formula (1) as examples of the above alkoxy ester derivative.

[0025]

[Chemical 1]

(In the formula, R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is 1 to 1 carbon atoms.
8, an organic group, R ³ and R ⁴ may combine with each other to form a heterocycle having Y ¹ as a hetero atom, and Y ¹ is an oxygen atom or a sulfur atom. The compound which has 2 or more, preferably 2 to 50 functional groups in each molecule is shown. The functional group represented by the general formula (1) includes a carboxyl group and a general formula (2).

[0027]

[Chemical 2]

(Wherein R ¹ , R ² , R ³ , R ⁴ and Y ¹ are
It has the same meaning as above. ), A vinyl ether compound, a vinyl thioether compound or a heterocyclic compound having a vinyl type double bond having an oxygen atom or a sulfur atom as a hetero atom can be easily formed.

R ¹ , R ² and R ³ in the general formulas (1) and (2) are each a hydrogen atom or a carbon number of 1 to 1.
18 is an organic group such as an alkyl group, an aryl group and an alkaryl group, R ⁴ is an organic group such as an alkyl group having 1 to 18 carbon atoms, an aryl group and an alkaryl group, and these organic groups are appropriately substituted. R ³ and R ⁴ may have a group.
May be bonded to each other to form a heterocycle having or not having a substituent in which Y ¹ is a heteroatom. R ¹ ,
R ² and R ³ are preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group or an alkaryl group, and the preferable ones of R ⁴ are an alkyl group having 1 to 10 carbon atoms or an aryl group. Group, an alkaryl group.

Suitable specific examples of the above alkyl group include:
For example, methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 2-methylbutyl, n-hexyl, isohexyl, 3-methylpentyl, ethylbutyl, n-heptyl, 2-methylhexyl, n -Octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, methyloctyl, ethylheptyl, n-decyl, n-undecyl,
n-dodecyl, n-tetradecyl, n-heptadecyl,
Examples thereof include n-octadecyl group, and the alkyl group also includes cycloalkyl groups such as cyclobutyl group and cyclohexyl group. Preferred alkyl groups are alkyl groups having 1 to 10 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 2-methylbutyl, n-hexyl, isohexyl, 3-methylpentyl, ethylbutyl, n-heptyl, 2-methylhexyl, n-octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, methyloctyl, Mention may be made of ethylheptyl, n-decyl and cyclohexyl groups. The alkyl group also includes an aralkyl group. Specific examples thereof include benzyl, 1-phenylethyl, 2-phenylethyl, 2-phenylpropyl, 3-
Phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 6-phenylhexyl, 1- (4-methylphenyl) ethyl, 2- (4-methylphenyl) ethyl,
2-methylbenzyl and the like can be mentioned.

Specific examples of suitable aryl groups and alkaryl groups include aryl groups such as phenyl, tolyl, xylyl and naphthyl; 4-methylphenyl,
3,4-dimethylphenyl, 3,4,5-trimethylphenyl, 2-ethylphenyl, n-butylphenyl, t
ert-butylphenyl, amylphenyl, hexylphenyl, nonylphenyl, 2-tert-butyl-5-
Methylphenyl, cyclohexylphenyl, cresyl,
Examples thereof include alkaryl groups such as oxyethyl cresyl, 2-methyl-4-tert-butylphenyl, dodecylphenyl, etc., preferably phenyl having 6 to 10 carbon atoms, tolyl, xylyl, 4-methylphenyl, 3,4. −
Dimethylphenyl, 3,4,5-trimethylphenyl,
2-ethylphenyl, n-butylphenyl, tert-
An aryl group such as butylphenyl and an alkaryl group are preferable.

Specific examples of the compound represented by the general formula (2) include methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether. Aliphatic vinyl ether compounds such as and aliphatic vinyl thioether compounds corresponding thereto, and further 2,3-dihydrofuran,
3,4-dihydrofuran, 2,3-dihydro-2H-pyran, 3,4-dihydro-2H-pyran, 3,4-dihydro-2-methoxy-2H-pyran, 3,4-dihydro-4,4 -Dimethyl-2H-pyran-2-one, 3,4
Examples thereof include cyclic vinyl ether compounds such as sodium dihydro-2-ethoxy-2H-pyran and sodium 3,4-dihydro-2H-pyran-2-carboxylate, and cyclic vinyl thioether compounds corresponding to these.

The compound of the component (A) is obtained by reacting a compound having two or more, preferably 2 to 50, carboxyl groups in one molecule with a compound represented by the general formula (2). be able to. Examples of the compound having two or more carboxyl groups in one molecule include succinic acid, adipic acid, azelaic acid, sebacic acid, decamethylenedicarboxylic acid, and other aliphatic polycarboxylic acids having 2 to 22 carbon atoms, phthalic acid, Aromatic polycarboxylic acids such as isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid,
Examples thereof include alicyclic polycarboxylic acids such as tetrahydrophthalic acid, hexahydrophthalic acid, and methylhexahydrophthalic acid, and polyester resins having two or more carboxyl groups in one molecule, acrylic resins, maleated polybutadiene resins, and the like. Further, a carboxyl group-containing silicone oil such as X-22-162A, X-22-
162C (both are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.).

The compound having two or more carboxyl groups in one molecule is, for example, (1) a polyol and an acid anhydride each having two or more hydroxyl groups, preferably 2 to 50 hydroxyl groups per molecule. Esterify,
(2) A polyisocyanate compound having 2 or more, preferably 2 to 50, isocyanate groups per molecule and a hydroxycarboxylic acid or an amino acid are added.
(3) homopolymerization of a carboxyl group-containing α, β-unsaturated monomer or copolymerization with another α, β-unsaturated monomer,
(4) Obtained by a method such as synthesizing a carboxyl group-terminated polyester resin.

Examples of the polyol having two or more hydroxyl groups per molecule include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,6-hexanediol, diethylene glycol, pentanediol, dimethylbutanediol, hydrogenated bisphenol A,
Glycerin, sorbitol, neopentyl glycol,
1,8-octanediol, 1,4-cyclohexanedimethanol, 2-methyl-1,3-propanediol,
Polyhydric alcohols such as 1,2,6-hexanetriol, 1,2,4-butanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, quinitol, mannitol, trishydroxyethyl isocyanurate and dipentaerythritol; these Ring-opening adducts of polyhydric alcohols with lactone compounds such as γ-butyrolactone and ε-caprolactone; alcohols of the polyhydric alcohols with isocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate Adducts in excess; the polyhydric alcohols and ethylene glycol divinyl ether, polyethylene glycol divinyl ether, butanediol divinyl ether, pen Tandiol divinyl ether,
Adducts with vinyl ether compounds such as hexanediol divinyl ether and 1,4-cyclohexanedimethanol divinyl ether in the presence of excess alcohol; and polyhydric alcohols and alkoxy silicone compounds such as KR-213, KR-217, KR- 9218 (all are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like, and a condensate in the presence of excess alcohol can be mentioned. further,
Hydroxyl group-containing silicone oil such as X-22-160
AS, KF-6001 (both are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.).

On the other hand, examples of acid anhydrides to be reacted with these polyols include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decamethylenedicarboxylic acid, phthalic acid, maleic acid, trimellitic acid and pyromellitic acid. Mention may be made of acid anhydrides of polycarboxylic acids such as acids, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid. Examples of the polyisocyanate compound having two or more isocyanate groups per molecule include p-phenylene diisocyanate, biphenyl diisocyanate, tolylene diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 1,4- Tetramethylene diisocyanate, hexamethylene diisocyanate, 2,
2,4-trimethylhexane-1,6-diisocyanate, methylenebis (phenylisocyanate), lysine methyl ester diisocyanate, bis (isocyanatoethyl) fumarate, isophorone diisocyanate,
Examples thereof include methylcyclohexyl diisocyanate, 2-isocyanate ethyl-2,6-diisocyanate hexanoate, and their burettes and isocyanurates.

Examples of hydroxycarboxylic acids include lactic acid, citric acid, hydroxypivalic acid, 12-hydroxystearic acid and malic acid, and examples of amino acids include DL-alanine, L-glutamic acid and glycine. , L-theanine, glycylglycine, γ-aminocaproic acid, L-aspartic acid, L-
Examples thereof include citrulline, L-arginine, L-leucine and L-serine.

Further, as the carboxyl group-containing α, β-unsaturated monomer, for example, acrylic acid, methacrylic acid,
Itaconic acid, mesaconic acid, maleic acid, fumaric acid, etc. can be mentioned, and other α, β-unsaturated monomers include, for example, methyl acrylate, ethyl acrylate,
n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate , Isobutyl methacrylate, sec-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, styrene, α
-Methylstyrene, p-vinyltoluene, acrylonitrile and the like can be mentioned.

Further, the carboxyl group-terminated polyester resin can be easily formed according to a general method for synthesizing a polyester resin in a polybasic acid excess with respect to a polyhydric alcohol. The reaction of the thus obtained compound having two or more carboxyl groups in one molecule with the compound represented by the general formula (2) is usually in the range of room temperature to 100 ° C. in the presence of an acid catalyst. Performed at temperature. Further, the compound of the component (A) has a carboxyl group-containing α,
It can also be obtained by homopolymerization of a reaction product of a β-unsaturated monomer and a compound represented by the general formula (2) or copolymerization with another α, β-unsaturated monomer. . Examples of the carboxyl group-containing α, β-unsaturated monomer include acrylic acid, methacrylic acid, itaconic acid, mesaconic acid, maleic acid, fumaric acid, and the like. Other α, β-unsaturated monomers Examples of the body include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate. , N-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-
Examples thereof include butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, styrene, α-methylstyrene, p-vinyltoluene and acrylonitrile. In the curable clear coat coating composition, the compound of the component (A) may be used alone or in combination of two or more kinds.

The curable clear coat coating composition comprises
A resin containing an epoxy group is contained as the component (B). (B)
The resin containing an epoxy group of the component reacts with the chemically functionalized group of the acid type curing agent of the component (A) when the free functional group is regenerated under heating or in the presence of an acid catalyst. Those having two or more, preferably 2 to 50, epoxy groups capable of forming a chemical bond in one molecule are used. Specific examples of such epoxy group-containing resins include bisphenol type epoxy resins, alicyclic epoxy resins, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate. Homopolymers or copolymers, copolymers of glycidyl allyl ether with vinylidene fluoride and vinyl ether, polyglycidyl compounds obtained by reaction of polycarboxylic acids or polyols with epichlorohydrin, and epoxy group-containing silicone oils such as K
F-101, KF-103, KF-105, X-22-
169AS (both are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.)
Examples thereof include epoxy group-containing compounds.

In the curable clear coat coating composition, at least one selected from the above-mentioned component (A) and / or component (B) is a polymer or polyester resin of an α, β-unsaturated compound. Is preferable, and the functional group represented by the general formula (1) in the composition and the epoxy group capable of forming a chemical bond with the functional group have an equivalent ratio of 0.2: 1.
It is desirable to add each component in a ratio of 0 to 1.0: 0.2.

The functional group represented by the general formula (1) of the component (A) in the curable clear coat coating composition regenerates a free carboxyl group under heating or in the presence of an acid catalyst, and the functional group of the component (B) is regenerated. Although it forms a chemical bond with an epoxy group, in addition to this reaction, an addition reaction can occur with the epoxy group of the component (B) as a so-called active ester based on the intramolecular polarization structure. In this case, since the elimination reaction is not accompanied during the crosslinking reaction, it is possible to contribute to the reduction of the emission of volatile organic substances.

A resin containing an epoxy group is most preferably used as the component (B) in the curable clear coat coating composition used in the present invention. Instead of the resin containing an epoxy group, an epoxy group is used. Other than the above, a reactive functional group capable of forming a chemical bond by reacting with the blocked functional group represented by the general formula (1) in the compound of the component (A) when the free carboxyl group is regenerated by heating. A compound having two or more, preferably 2 to 50 in one molecule can be used. The reactive functional group is not particularly limited as long as it has the above-mentioned properties, and examples thereof include an oxazoline group, a silanol group, an alkoxysilane group, a hydroxyl group, an amino group, an imino group, an isocyanate group, and a blocked isocyanate group. Preferred are cyclocarbonate group, vinyl ether group, vinyl thioether group, aminomethylol group, alkylated aminomethylol group, acetal group, ketal group and the like. One of these reactive functional groups may be contained, or two or more thereof may be contained.

Specific examples of such a substitute compound for the component (B) include 1,2-bis (2-oxazolinyl-2).
Ethane, 1,4-bis (2-oxazolinyl-2) butane, 1,6-bis (2-oxazolinyl-2) hexane, 1,8-bis (2-oxazolinyl-2) octane, 1,4-bis ( 2-oxazolinyl-2) oxazoline compounds having an oxazoline ring bonded to an alkyl chain such as cyclohexane, 1,2-bis (2-oxazolinyl-
2) benzene, 1,3-bis (2-oxazolinyl-
2) benzene, 1,4-bis (2-oxazolinyl-
2) benzene, 5,5'-dimethyl-2,2'-bis (2-oxazolinyl-2) benzene, 4,4,4 ',
4'-tetramethyl-2,2'-bis (2-oxazolinyl-2) benzene, 1,2-bis (5-methyl-2-)
Two oxazolines in an aromatic nucleus such as oxazolinyl-2) benzene, 1,3-bis (5-methyl-2-oxazolinyl-2) benzene, and 1,4-bis (5-methyl-2-oxazolinyl-2) benzene. A ring-bonded oxazoline compound, and 2,2′-bis (2-oxazoline),
2,2'-bis (4-methyl-2-oxazoline),
Bis (2-oxazoline) compounds such as 2,2′-bis (5-methyl-2-oxazoline), polyvalent oxazoline compounds obtained by the reaction of hydroxyalkyl-2-oxazoline with the polyisocyanate compound, and further 2 -Vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2
-Oxazolines such as oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline homopolymers or copolymers Group-containing compounds, and further commercially available oxazoline group-containing compounds, for example, trade names CX-RS-1200 and CX-R
S-3200 (all manufactured by Nippon Shokubai Co., Ltd.), general formula (3)

[0045]

[Chemical formula 3] (R )_mSi (OR ’)_4-m    ... (3)

(R in the formula And R 'Has 1 carbon each
To 18 alkyl or aryl groups, m is 0, 1 or 2
Is. ) Condensates of compounds represented by
Xypropyltrimethoxysilane, methacryloyloxy
Cypropyltrimethoxysilane, methacryloyloxy
Α, β-unsaturation of propyltri-n-butoxysilane, etc.
Homopolymers or copolymers of silane compounds, and these
Silanol groups and alkoxys such as hydrolysis products of compounds
Silane group-containing compound; Aliphatic polyols, phenol
, Polyalkyleneoxy glycols, 2-hydroxy
Ciethyl acrylate, 2-hydroxyethyl methacrylate
Rate, 2-hydroxypropyl acrylate, 2-hi
Α, β-unsaturation of droxypropyl methacrylate
Compound homopolymers or copolymers, and their
Group containing hydroxyl groups such as ε-caprolactone adducts
Organic compounds: Aliphatic and aromatic diamino compounds and polyamines
No compound and cyanoethylation reaction of the polyol
Containing amino groups such as polyamino compounds obtained by reducing compounds
Compounds: imino such as aliphatic and aromatic polyimino compounds
Group-containing compound; p-phenylene diisocyanate, bif
Phenyl diisocyanate, tolylene diisocyanate,
3,3'-dimethyl-4,4'-biphenylene diisocyanate
Anate, 1,4-tetramethylene diisocyanate,
Hexamethylene diisocyanate, 2,2,4-trimethyl
Cylhexane-1,6-diisocyanate, methylenebi
Su (phenyl isocyanate), lysine methyl ester
Diisocyanate, bis (isocyanatoethyl) fumara
Rate, isophorone diisocyanate, methylcyclohexyl
Xyl diisocyanate, 2-isocyanate ethyl-
2,6-diisocyanate hexanoate and their
Burette and isocyanurate, as well as these
Adduct compound of isocyanates and the polyol
Isocyanate group-containing compounds such as the above;
Group-containing compounds phenols, lactams, active methyl
Amines, alcohols, acid amides, imides, amines
, Imidazoles, ureas, imines, oximes
Blocked products such as blocked products containing isocyanate groups
Compound; 3-acryloyloxypropylene carbon
G, 3-methacryloyloxypropylene carbonate
Homopolymer or copolymer of the above, the epoxy group-containing compound
Polycarbocarbon obtained by the reaction of carbon dioxide with carbon dioxide
Cyclocarbonate-containing compounds such as nate-group-containing compounds
Compound; the compound having a polyvalent hydroxyl group and a halogenated compound
Polyvalents obtained by reaction with ruby vinyl ethers
Vinyl ether compound, hydroxyalkyl vinyl a
Tellurides and polyvalent carboxyl group-containing compounds and the above polyiso
Polyvinyl ether obtained by reaction with cyanate compound
Ether compounds, vinyloxyalkyl acrylates,
Vinyloxyalkylmethacrylates and α, β-saturation
Vinyl ether compounds such as copolymers with solvates, and
Vinyls such as vinyl thioether compounds corresponding to these
Compounds containing ether groups and vinyl thioether groups; Melami
Formaldehyde resin, glycolyl formaldehyde
Resin, urea-formaldehyde resin, aminomethylol group
And alkylated aminomethylol group-containing α, β-desaturation
Aminomethylol groups such as compound homopolymers or copolymers
And alkylated aminomethylol group-containing compounds; polyvalent keto
And polyhydric aldehyde compounds, polyhydric vinyl ethers
For the reaction of compounds with alcohols and orthoacid esters
The resulting polyvalent acetal compounds, and these and polyacetal compounds
Condensates with liol compounds, and further vinyloxy
Alkyl acrylate and vinyloxyalkylmethacrylate
Adducts of rate with alcohols and orthoesters
Acetal group or ketal group such as homopolymer or copolymer
Including compounds and the like. R in the general formula (3)
And R As a suitable specific example of ', for example, the general formula (1)
R¹The same as the specific examples described in
It The curable clear coat coating composition should not be heated.
Thermosetting clear coat coating composition that is cured by
And a room temperature curable clear that can be cured at room temperature
There is a coating composition.

In the thermosetting clear coat coating composition, a thermal latent acid catalyst is used as the component (C), if necessary. This heat-latent acid catalyst accelerates the curing reaction during curing of the thermosetting clear coat coating composition, imparts good chemical performance, physical performance, weather resistance and stain resistance to the cured product, and It is an important component for achieving long-term stability during storage.

As the thermal latent acid catalyst of the component (C), a compound obtained by neutralizing a Bronsted acid or a Lewis acid with a Lewis base, a complex compound consisting of a Lewis acid and a Bronsted acid or a Lewis acid and a Bronsted salt, Examples include sulfonic acid esters, phosphoric acid esters, and onium compounds. The Bronsted acid constituting the thermal latent acid catalyst is a substance which dissociates protons and exhibits acidity, and sulfuric acid, sulfonic acid, phosphoric acid, boric acid, carboxylic acid and derivatives thereof are preferable. Specific examples thereof include sulfuric acid, sulfuric acid monoesters, phosphoric acid, phosphoric acid mono- and diesters, polyphosphoric acid esters, boric acid mono- and diesters, sulfonic acids, carboxylic acids, halogenocarboxylic acids, and the like, preferably dodecylbenzene. Alkylbenzene sulfonic acid having 1 to 50 carbon atoms such as sulfonic acid, 1 to 5 carbon atoms such as chloroacetic acid and dichloroacetic acid
Examples thereof include mono- or di-halogenocarboxylic acid of 0, monomethyl phosphate, dimethyl phosphate and other alkyl monoesters and diesters having 1 to 50 carbon atoms.
One of these Bronsted acids may be used,
You may combine 2 or more types. The Lewis acid constituting the above thermal latent acid catalyst is a compound exhibiting an electron accepting property, and a metal halide and an organometallic compound represented by the following general formula (4) are preferable.

[0049]

[Chemical 4]

(In the formula, R ⁵ is a halogen atom and has 1 to 1 carbon atoms.
20 alkyl groups, aryl groups, alkoxy groups, acyloxy groups, or one or more organic groups selected from carbonyl groups adjacent to an active methylene group, M is B, M
g, Al, Ca, Sn, Pb or fourth in the long periodic table
3A to 7A, 8A, 1B in the 6th cycle
N is an integer of 1 to 6, which is a transition metal atom belonging to Group 2 and Group 2B. The classification of the metal atoms constituting the Lewis acid in the long periodic table is according to the IUPAC inorganic chemistry nomenclature in 1988.

Specific examples thereof include the same as the above-mentioned Lewis acid. These Lewis acids are
They may be used alone or in combination of two or more.

The Lewis base used for neutralizing the above Bronsted acid and Lewis acid is a compound exhibiting an electron donor property, and more specifically, ammonia, triethylamine, pyridine, aniline, morpholine, N-methylmorpholine, pyrrolidine, N-methylpyrrolidine,
Piperidine, N-methylpiperidine, cyclohexylamine, n-butylamine, dimethyloxazoline, imidazole, N-methylimidazole, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dipropylethanolamine, N , N-dibutylethanolamine, N, N-dimethylisopropanolamine, N, N-diethylisopropanolamine, N, N-dipropylisopropanolamine, N,
N-dibutylisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-
Propyldiethanolamine, N-butyldiethanolamine, N-methyldiisopropanolamine, N-ethyldiisopropanolamine, N-propyldiisopropanolamine, N-butyldiisopropanolamine, triethanolamine, triisopropanolamine, tri-s-butanolamine Amines such as N,
N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, amide compounds such as hexamethylphosphoric triamide, sulfoxide compounds such as dimethyl sulfoxide, ether compounds such as diethyl ether and tetrahydrofuran, dimethyl Thioether compounds such as sulfides, phosphoric acid ester compounds such as trimethylphosphoric acid, triethylphosphoric acid and tributylphosphoric acid, boric acid ester compounds such as trimethylboric acid, carboxylic acids such as ethyl acetate and butyl acetate Examples thereof include ester compounds, carbonate ester compounds such as ethylene carbonate, and trialkylphosphine compounds such as tributylphosphine. The thermal latent acid catalyst obtained by neutralizing the above-mentioned Bronsted acid or Lewis acid with the above Lewis base has a ratio of the base activity of the Lewis base to the acid activity of each acid of 0.
It is preferably in the range of 1-10.

Examples of the sulfonic acid esters used as the thermal latent acid catalyst of the component (C) include compounds represented by the general formula (5)

[0054]

[Chemical 5]

(Wherein R ⁶ is phenyl group, substituted phenyl group, naphthyl group, substituted naphthyl group or alkyl group, R 6
⁷ is an alkyl group, an alkenyl group, an aryl group, an alkaryl group, an alkanol group having 3 to 18 carbon atoms which is bonded to a sulfonyloxy group through a primary carbon or a secondary carbon.
It is a saturated or unsaturated cycloalkyl or hydroxycycloalkyl group. ), Specifically, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, nonylnaphthalenesulfonic acid and other sulfonic acids, and n-propanol, n-butanol, Primary alcohols such as n-hexanol and n-octanol or esterified products with secondary alcohols such as isopropanol, 2-butanol, 2-hexanol, 2-octanol and cyclohexanol, and further the sulfonic acids and oxirane. Examples thereof include β-hydroxyalkyl sulfonates obtained by reaction with a group-containing compound.

Examples of the phosphoric acid esters include those represented by the general formula (6)

[0057]

[Chemical 6]

(R in the formula⁸ Is an alkyl having 3 to 10 carbon atoms
A group, a cycloalkyl group or an aryl group, r is 1 or
Is 2. ), A compound represented by
Specifically, n-propanol, n-butanol, n-hex
Sanol, n-octanol, 2-ethylhexanol
Primary alcohols such as, and isopropanol,
2-butanol, 2-hexanol, 2-octanol
And secondary alcohols such as cyclohexanol
Phosphoric acid monoesters or phosphoric acid diesters are listed.
You can In addition to these, phosphoric acid and oxirane compounds
Β-hydroxy ester compound obtained by reaction with
Can also be mentioned.

The onium compound is, for example, a compound represented by the general formula

Embedded image ((R ⁹ ) ₃ NR ¹⁰ ) ⁺ X ⁻ (7) ((R ⁹ ) ₃ PR ¹⁰ ) ⁺ X ⁻ (8) ((R ⁹ ) ₃ OR ¹⁰ ) ⁺ X ⁻ (9) ( _{^{(R 9) 3 SR 10)}} + X - (10)

(In the formula, R ⁹ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an aryl group, an alkaryl group, an alkanol group, or a cycloalkyl group, and two R 2
⁹ may be bonded to each other to form a heterocycle having N, P, O or S as a hetero atom, R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an aryl group,
Alkaryl group, X ^- is _{^{SbF - 6, AsF - 6,}} PF - 6
Or BF ^- ₄ . ) And the like.

The Bronsted salt which constitutes the complex compound of a Lewis acid and a Bronsted salt is a compound obtained by neutralizing the above-mentioned Bronsted acid with a basic substance, for example, sulfuric acid, sulfuric acid monoester, phosphoric acid, phosphoric acid. Bronsted acids such as mono- and diesters, polyphosphoric acid esters, boric acid mono- and diesters, sulfonic acids, carboxylic acids, and halogenocarboxylic acids are treated with ammonia, triethylamine, pyridine, aniline, morpholine, N-methylmorpholine, pyrrolidine, N-methyl. Pyrrolidine, piperidine, N-methylpiperidine, cyclohexylamine, n
-Butylamine, diethanolamine, triethanolamine, imidazole, various amines such as N-methylimidazole, trialkylphosphine such as tributylphosphine, compounds blocked with triarylphosphine such as triphenylphosphine, and acid-base Examples of commercially available blocked catalysts include NURECURE 2500X, 3525, 5225 (trade name, manufactured by King Industry).

The complex compound consisting of a Lewis acid and a Bronsted acid or a Lewis acid and a Bronsted salt is a complex compound having a catalytic activity of a Lewis acid, in which an empty electron orbital is coordinated with a conjugate base of the Bronsted acid or a Bronsted salt. , A complexed compound of the above-mentioned Lewis acid and the above-mentioned Bronsted acid or the above-mentioned Bronsted salt with respect to an empty electron orbit of the Lewis acid, and the molar ratio of the Bronsted acid or the Bronsted salt is 0. It can be easily obtained by mixing in the range of 1 to 4.

In the thermosetting clear coat coating composition, the heat-latent acid catalyst of the component (C) may be used alone or in combination of two or more, and the blending amount thereof is , The total solid content of the components (A) and (B) is 100
It is usually selected in the range of 0.01 to 20 parts by weight, preferably 0.02 to 10 parts by weight, per part by weight.

When the amount of the heat-latent acid catalyst is less than 0.01% by weight, the amount of the catalyst is too small and the effect of accelerating the reaction is not sufficiently exhibited. Further, the amount of the thermal latent acid catalyst is 20% by weight.
If the amount exceeds the above range, the effect of accelerating the reaction is not improved in the proportion of the amount, but rather the problem of deterioration of the physical properties of the coating film occurs due to the large amount of catalyst remaining in the thermosetting clear coat coating composition. There is a possibility that it is not preferable. Also,
As the thermal latent acid catalyst of the component (C), (a) (i) a compound containing an epoxy group, (ii) a general formula (11)

[0065]

Embedded image R ¹¹ —S—R ¹² (11)

(In the formula, R ¹¹ and R ¹² each represent a hydrogen atom or an organic group having 1 to 40 carbon atoms, which may be the same or different and may be bonded to each other to form a ring structure. .), And (iii) the general formula (12).

[0067]

_{Embedded image} (X ¹ ) _n1 −M ¹ − (R ¹³ ) _n2 (12)

(Wherein M ¹ represents boron, aluminum, tin, lead or a transition element, X ¹ represents one or more halogen atoms, and R ¹³ represents one or more carbon atoms. 1 to 40 organic groups, R ¹³ may be coordinated to the M ¹ atom to form a chelate ring, and n 1 and n 2 are each 0 to
6 is an integer, and n1 + n2 is an integer of 1 to 6. )
And a thermal latent acid catalyst comprising (iv) a carboxylic acid compound and / or a carboxylic acid anhydride compound, if necessary.

The heat-latent acid catalyst has a complex action of both (i) a compound containing an epoxy group and (ii) a sulfur-containing compound represented by the general formula (11). It is characterized by developing thermal latentity by protecting the empty electron orbit of the Lewis acid represented by the formula (12). The thermal latent acid catalyst is, in addition to the above three components, further
(Iv) A carboxylic acid compound and / or a carboxylic acid anhydride compound may be contained. The action of the carboxylic acid compound and / or the carboxylic acid anhydride compound improves the solubility in an organic solvent. That is, when an inorganic metal salt such as a halide of a transition metal is used as the Lewis acid, (i) a compound containing an epoxy group, (i)
i) a sulfur-containing compound represented by the general formula (11), (i
ii) The thermal latent acid catalyst obtained by mixing the Lewis acid represented by the general formula (12) has poor solubility in an organic solvent and has a narrow application range. And / or the thermal latent acid catalyst which is caused to act on the carboxylic acid anhydride has improved solubility in an organic solvent,
Excellent in practicality. In the thermal latent acid catalyst,
The compound used as the component (i) is a compound containing an epoxy group. The compound may be a monomolecular compound or a high molecular compound as long as it is a compound containing one or more epoxy groups in the molecule.

Examples of the epoxy group-containing compound of component (i) include aliphatic monoepoxide compounds derived from alkenes such as propylene oxide and butylene oxide, cyclohexene oxide, and ceroxide 20.
00 (trade name, manufactured by Daicel Chemical Industry Co., Ltd.), Celoxide 3000 (trade name, manufactured by Daicel Chemical Industry Co., Ltd.),
Rika Resin E-8 (trade name, manufactured by Shin Nippon Rika Co., Ltd.),
3,4-epoxycyclohexyl methyl acrylate,
Alicyclic monoepoxide compounds derived from cycloalkene such as 3,4-epoxycyclohexylmethyl methacrylate, aromatic monoepoxide compounds having an aromatic ring such as styrene oxide and stilbene oxide, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl Glycidyl ethers such as ether, butyl glycidyl ether, octyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, polyalkylene oxide monoglycidyl ether, glycidyl isobutyrate, cardura E-1
0 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.), glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, Sansocizer E-4030 (trade name, manufactured by Shin Nippon Rika Co., Ltd.), Sansocizer E-600
0 (trade name, manufactured by Shin Nippon Rika Co., Ltd.), an epoxy-based plasticizer, a homopolymer of a monomer such as glycidyl acrylate, allyl glycidyl acrylate, or a copolymer with another monomer, Bisphenol type epoxy resin,
Examples thereof include polymer compounds having an epoxy group such as polyglycidyl compounds obtained by the reaction of polycarboxylic acid and epichlorohydrin or polyol and epichlorohydrin. Of these, particularly preferred are propylene oxide, butylene oxide, Sansocizer E-4030 (trade name, manufactured by Shin Nippon Rika Co., Ltd.),
Sanso Sizer E-6000 (trade name, manufactured by Shin Nippon Rika Co., Ltd.), Lycarezin E-8 (trade name, manufactured by Shin Nippon Rika Co., Ltd.), cyclohexene oxide, celoxide 3
000 (trade name, manufactured by Daicel Chemical Industries, Ltd.), methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether,
Examples include Cardura E-10 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.). Glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethylmethacrylate homopolymer or copolymer with other monomers are also particularly preferred. . Here, when the compound containing an epoxy group is a polymer compound, the epoxy content is preferably in the range of 0.1 to 7 mol / kg, and particularly preferably in the range of 0.35 to 5 mol / kg. (I) The epoxy group-containing compound may be used alone or in combination of two or more.

The compound used as the component (ii) in the thermal latent acid catalyst is a sulfur-containing compound represented by the general formula (11). In the general formula (11), R ¹¹
And R ¹² each represent a hydrogen atom or an organic group having 1 to 40 carbon atoms, which may be the same or different and may be bonded to each other to form a ring structure. Preferred organic groups are those having 1 to 18 carbon atoms, and particularly preferred are organic groups having 1 to 10 carbon atoms. Examples of the organic group include an alkyl group, an aryl group, an alkaryl group,
Examples thereof include organic groups such as alkoxyl group, acyl group, acyloxyl group or alkoxycarbonyl group, functional groups such as hydroxyl group, amino group, nitrile group and carboxyl group, and those obtained by substituting the organic group with these functional groups. .

Suitable specific examples of the alkyl group, aryl group and alkaryl group are the same as the specific examples described for R ¹ in the general formula (1). Specific examples of suitable alkoxyl groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, pentyloxy, hexyloxy groups, and the like, preferably methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert.
A butoxy group.

Specific examples of suitable acyl groups include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, oxalyl, succinyl, bivaloyl, stearoyl, benzoyl, phenylpropionyl, toluoyl, naphthoyl, phthaloyl,
Examples thereof include indancarbonyl, p-methoxybenzoyl, cyclohexylcarbonyl group, and the like, with preference given to acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, oxalyl, benzoyl and cyclohexylcarbonyl groups.

Specific examples of suitable acyloxyl groups include acetoxy, propionyloxy, butanoyloxy, isobutanoyloxy, hexanoyloxy, octanoyloxy, 2-ethylhexanoyloxy, decanoyloxy, dodeca. Noyloxy, stearoyloxy, benzoyloxy, naphthoyloxy, cyclopentylcarbonyloxy, cyclohexylcarbonyloxy, furoyloxy, senoyloxy and the like, preferably acetoxy, propionyloxy,
Butanoyloxy, hexanoyloxy, octanoyloxy, 2-ethylhexanoyloxy, benzoyloxy and cyclohexylcarbonyloxy groups.

Specific examples of suitable alkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, 1-cyclopropylethoxycarbonyl. , Cyclohexyloxycarbonyl and the like, and preferably methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, tert-butoxycarbonyl and cyclohexyloxycarbonyl groups.

Suitable specific examples of the (ii) sulfur-containing compound include, for example, methyl sulfide, ethyl sulfide,
n-propyl sulfide, n-butyl sulfide, n-
Hexyl sulfide, isopropyl sulfide, sec
-Butyl sulfide, tert-butyl sulfide, n
-Alkyl sulfides such as octyl sulfide and 2-ethylhexyl sulfide, hydroxyalkyl sulfides such as 2- (ethylthio) ethanol, 2,2'-thiodiethanol and bis (2-methoxyethyl) sulfide, and their derivatives, diphenyl sulfide and thiol Sulfur-containing compounds having an aromatic ring such as anisole, methyl-containing thioacetate compounds such as methylthioacetate, ethyl methylthiopropionate and dimethylthiodipropionate, and sulfur-containing compounds containing nitrile groups such as thiodipropionitrile , Tetrahydrothiophene, tetrahydrothiapyran, 1,2-oxathiolane, 1,3-oxathiolane, 1,3-oxathiane,
Examples include cyclic sulfur-containing compounds such as 1,4-oxathiane, preferably n-propyl sulfide and n-
Butyl sulfide, n-hexyl sulfide, isopropyl sulfide, sec-butyl sulfide, tert
-Butyl sulfide, n-octyl sulfide, alkyl sulfides such as 2-ethylhexyl sulfide and 2- (ethylthio) ethanol, bis (2-methoxyethyl) sulfide, methyl methylthioacetate, ethyl methylthiopropionate, tetrahydrothiophene, 1,
4-oxathian is mentioned. The sulfur-containing compound (ii) may be used alone or in combination of two or more.

In the thermal latent acid catalyst, the compound used as the component (iii) is the Lewis acid represented by the general formula (12). In the general formula (12), M ¹ represents boron, aluminum, tin, lead or a transition element,
X ² represents one or more halogen atoms, R ¹³ represents one or more organic groups having 1 to 40 carbon atoms, R ^13
13 may coordinate to the M ¹ atom to form a chelate ring, and n
1 and n2 each represent an integer of 0 to 6, and n1 + n2
Is an integer of 1 to 6.

The transition element is an atom belonging to groups 3 to 12 of the 4th to 6th periods in the new periodic table of IUPAC, specifically, scandium, yttrium, lanthanoid, titanium, zirconium, hafnium, Vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc,
Cadmium and mercury. Preferred M ¹ is boron, aluminum, tin, lead, titanium, zinc, iron, copper,
Zirconium, particularly preferably aluminum, tin, titanium, zinc or zirconium.

Examples of the halogen atom for X ² include fluorine, chlorine, bromine and iodine, preferably fluorine,
Chlorine and bromine. Preferred organic groups for R ¹³ are
An organic group having 1 to 18 carbon atoms, particularly preferred is
It is an organic group having 1 to 10 carbon atoms. As this organic group,
Examples thereof include an alkyl group, an aryl group, an alkaryl group, an alkoxyl group, an acyl group, an acyloxyl group and an alkoxycarbonyl group, and preferably an alkyl group, an alkoxyl group, an acyl group or an acyloxyl group.

Suitable specific examples of the alkyl group, aryl group and alkaryl group are the same as the specific examples described for R ¹ in the general formula (1). Suitable specific examples of the alkoxyl group, acyl group, acyloxyl group and alkoxycarbonyl group include the same as the specific examples described for R ¹¹ in the general formula (11).

Suitable specific examples of the (iii) Lewis acid include, for example, boron trifluoride, aluminum trichloride, titanium chloride, ferric chloride, ferrous chloride, ferric chloride, zinc chloride, Metal halides such as zinc bromide, stannous chloride, stannic chloride, stannous bromide, stannic bromide, trialkylboron, trialkylaluminum,
Organometallic compounds such as aluminum dialkyl halides, aluminum monoalkyl halides, tetraalkyl tin, aluminum diisopropoxyethylacetoacetate, aluminum tris (ethylacetoacetate), aluminum isopropoxybis (ethylacetoacetate), monoacetylacetonate -Bis (ethyl acetoacetate) aluminum, tris (n-propyl acetoacetate) aluminum, tris (n-
Butylacetoacetate) aluminum, monoethylacetoacetate bis (acetylacetonato) aluminum, tris (acetylacetonato) aluminum, tris (propionylacetonato) aluminum, acetylacetonato bis (propionylacetonato) aluminum, diisopropoxy Bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetonato) titanium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetonato) zirconium, tetrakis (ethylacetoacetate) zirconium, dichlorobis (Acetylacetonato) tin, dibutylbis (acetylacetonato) tin, Tris (acetylacetonato) iron, Tris (acetylacetona) ) Chromium, tris (acetylacetonato) rhodium, bis (acetylacetonato) zinc,
Metal chelate compounds such as tris (acetylacetonato) cobalt, dibutyltin dilaurate, dioctyltin ester malate, magnesium naphthenate, calcium naphthenate, manganese naphthenate, iron naphthenate,
Cobalt naphthenate, copper naphthenate, zinc naphthenate,
Zirconium naphthenate, lead naphthenate, calcium octylate, manganese octylate, iron octylate, cobalt octylate, zinc octylate, zirconium octylate, tin octylate, lead octylate, zinc laurate,
Magnesium stearate, aluminum stearate, calcium stearate, cobalt stearate,
Examples include metal soaps such as zinc stearate and lead stearate. Among these, preferred are chelate compounds of boron, aluminum, tin, titanium, zinc and zirconium, metal soaps, and halides. Furthermore, when a carboxylic acid compound and / or a carboxylic acid anhydride compound is not used, a chelate compound of boron, aluminum, tin, titanium, zinc and zirconium and a metal soap are particularly preferable from the viewpoint of solubility in an organic solvent. To be The Lewis acid (iii) may be used alone or in combination of two or more.

Suitable specific examples of the (iv) carboxylic acid compound used in the thermal latent acid catalyst include acetic acid, propionic acid, butyric acid, 2-ethylhexylic acid, lauric acid, stearic acid, oleic acid, linoleic acid, Monovalent carboxylic acid compounds such as linolenic acid, acrylic acid, methacrylic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decamethylenedicarboxylic acid, phthalic acid, maleic acid Acids, trimetic acid, pyromettic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, itaconic acid, mesaconic acid, fumaric acid and other polyvalent carboxylic acid compounds, and carboxyl group-containing acrylic resin, carboxyl group-containing polyester Resin etc. are mentioned. Among these, monovalent or polyvalent carboxylic acid compounds having a relatively low molecular weight are preferable, and monovalent or polyvalent carboxylic acid compounds having a molecular weight of 3000 or less are particularly preferable.

Suitable specific examples of the (iv) carboxylic acid anhydride compound used in the thermal latent acid catalyst are acetic anhydride and
Propionic anhydride, butyric anhydride, isobutyric anhydride, lauric anhydride, oleic anhydride, linoleic anhydride, stearic anhydride, linolenic anhydride, succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyro Mellitic acid, isovaleric anhydride, n-caproic anhydride, n-caprylic anhydride, n-capric anhydride, citraconic anhydride, glutaric anhydride, itaconic anhydride, chlorendic anhydride, palmitic anhydride, myristic anhydride, Tetrapropenyl succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic acid, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrachlorophthalic anhydride, anhydrous 3 -Ditrophthalic acid, trichloroacetic anhydride, Lolo acetic anhydride monochloroacetic acid,
Examples thereof include low molecular weight carboxylic acid anhydride compounds such as trifluoroacetic anhydride and heptafluorobutyric acid anhydride, and high molecular weight carboxylic acid anhydride compounds such as carboxyl group-containing acrylic resin and carboxyl group-containing polyester resin.

Of these, particularly preferred are acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride,
Lauric anhydride, oleic anhydride, stearic anhydride,
Examples include n-caproic anhydride, n-caprylic anhydride, n-capric anhydride, palmitic anhydride, myristic anhydride, trichloroacetic anhydride, dichloroacetic anhydride, monochloroacetic anhydride, trifluoroacetic anhydride, and heptafluorobutyric anhydride. To be The improvement of the solubility of the (iv) carboxylic acid compound and carboxylic acid anhydride compound in an organic solvent is remarkable when the Lewis acid is a metal halide. The (iv) carboxylic acid compound and the carboxylic acid anhydride compound may be used alone or in combination of two or more kinds.

The mixing ratio of each component for producing the thermal latent acid catalyst is not particularly limited, but M ^{1 of the} Lewis acid represented by the general formula (12), which is the component (iii), is used. The equivalent ratio of the epoxy group of the compound containing the epoxy group of the component (i) to the atom and the sulfur atom of the sulfur-containing compound of the component (ii) is preferably in the range of 0.2 to 10, It is preferably in the range of 0.5 to 5, respectively. If this equivalent ratio is less than 0.2, the activity of the Lewis acid may not be sufficiently suppressed during storage. Further, if the equivalent ratio exceeds 10, it may be difficult to generate a catalyst during heating. Further, in the thermal latent acid catalyst, the carboxyl group and / or carboxylic acid anhydride of the carboxylic acid compound which is the component (iv) with respect to the M ¹ atom of the Lewis acid represented by the general formula (12) which is the component (iii) The equivalent ratio of the acid anhydride group of the compound is not particularly limited, but is preferably in the range of 0.05 to 10, and particularly preferably in the range of 0.1 to 5. When this equivalent ratio is less than 0.05, the thermal latent acid catalyst may have insufficient solubility in an organic solvent. Also,
If this equivalent ratio exceeds 10, the activity of the Lewis acid may not be sufficiently suppressed during storage.

The thermolatent acid catalyst is (i) a compound containing an epoxy group in the presence or absence of a solvent, (ii)
It can be easily produced by mixing the respective components of the sulfur-containing compound and the (iii) Lewis acid in any order. Among these, (i) a compound containing an epoxy group and (ii) a sulfur-containing compound are mixed in advance, and then (iii) a Lewis acid is mixed, or (ii) a sulfur-containing compound and (iii) a Lewis acid are mixed. A manufacturing method in which (i) a compound containing an epoxy group is mixed after being mixed in advance is preferable. Further, the order of mixing the (iv) carboxylic acid compound and / or the carboxylic acid anhydride compound can be arbitrarily set. Among these,
(I) a compound containing an epoxy group, (ii) a sulfur-containing compound, and (iii) a Lewis acid are mixed in advance,
(Iv) It is preferable to mix the carboxylic acid compound and / or the carboxylic acid anhydride compound. Furthermore, in the production of the heat-latent acid catalyst, after mixing two components, three components, and optionally four components or five components, and then heating at room temperature to 100 ° C. for 10 minutes to 10 hours It may be preferable because the thermal latent reaction of the acid is promoted more. Examples of the solvent used here include an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, an ether solvent, an alcohol solvent, an ester solvent, a ketone solvent, and a mixed solvent thereof. The amount of the solvent used may be appropriately selected, but it is usually preferable to set the thermal latent acid catalyst to 1 to 90% by weight.

In the thermal latent acid catalyst, the thermal latentizing action of (iii) the compound containing an epoxy group and (iii) the sulfur-containing compound with respect to a Lewis acid is complicated, but for example, oxygen of the epoxy group is used. The effect of both the unshared electron pair of the atom and the unshared electron pair of the sulfur atom of the sulfur-containing compound suggests the mechanism by which the thermal potential is developed by protecting the empty electron orbit of the Lewis acid. Further, the action of (iv) the carboxylic acid compound and the carboxylic acid anhydride compound to significantly improve the solubility of the thermal latent acid catalyst in an organic solvent is, for example, by reacting with the thermal latent acid catalyst,
The mechanism of development is presumed from the change of the ligand of the thermal latent acid catalyst or a part thereof. Furthermore, it is presumed that the thermal latent acid catalyst decomposes to regenerate the Lewis acid under heating. By this mechanism, the thermolatent acid catalyst exhibits acid catalytic activity only when heated.

The heat-latent acid catalyst as the component (C) keeps the storage stability of the thermosetting clear coat coating composition good for a long period of time and accelerates the curing reaction when it is cured at a low temperature in a short time. However, it is used for the purpose of imparting good chemical performance and physical performance to the cured product. Therefore, the thermal latent acid catalyst is preferably a compound that exhibits acid catalytic activity at a temperature of 50 ° C. or higher. When the heat-latent acid catalyst exhibits an acid catalytic activity at a temperature lower than 50 ° C., the resulting composition may cause an undesirable situation such as thickening or gelation during storage. The thermal latent acid catalyst is (i) a compound containing an epoxy group, (ii) a sulfur-containing compound, (ii)
By changing the type and amount of each of i) a Lewis acid and (iv) a carboxylic acid compound and / or a carboxylic acid anhydride compound used as necessary, the temperature at which the acid catalytic activity is exhibited can be relatively easily obtained. You can control. In the thermosetting clear coat coating composition, the thermal latent acid catalyst of the component (C) may be used alone or in combination of two or more, and the blending amount thereof is (A ) Component and (B) component, based on 100 parts by weight of the total solid content, the Lewis acid is usually in the range of 0.01 to 20 parts by weight, preferably 0.0.
It is selected so as to be compounded in the range of 2 to 10 parts by weight.

When the amount of the heat-latent acid catalyst is less than 0.01% by weight, the amount of the catalyst is too small and the effect of accelerating the reaction is not sufficiently exhibited. Further, the amount of the thermal latent acid catalyst is 20% by weight.
If the amount exceeds the above range, the effect of accelerating the reaction is not improved in terms of the amount, but rather the physical properties of the coating film may be deteriorated due to the large amount of catalyst remaining in the thermosetting clear coat coating composition, which is preferable. Absent.

Further, as the thermal latent acid catalyst of the component (C) in the above-mentioned thermosetting clear coat coating composition,
(B) (v) General formula (13)

[0091]

[Chemical 10]

(Y ² in the formula represents a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom, and R ¹⁴ is selected from an alkyl group, an alkenyl group, an aryl group, an alkaryl group or an alkanol group having 1 to 12 carbon atoms. And two R ^14's may combine with each other to form a heterocycle having Y ² as a heteroatom, and n3 represents an integer of 2 or 3.). A nitrogen-containing, oxygen, phosphorus or sulfur compound represented by (vi) the general formula (14)

[0093]

[Chemical 11]

(In the formula, R ¹⁵ is a benzyl group having 1 to 12 carbon atoms, a substituted benzyl group, an allyl group, a substituted allyl group, a cycloalkyl group, a substituted cycloalkyl group, a secondary alkyl group, a substituted secondary alkyl group. Group, an organic group selected from a tertiary alkyl group or a substituted tertiary alkyl group, and X ² represents a halogen atom), and (vii) a general formula (15)

[0095]

[Chemical 12]

(M in the formula² Is aluminum atom, zinc atom
Represents a child or tin atom, X³Is one or more than one halo
Indicates a gen atom, R¹⁶Is 1 or 2 or more carbon atoms 1 to
20 organic groups, R¹⁶Is M²Chelate by coordinating to an atom
A ring may be formed, and n4 and n5 are each 0 to 6
An integer is shown and n4 + n5 shows an integer of 1-6. )
Containing aluminum, zinc or tin atoms
Thermally latent acid catalysts consisting of Lewis acids can be used
It

In the thermal latent acid catalyst, the compound used as the component (v) is a nitrogen-containing, oxygen, phosphorus or sulfur compound represented by the general formula (13). In the general formula (13), Y ² is a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom, and R ¹⁴ is an alkyl group, an alkenyl group, an aryl group, an alkaryl group or an alkanol group having 1 to 12 carbon atoms. One or two or more kinds of selected organic groups, which may have an appropriate substituent, and two R ^14's are bonded to each other to form a hetero atom having Y ² as a hetero atom. You may form a ring. Further, n3 is an integer of 2 or 3. Preferred values for R ¹⁴ include
An alkyl group, an alkenyl group, an aryl group, an alkaryl group, and an alkanol group having 1 to 10 carbon atoms are preferable, and an alkyl group, an aryl group, and an alkanol group are particularly preferable.

Suitable specific examples of the above alkyl group, aryl group and alkaryl group include, for example, 1 to 1 carbon atoms.
The same specific examples as those described for R ¹ in the general formula (1) of 2 are mentioned. As the alkenyl group, vinyl, allyl, isopropenyl, 2-butenyl, 2-methylallyl, 1,1-dimethylallyl, 3-methyl-2.
-Butenyl, 3-methyl-3-butenyl, 4-pentenyl, hexenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl group and the like can be mentioned, preferably vinyl, allyl, isopropenyl having 2 to 10 carbon atoms,
Alkenyl groups such as 2-butenyl, 2-methylallyl, 1,1-dimethylallyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 4-pentenyl, hexenyl, octenyl, nonenyl and decenyl groups can be mentioned. .

Specific examples of suitable alkanol groups include hydroxymethyl, 2-hydroxyethyl,
2-hydroxypropyl, 3-hydroxypropyl, 4
-Hydroxybutyl, 2-hydroxybutyl, 2,2-
Dimethyl-2-hydroxyethyl, 5-hydroxypentyl, 6-hydroxyhexyl, 7-hydroxyheptyl, 8-hydroxyoctyl, 9-hydroxynonyl,
Examples thereof include 10-hydroxydecyl, 11-hydroxyundecyl, and 12-hydroxydodecyl groups, and preferably C1-C10 hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxy. Alkanols such as butyl, 2-hydroxybutyl, 2,2-dimethyl-2-hydroxyethyl, 5-hydroxypentyl, 6-hydroxyhexyl, 7-hydroxyheptyl, 8-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl. Groups.

The substituent for substituting these organic groups is not particularly limited, and examples thereof include a halogen atom, a lower alkyl group, a lower alkoxyl group, an aryloxy group, a lower haloalkyl group, an acyloxyl group, an acylamino group, a hydroxyl group, Examples thereof include a nitro group.

Specific examples of the compound as the component (v) include, for example, trimethylamine, triethylamine,
Tri-n-butylamine, triallylamine, dimethyl-n-octylamine, dimethylbenzylamine, triethanolamine, pyridine, 2-picoline, 3-picoline, 4-picoline, N-methylpiperidine, N-methylpyrrolidine, N- Various tertiary amines such as methylimidazole and N-methylmorpholine, diethyl ether,
Di-n-butyl ether, anisole, diphenyl ether, benzyl ethyl ether, dibenzyl ether,
Various ethers such as 1,4-dioxane, 1,3,5-trioxane, furan, tetrahydrofuran and tetrahydropyran, various phosphines such as tributylphosphine, tricyclohexylphosphine and triphenylphosphine, diethyl sulfide, dipropyl sulfide, di -N-butyl sulfide, di-sec-butyl sulfide, di-tert-butyl sulfide, diisobutyl sulfide, di-n-hexyl sulfide, di-n
-Octyl sulfide, methyl-n-octyl sulfide, 2,2'-thiodiethanol, bis (2-methoxyethyl) sulfide, 2- (ethylthio) ethanol,
Methyl methyl thioacetate, ethyl methyl thiopropionate, dimethyl thiodipropionate, thiodipropionitrile, thioanisole, diphenyl sulfide, 1,4
-Thioxane, thiophene, tetrahydrothiophene,
Examples include various sulfides such as tetrahydrothiopyran. One of these compounds may be used, or 2
You may use it in combination of 2 or more types.

In the heat-latent acid catalyst, (vi)
The compound used as the component is a halogen-containing compound represented by the general formula (14). The general formula (14)
Wherein R ¹⁵ is an organic group selected from a benzyl group having 1 to 12 carbon atoms, an allyl group, a cycloalkyl group, a secondary alkyl group or a tertiary alkyl group, and these organic groups have an appropriate substituent. You may have. X ² is a halogen atom, specifically fluorine, chlorine, bromine, iodine or the like. R ¹⁵ preferably has 1 to 1 carbon atoms.
10 benzyl group, substituted benzyl group, allyl group, substituted allyl group, cycloalkyl group, substituted cycloalkyl group, secondary alkyl group, substituted secondary alkyl group, tertiary alkyl group or substituted tertiary alkyl group And particularly preferred are benzyl group, substituted benzyl group, allyl group, substituted allyl group, cycloalkyl group and substituted cycloalkyl group.

Suitable specific examples of the above cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 2-hydroxycyclohexyl. , 3-hydroxycyclohexyl, 4-hydroxycyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl group and the like, preferably cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 3-methyl having 3 to 10 carbon atoms. Cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 2-hydroxycyclohexyl, 3-hydroxycyclohexyl, 4-hydroxycyclohexyl Sill, cyclooctyl, a cycloalkyl group such as cyclodecyl.

Specific examples of suitable secondary alkyl groups include, for example, isopropyl, sec-butyl, 1-methylbutyl, 1-methylpentyl, 1-methylheptyl,
1-Ethylpropyl, 1-methylisobutyl, 1-methylisopentyl, 1-methylhexyl, 1-methylheptyl, 1-methyloctyl, 1-ethyl-3-methylbutyl and the like can be mentioned. Specific examples of suitable tertiary alkyl groups include tert-butyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl and 1,1-
Dimethylpentyl, 1,1-dimethylhexyl, 1,1
-Dimethylheptyl, 1,1-dimethyloctyl, 1-
Ethyl-1-methylpropyl and the like can be mentioned. Substituents substituting these organic groups are not particularly limited, for example, halogen atom, lower alkyl group, lower alkoxyl group, aryloxyl group, lower haloalkyl group,
Examples thereof include an acyloxyl group, an acylamino group, a hydroxyl group, and a nitro group.

Specific examples of the component (vi) include:
For example, benzyl chloride, 4- (tert-butyl)
Benzyl chloride, 3-methoxybenzyl chloride, 4-methoxybenzyl chloride, 2-methylbenzyl chloride, 3-methylbenzyl chloride, 4-
Methylbenzyl chloride, 3-vinylbenzyl chloride, 4-vinylbenzyl chloride, 2-chlorobenzyl chloride, 3-chlorobenzyl chloride, 4-
Chlorobenzyl chloride, 2-nitrobenzyl chloride, 3-nitrobenzyl chloride, 4-nitrobenzyl chloride, 2,3-dichlorobenzyl chloride, 2,4-dichlorobenzyl chloride, 2,6-dichlorobenzyl chloride, 3,4- Dichlorobenzyl chloride, α, α′-dichloroparaxylene, allyl chloride, 1-chloro-2-butene, 1-chloro-3
-Methyl-2-butene, cyclobutyl chloride, cyclopentyl chloride, cyclohexyl chloride, 2
-Chlorocyclohexanol, 2-chlorocyclohexanone, isopropyl chloride, sec-butyl chloride, chlorinated compounds such as tert-butyl chloride, benzyl bromide, 2-bromobenzyl bromide, 3-bromobenzyl bromide, 4-bromobenzyl bromide, 2-nitrobenzyl bromide, 3-nitrobenzyl bromide, 4-nitrobenzyl bromide, allyl bromide, 1-bromo-2-butene, 1-
Bromine-containing compounds such as bromo-3-methyl-2-butene, cyclobutyl bromide, cyclopentyl bromide, cyclohexyl bromide, isopropyl bromide, sec-butyl bromide, tert-butyl bromide, allyl iodide, cyclohexyl iodide, isopropyl iodide , Sec-butyl iodide, tert-butyl iodide, and other iodine-containing compounds, and the corresponding fluorine-containing compounds. One of these compounds may be used, or 2
You may use it in combination of 2 or more types.

Further, in the thermal latent acid catalyst, (vi
The compound used as the component i) has the general formula (1)
It is a Lewis acid containing an aluminum atom, a zinc atom or a tin atom represented by 5). In the general formula (15), M ² is an aluminum atom, a zinc atom or a tin atom, X ³ is one kind or two or more kinds of halogen atoms,
R ¹⁶ is one or more organic groups having 1 to 20 carbon atoms, R ¹⁶ may be coordinated with M ² atom to form a chelate ring, and n 4 and n 5 are each an integer of 0 to 6. And n4
+ N5 is an integer of 1-6. Preferred organic groups for R ¹⁶ are organic groups having 1 to 18 carbon atoms, and particularly preferred are organic groups having 1 to 10 carbon atoms.

Examples of the organic group include an alkyl group,
An aryl group, an alkaryl group, an acyl group, an alkoxycarbonyl group, an alkoxyl group, an acyloxyl group and the like can be mentioned, preferably an alkyl group, an alkoxyl group,
Examples thereof include an acyl group and an acyloxyl group. Suitable specific examples of the alkyl group, aryl group and alkaryl group include the same as the specific examples described for R ¹ in the general formula (1). Suitable specific examples of the alkoxyl group, acyl group, acyloxyl group and alkoxycarbonyl group include the same as the specific examples described for R ¹¹ in the general formula (11). Examples of the halogen atom for X ³ include fluorine, chlorine, bromine, iodine and the like.

Specific examples of the component (vii) include aluminum trifluoride, aluminum trichloride, aluminum tribromide, aluminum triiodide, trialkylaluminum, dialkylaluminum halide, monoalkylaluminum halide. , Diisopropoxyethylacetoacetate aluminum, isopropoxybis (ethylacetoacetate) aluminum, tris (ethylacetoacetate) aluminum,
Acetylacetonato bis (ethylacetoacetate) aluminum, ethylacetoacetate bis (acetylacetonato) aluminum, tris (acetylacetonato) aluminum, tris (n-propylacetoacetate) aluminum, tris (n-butylacetoacetate) aluminum, Aluminum-containing compounds such as tris (propionylacetonato) aluminum, acetylacetonatobis (propionylacetonato) aluminum and aluminum stearate, zinc fluoride, zinc chloride, zinc bromide, zinc iodide, bis (acetylacetonato) Zinc-containing compounds such as zinc, zinc naphthenate, zinc octylate, zinc laurate and zinc stearate, stannous fluoride, stannous chloride, stannic chloride, stannous bromide, stannic bromide Tin, yo Of stannous, tetraalkyl tin, dichlorobis (acetylacetonato) tin, dibutylbis (acetylacetonato) tin, dibutyltin dilaurate, dioctyltin ester maleate, tin-containing compounds such as tin octylate and the like. These compounds may be used alone or in combination of two or more.

The thermal latent acid catalyst is (v) the above-mentioned nitrogen-containing,
An oxygen, phosphorus or sulfur compound (vi) a halogen-containing compound and (vii) a Lewis acid containing an aluminum atom, a zinc atom or a tin atom, wherein the thermal latent acid catalyst has the general formula (16)

[0110]

[Chemical 13]

(Wherein M ² , X ² , X ³ , Y ² , R ¹⁴ ,
R ¹⁵ , R ¹⁶ , n3, n4 and n5 have the same meanings as described above. Moreover, s shows the integer of 1-3. ) It is presumed to be a compound having a structure represented by and / or a mixture thereof. That is, the thermal latent acid catalyst is an onium compound characterized in that an anion contains an aluminum atom, a zinc atom or a tin atom. These do not show acid catalytic activity at temperatures near room temperature, but they decompose by heating,
A Lewis acid containing an aluminum atom, a zinc atom or a tin atom is regenerated to exhibit acid catalytic activity. Further, the thermal latent acid catalyst is characterized by producing a relatively stable carbocation such as benzyl cation, allyl cation, secondary carbocation or tertiary carbocation upon thermal decomposition. This is necessary to bring the thermal decomposition temperature of the heat-latent acid catalyst to a relatively low temperature, and to show the acid-catalytic activity of the heat-latent acid catalyst at a relatively low temperature. This is why the halogen-containing compound as the component (vi) is particularly limited as described above.

The mixing ratio of the respective components in the production of the thermal latent acid catalyst is not particularly limited, but the aluminum atom represented by the general formula (15) which is the component (vii),
A nitrogen-containing compound represented by the general formula (13) which is a component (v) with respect to M ² atom of a Lewis acid containing a zinc atom or a tin atom,
Y ² atom of oxygen, phosphorus or sulfur compound and X of halogen-containing compound represented by the general formula (14) which is the component (vi).
The equivalent ratio of ^two atoms is preferably in the range of 0.5 to 10, and particularly preferably in the range of 1 to 5, respectively. In addition, the mixing order of the respective components when producing the thermal latent acid catalyst is not particularly limited, each component may be added and mixed at the same time, first (v) nitrogen-containing, oxygen,
General formula (17) comprising a phosphorus or sulfur compound and (vi) a halogen-containing compound

[0113]

[Chemical 14]

An onium compound having a halogen anion represented by the formula (wherein X ² , Y ² , R ¹⁴ , R ¹⁵ and n3 have the same meanings as described above) was prepared, and then (vii) an aluminum atom. Alternatively, a Lewis acid containing a zinc atom or a tin atom may be added and mixed. Further, in the production of the heat-latent acid catalyst, after mixing two or three components, the temperature is from room temperature to 1
Heating in the range of 00 ° C. for 10 minutes to 10 hours may be preferable because the thermal latent reaction of the Lewis acid is further promoted.
When producing the thermal latent acid catalyst, it may be in the presence or absence of a solvent. Examples of the solvent used here include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, ether solvents, alcohol solvents, ester solvents, ketone solvents and mixed solvents thereof. The amount of the solvent used may be appropriately selected, but it is usually preferable to set the thermal latent acid catalyst to 1 to 80% by weight.

The heat-latent acid catalyst as the component (C) keeps the storage stability of the thermosetting clear coat coating composition good for a long period of time, and accelerates the curing reaction when curing at low temperature for a short time. However, it is used for the purpose of imparting good chemical performance and physical performance to the cured product. Therefore, the thermal latent acid catalyst is preferably a compound that exhibits acid catalytic activity at a temperature of 50 ° C. or higher. When the heat-latent acid catalyst exhibits an acid catalytic activity at a temperature lower than 50 ° C., the resulting composition may cause an undesirable situation such as thickening or gelation during storage. The thermal latent acid catalyst is (v) each component of nitrogen-containing, oxygen, phosphorus or sulfur compound (vi) halogen-containing compound, and (vii) type of Lewis acid containing aluminum atom, zinc atom or tin atom. By changing the amount and the amount, the temperature at which the acid catalytic activity is exhibited can be controlled relatively easily. In the thermosetting clear coat coating composition, the thermal latent acid catalyst of the component (C) may be used alone or in combination of two or more, and the blending amount thereof is (A ) Component and (B) component total solid content 100
The Lewis acid is usually added in an amount of 0.01 to 20 parts by weight, preferably 0.02 to 10 parts by weight, based on parts by weight.

If the amount of the heat-latent acid catalyst is less than 0.01% by weight, the amount of the catalyst is too small and the effect of promoting the reaction cannot be sufficiently exhibited. Further, the amount of the thermal latent acid catalyst is 20% by weight.
If the amount exceeds the above range, the effect of accelerating the reaction is not improved in terms of the amount, but rather the physical properties of the coating film may be deteriorated due to the large amount of catalyst remaining in the thermosetting clear coat coating composition, which is preferable. Absent.

Further, as the component (C) in the thermosetting clear coat coating composition, (c) (viii) a metal chelate compound and (ix) the general formula (18)

[0118]

[Chemical 15]

(In the formula, R ¹⁷ is an alkyl group having 1 to 18 carbon atoms, an aryl group or an alkenyl group, R ¹⁸ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group or an alkaryl group, R ¹⁹ and R ²⁰ is an alkyl group or aryl group having 1 to 18 carbon atoms, and n 6, n 7, n 8 and n 9 are 0 to 4
Is an integer of n6 + n7 + n8 + n9 = 4. A mixture with an organosilicon compound represented by the formula) or a condensate thereof can be used.

Examples of the (viii) metal chelate compound as the component (C) include diisopropoxyethylacetoacetate aluminum, tris (ethylacetoacetate) aluminum, isopropoxybis (ethylacetoacetate) aluminum, and monoacetylacetonato bis. (Ethyl acetoacetate) aluminum, tris (n-propyl acetoacetate) aluminum, tris (n-
Aluminum chelates such as butylacetoacetate) aluminum, monoethylacetoacetate bis (acetylacetonato) aluminum, tris (acetylacetonato) aluminum, tris (propionylacetonato) aluminum, and acetylacetonato bis (propionylacetonato) aluminum. Compounds; titanium chelate compounds such as diisopropoxy bis (ethylacetoacetate) titanium and diisopropoxy bis (acetylacetonato) titanium; tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetonato) zirconium Zirconium chelate compounds such as zirconium, tetrakis (ethylacetoacetate), and dichlorobis (acetate) are preferred. Ruasetonato) tin, dibutyl
Bis (acetylacetonato) tin, tris (acetylacetonato) iron, tris (acetylacetonato) chromium,
Examples also include tris (acetylacetonato) rhodium, bis (acetylacetonato) zinc, tris (acetylacetonato) cobalt and the like.

Of these metal chelate compounds, particularly preferred are diisopropoxyethylacetoacetate aluminum, tris (ethylacetoacetate) aluminum, isopropoxybis (ethylacetoacetate) aluminum, monoacetylacetonato bis (ethylacetoacetate). Acetate) Aluminum, Tris (n
-Propylacetoacetate) aluminum, tris (n-butylacetoacetate) aluminum, monoethylacetoacetate bis (acetylacetonato) aluminum, tris (acetylacetonato) aluminum, tris (propionylacetonato) aluminum,
Acetylacetonato bis (propionylacetonate)
Examples thereof include aluminum chelate compounds such as aluminum, and zirconium chelate compounds such as tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetonato) zirconium, and tetrakis (ethylacetoacetate) zirconium. These metal chelate compounds may be used alone or in combination of two or more.

The compound used as the component (ix) of the component (C) in the thermosetting clear coat coating composition is the organosilicon compound represented by the general formula (18) or a condensate thereof. R ¹⁷ in the general formula (18)
Is an organic group such as an alkyl group, aryl group or alkenyl group having 1 to 18 carbon atoms, R ¹⁸ is a hydrogen atom, 1 to 18 carbon atoms
, An alkyl group, an aryl group or an alkaryl group, R ¹⁹ and R ²⁰ are an alkyl group or an aryl group having 1 to 18 carbon atoms, and these organic groups may have a suitable substituent, Further, n6, n7, n8 and n9 are integers of 0 to 4, and n6 + n7 + n8 + n9 = 4. R ¹⁷ is preferably an alkyl group, aryl group or alkenyl group having 1 to 10 carbon atoms, and R ¹⁸ is preferably hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group or alkaryl group. The preferred group of R ¹⁹ and R ²⁰ is an alkyl group having 1 to 10 carbon atoms or an aryl group.

In the general formula (18), R ¹⁷ , R ¹⁸ and R
Suitable specific examples of the alkyl group and the aryl group in ¹⁹ and R ²⁰ include the same as the specific examples described in R ¹ of the general formula (1). Further, as a suitable specific example of the alkenyl group for R ¹⁷ , for example, the same as the specific examples described for R ¹⁴ in the general formula (13) can be mentioned. Further, as suitable specific examples of the alkaryl group for R ¹⁸ , there can be mentioned the same as the specific examples described for R ¹ in the general formula (1).

Examples of the organosilicon compound represented by the general formula (18) and its condensates include triphenylsilanol, diphenylvinylsilanol, diphenylmethylsilanol, dimethylphenylsilanol, diphenylsilanediol, dimethylsilanediol, diphenyldimethoxy. Silane, diphenyldiethoxysilane,
Examples include diphenyldiisopropoxysilane, triphenylmethoxysilane, triphenylethoxysilane, diphenylvinylethoxysilane, diphenyldimethoxycarbonylsilane, triphenylsilyl-2-nitrobenzyl ether, and one or more condensates thereof. Trimethylsilyl-t-butylperoxide, triphenylsilyl-t-butylperoxide, tris (4-chlorophenyl) silyl-t-butylperoxide, naphthyldiphenylsilyl-t-butylperoxide, tri-2-naphthyl. Silyl-peroxides such as silyl-t-butyl peroxide, triphenylsilyl cumenyl peroxide, di (2-naphthyl) di (t-butylperoxy) silane, and further acryloyloxy Homopolymers or copolymers of α, β-unsaturated silane compounds such as ropyltrimethoxysilane, methacryloyloxypropyltrimethoxysilane and methacryloyloxypropyltri-n-butoxysilane, and hydrolysis products of these compounds Examples thereof include compounds containing silanol groups and alkoxysilane groups. These organosilicon compounds may be used alone or in combination of two or more.

The mixing ratio of the metal chelate compound which is the component (viii) and the organosilicon compound which is the component (ix) or a condensate thereof in the mixture of the component (C) is not particularly limited, but (viii ) The equivalent ratio of (ix) the silicon atom of the organosilicon compound or its condensate to the metal atom of the metal chelate compound is preferably in the range of 0.2 to 10, and particularly preferably in the range of 0.5 to 5. preferable.
When the mixture is produced, it may be in the presence or absence of a solvent. Examples of the solvent used here include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, ether solvents, alcohol solvents, ester solvents, ketone solvents and mixed solvents thereof. The amount of the solvent used may be appropriately selected, but it is usually preferred that the metal chelate compound is blended in the range of 0.1 to 80% by weight.

In the thermosetting clear coat coating composition, the mixture of the component (C) is heated (vii
It is presumed that i) the metal chelate compound and (ix) the organosilicon compound or a condensate thereof form a complex and exhibit acid catalytic activity. The complex shows much higher acid catalytic activity than when the (viii) metal chelate compound is used alone.
The mixture of the component (C) keeps the storage stability of the thermosetting clear coat coating composition good for a long period of time, and accelerates the curing reaction when curing at low temperature for a short time, which is good for the cured product. Used for the purpose of imparting chemical and physical properties. Therefore, it is desirable that the mixture is a compound that exhibits acid catalytic activity at a temperature of 50 ° C. or higher. The mixture is 5
When the composition exhibits acid catalytic activity at a temperature lower than 0 ° C., the composition obtained may have an unfavorable situation such as thickening or gelation during storage. The mixture is (vi
ii) by changing the type and amount of the metal chelate compound and (ix) the organosilicon compound or its condensate,
The temperature at which the acid catalytic activity is exhibited can be controlled relatively easily.

In the thermosetting clear coat coating composition, one kind of the mixture of the component (C) may be used, or 2 kinds thereof may be used.
You may use in combination of 2 or more types, and the compounding quantity is a range of 0.01-20 weight part of a metal chelate compound normally with respect to 100 weight part of total solid content of (A) component and (B) component, Preferably Is selected to be compounded in the range of 0.02 to 10 parts by weight. The method for adding the mixture of the component (C) to the thermosetting clear coat coating composition is not particularly limited, but for example, (viii) a metal chelate compound and (ix) an organosilicon compound or a condensate thereof may be added. After premixing to prepare a mixture, the components (A) and (B)
It may be added to the components, or (viii) the metal chelate compound and (ix) the organosilicon compound or a condensate thereof may be separately added to the components (A) and (B), and as a mixture therein. Good.

Further, in other thermosetting clear coat coating composition, an acid catalyst is used as the component (C) in the above thermosetting clear coating coating composition, and a volatile organic compound is not substantially used as a diluent. A thermosetting clear coat coating composition characterized by: In the thermosetting clear coat coating composition, the acid catalyst used as the component (C) accelerates the curing reaction during curing of the composition, and imparts good chemical performance and physical performance to the cured product. It is an important ingredient. Examples of the acid catalyst as the component (C) include Bronsted acids, Lewis acids, and thermally latentized ones thereof.

Here, the Bronsted acid is a substance which dissociates protons and exhibits acidity, and includes, for example, sulfuric acid, sulfuric acid monoester, sulfonic acid, phosphoric acid, phosphoric acid mono- and diesters, polyphosphoric acid esters, boric acid mono- and diesters. , Carboxylic acids, halogenocarboxylic acids and the like,
Preferably, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, etc., alkylbenzenesulfonic acid having 1 to 50 carbon atoms, chloroacetic acid, dichloroacetic acid, etc.,
50 mono- or di-halogenocarboxylic acid, monomethyl phosphate, dimethyl phosphate, and other alkyl phosphate monoesters and diesters having 1 to 50 carbon atoms can be mentioned. Specific examples of the Lewis acid include the same as the specific example described in (iii).

Specific examples of the thermally hidden latent Bronsted acid or Lewis acid include the thermally hidden latent examples of the above Bronsted acid or Lewis acid. Among these, preferred are triethyl borate, boron compounds such as boron trifluoride, trialkyl aluminum, aluminum dialkyl halides, aluminum monoalkyl halides, aluminum halides, aluminum compounds such as aluminum stearate, 2-ethyl. Zinc hexylate, zinc stearate, zinc chloride, zinc compounds such as zinc bromide, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin acetylacetonate, dioctyltin diacetate, 2-ethyl tin hexylate, tin stearate, chloride (II) tin, (IV) tin chloride, tin (II) bromide, tin (IV) bromide, and other tin compounds, titanium acetylacetonate, titanium cene dichloride, titanium (IV) chloride, and other titanium compounds, zirconium Examples thereof include conoacetylacetonate, zirconocene dichloride, zirconium compounds such as (IV) zirconium chloride, benzyl cation-type Lewis acid, and thermal latentization thereof. These acid catalysts may be used alone or in combination of two or more.

In the thermosetting clear coat coating composition, the amount of the acid catalyst as the component (C) is usually 0.01 per 100 parts by weight of the total solid content of the components (A) and (B). To 20 parts by weight, preferably 0.02-1
It is selected in the range of 0 parts by weight. If the amount of the acid catalyst is less than 0.01% by weight, the amount of the catalyst is too small and the effect of accelerating the reaction is not sufficiently exhibited. On the other hand, when the amount of the acid catalyst exceeds 20% by weight, the effect of accelerating the reaction is not improved regardless of the amount, but rather a large amount of the catalyst remains in the thermosetting clear coat coating composition, which results in the coating. The physical properties of the film may deteriorate, which is not preferable.

On the other hand, as the room temperature curable clear coat coating composition, a main agent or a solution containing the components (A) and (B) in the thermosetting clear coat coating composition as essential components, and a blend A two-pack type comprising a composition obtained by mixing at least one acid catalyst selected from a mixture of a Sted acid, a Lewis acid or a metal chelate compound and a silanol group-containing compound, or a solution thereof. A room temperature curable clear coat coating composition is included.

In preparing the room temperature curable clear coat coating composition, the above-mentioned component (A) and / or (B) is used.
A base material or a solution thereof containing at least one selected from the components as an essential component is prepared. The solvent used for the base material solution is not particularly limited as long as it can dissolve the respective base materials.
-Hexane, n-heptane, n-octane and other aliphatic hydrocarbons, benzene, toluene, xylene and other aromatic hydrocarbons, chloroform, carbon tetrachloride and other halogenated hydrocarbons, methanol, ethanol, isopropanol, Ordinary paint solvents such as alcohols such as butanol, ethers such as dibutyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate, n-propyl acetate and n-butyl acetate. What is used as. These solvents may be used alone or in combination of two or more. The concentration of the essential component in the main agent solution is not particularly limited, but is usually 10 to 95% by weight, preferably 30 to 80% by weight.

Examples of the acid catalyst in the room temperature curable clear coat coating composition include Bronsted acid, Lewis acid, or a mixture of a metal chelate compound and a silanol group-containing compound. These acid catalysts may be used alone or in combination of two or more. Specific examples of the Bronsted acid include those similar to the specific examples of the Bronsted acid described above, and preferable ones are also the same as the above. These Bronsted acids may be used alone or in combination of two or more. Further, specific examples of the Lewis acid include the same as the specific example described in (iii). The Lewis acid may be used alone or in combination of two or more kinds.

Further, a mixture of a metal chelate compound and a silanol group-containing compound forms a complex having an acid catalytic activity, and thus can be used in a room temperature curable clear coat coating composition. Specific examples of the metal chelate compound include the same as the specific examples described in (viii). These metal chelate compounds are 1
One kind may be used, or two or more kinds may be used in combination.

Examples of the silanol group-containing compound include triphenylsilanol, diphenylvinylsilanol, diphenylmethylsilanol, dimethylphenylsilanol, diphenylsilanediol, dimethylsilanediol, and one or more condensates thereof. Further, acryloyloxypropyltrimethoxysilane, methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyltri-n-
Examples thereof include silanol group-containing compounds obtained by hydrolyzing a homopolymer or copolymer of an α, β-unsaturated silane compound such as butoxysilane. These silanol group-containing compounds may be used alone or in combination of two or more. The mixing ratio in the mixture of the metal chelate compound and the silanol group-containing compound is
The equivalent ratio of the silanol group of the silanol group-containing compound to the metal atom of the metal chelate compound is preferably in the range of 0.2 to 10, particularly preferably 0.5 to 5.

In the room temperature curable clear coat coating composition, the amount of the acid catalyst blended is such that, based on 100 parts by weight of the total solid content of the components (A) and (B), a Bronsted acid, a Lewis acid, or a metal chelate compound. The metal chelate compound in the mixture of the compound with a silanol group-containing compound is preferably in the range of 0.01 to 20 parts by weight, more preferably 0.0.
It is selected so as to be compounded in the range of 2 to 10 parts by weight. Further, it is desirable that the acid catalyst is usually added and mixed immediately before or 48 hours before using the room temperature curable clear coat coating composition, more preferably immediately before or 24 hours before use.

When preparing a room temperature curable clear coat coating composition, the above-mentioned acid catalyst may be added as it is, or an acid catalyst solution containing them may be prepared and added. The solvent used in this acid catalyst solution is not particularly limited as long as it can dissolve the acid catalyst, but aliphatic hydrocarbons such as n-hexane, n-heptane and n-octane, benzene, Aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chloroform and carbon tetrachloride, alcohols such as methanol, ethanol, isopropanol and butanol, ethers such as dibutyl ether, tetrahydrofuran and dioxane, acetone, methyl ethyl ketone ,
Ketones such as methyl isobutyl ketone, ethyl acetate,
Examples thereof include those usually used as a coating solvent such as esters such as n-propyl acetate and n-butyl acetate.
Moreover, you may use what mixed the soluble amount of water to these solvents, and used them as a solvent. These solvents may be used alone or in combination of two or more. The concentration of the acid catalyst in the acid catalyst solution is not particularly limited, but is usually in the range of 1 to 95% by weight, preferably 2 to 60% by weight. The room temperature curable clear coat coating composition is prepared by mixing the above-mentioned main agent or a solution thereof with the above acid catalyst or a solution thereof.

The curable base coat coating composition of the present invention is prepared by coating a curable base coat coating composition on the surface of an object to be coated, and further using a polyol as a main resin on this base coat and curing with an amino resin. /
Melamine-based and / or polyol / melamine / using a polyisocyanate compound or a block thereof as a curing agent
It is particularly effective when used as the curable base coat coating composition in a coating film forming method in which a curable clear coat coating composition comprising a polyisocyanate system is applied by wet-on-wet. Examples of the polyol which is one component of the curable clear coat coating composition include hydroxyl group-containing polymers such as acrylic polyol and polyester polyol. An aminoplast resin as an example of an amino resin which is another component of the curable clear coat coating composition is a compound containing an amino group or an amide group, such as melamine, benzoguanamine, urea, dicyandiamide, and glycolurea. , Ethyl alcohol, propyl alcohol
A resin obtained by dehydration condensation with formaldehyde in the presence of alcohols such as diol, n-butyl alcohol and isobutyl alcohol. The mixing ratio of the polyol resin component and the aminoplast resin used in the curable clear coat coating composition is 8 based on the resin solid content.
Suitable is 0:20 to 50:50, preferably 7
It is 0:30 to 60:40.

On the other hand, as the polyisocyanate compound, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and isophorone diisocyanate are used.
And aliphatic and alicyclic diisocyanate compounds such as glutamine, 4,4′-diisocyanatoethyldicyclohexylmethane and their nuretes, burettes and adducts. Further, there may be mentioned block isocyanates obtained by chemically blocking the isocyanate group of the above compound with active methylene, oxime, lactam, alcohol, phenol and the like. The mixing ratio of the main resin component used in the curable clear coat coating composition to the polyisocyanate compound was 1: 0.
7 to 0.7: 1 is suitable. Further, as such a curable clear coat coating composition, an acrylic / melamine type bell coat No. 6200 (trade name: manufactured by Nippon Oil & Fats Co., Ltd.) or acrylic / fluorine resin / melamine-based Bellflon No. 7200 (trade name: NOF Corporation)
Or acrylic / melamine / polyisocyanate type Froshine H3 (trade name: NOF Corporation)
Etc.

The curable clear coat coating composition is used as it is, or if necessary, various additives such as color pigments, fillers, solvents, ultraviolet absorbers, light stabilizers, antioxidants and flow regulators are added. Can be used.
The curable clear coat coating composition can be produced by mixing the above components and, if necessary, incorporating various additives. The method of mixing each component and the method of adding various additives are not particularly limited, and various methods can be used, and the mixing order and the addition order can also be performed in various orders.

If necessary, a pigment, various additives and a dye having good weather resistance may be added to the curable clear coat coating composition to the extent that transparency is not impaired. As the pigment, various pigments such as organic pigments and inorganic pigments are used.For example, surface-treated aluminum, copper, brass, bronze, stainless steel, or mica-like iron oxide, scale-like metallic powder, and oxide are used. Metallic pigments such as mica flakes coated with titanium or iron oxide are used. In addition, other inorganic pigments such as titanium dioxide, iron oxide, yellow iron oxide, carbon black, organic pigments such as phthalocyanine blue, phthalocyanine green, and quinacridone red pigment, extender barium sulfate, clay, silica, talc and other extender pigments. And so on.

The base material to which the coating material is applied is not particularly limited, and various base materials can be used, such as wood, glass, metal, cloth, plastic, foam,
Examples thereof include elastic materials, paper, ceramics, concrete, organic materials such as gypsum board, and inorganic materials.

The curable base coat coating composition of the present invention comprises the step of coating the curable base coat coating composition on the surface of an object to be coated, and further the wet coating of the curable clear coat coating composition on the base coat. It is preferably applied to a coating film forming method including a painting step. A suitable method for forming a coating film using a thermosetting clear coat coating composition is, for example, after diluting the curable base coat coating composition to a desired viscosity with a suitable diluent such as an organic solvent, then air spraying, Using a commonly used coating machine such as an electrostatic air spray, a roll coater, a flow coater, a dipping type coating machine, or a brush, bar coater, applicator, etc., the film thickness after drying is usually 5 to 50 μm, preferably 10 to 30 μm, and left at room temperature to 100 ° C. for 1 to 20 minutes. Then, a clear top coat coating composition by the thermosetting clear coat coating composition was dried using the above method. The film thickness is 10 to 100 μm, preferably 20 to 8
Examples include a method of coating so as to have a thickness of 0 μm, and heat curing at a temperature of 50 to 300 ° C., preferably 100 to 180 ° C. for 5 seconds to 2 hours, preferably 5 to 90 minutes. Of the above methods, spray coating is preferable as the coating method. A suitable method for forming the coating film using the room temperature curable clear coat coating composition is the same method as described above. In this case, the curing condition is usually in the temperature range of 0 ° C or higher and lower than 50 ° C for 30 minutes to 10 minutes. It will be left for about a day. For the purpose of further promoting the curing and shortening the time required for the curing, 50
There is no problem even if it is heated to a temperature of ℃ or more.

Examples of coated articles obtained by applying the curable base coat coating composition of the present invention include structures, wood products, metal products, plastic products, rubber products, processed paper, ceramic products, glass products and the like. . More specifically, examples thereof include automobiles, metal plates such as steel plates, motorcycles, ships, railway vehicles, aircraft, furniture, musical instruments, home appliances, building materials, containers, office supplies, sports equipment, toys, and the like.

[0146]

EXAMPLES Next, the present invention will be described more specifically by way of examples. The present invention is not limited to these examples. The parts and% in the examples and comparative examples are based on weight.

Production Example 1 Production of thermosetting clear coat coating composition (1) Production of chemically blocked acid type curing agent solution (A) (i) Production of polycarboxylic acid compound solution Thermometer, reflux cooling Charge the following ingredients into a four-necked flask equipped with a vessel, stirrer, and dropping funnel, and heat with stirring.
The temperature was raised to 0 ° C. Pentaerythritol 136.0 parts by weight Methyl isobutyl ketone 538.7 parts by weight Then, 672.0 parts by weight of methylhexahydrophthalic anhydride was added dropwise over 2 hours while maintaining 120 ° C. to obtain an acid value (pyridine / water) of the mixture. (Weight ratio) = Dilute about 50 times by weight with a 9/1 mixture, and heat and stir until the solution heat-treated at 90 ° C for 30 minutes is titrated with a potassium hydroxide standard solution) to 170 or less. Thus, a tetrafunctional polycarboxylic acid compound solution was obtained.

(Ii) Production of chemically blocked acid type curing agent solution (A) Using the polycarboxylic acid compound solution obtained by the above method, a mixture having the following composition was placed in the same flask as above. The mixture was charged and stirred at 50 ° C. Polycarboxylic acid compound solution of (i) 336.7 parts by weight isobutyl vinyl ether 120.2 parts by weight 35% by weight hydrochloric acid 0.2 parts by weight methyl isobutyl ketone 46.3 parts by weight Where the acid value of the mixture is 12 or less. After the reaction was completed and the mixture was allowed to cool, the product was transferred to a separating funnel. The obtained product was washed with 100 parts by weight of a 10% by weight aqueous sodium carbonate solution in a separating funnel with alkali, and then repeatedly washed with 300 parts by weight of deionized water until the pH of the washing solution was 7 or less. Then molecular sieve 4A1 / 1 in the organic layer
6 was added and dried at room temperature for 3 days to obtain a chemically blocked acid type curing agent solution (A) having a nonvolatile content of 60.0 wt% and a Gardner viscosity EF (25 ° C.).

(2) Production of Epoxy Group-Containing Acrylic Resin Solution (B) A four-necked flask equipped with a thermometer, a reflux condenser and a stirrer was charged with 40.0 parts of xylene as an initial charge solvent, and the mixture was stirred. It heated and kept at 100 degreeC. On the other hand, glycidyl methacrylate 28.4 parts, butyl methacrylate 2
0.0 parts, 27.7 parts of methyl methacrylate, 23.9 parts of 2-ethylhexyl acrylate, 2.0 parts of azobisisobutyronitrile and 5 parts of acetic acid normal butyl ester
It was mixed and dissolved in 4.0 parts to be a dropping component. Then 100 ℃
The above-mentioned dropping components were dropped at a constant rate from the dropping funnel at the temperature of 2 hours. After completion of the dropping, the temperature of 100 ° C. was maintained for 1 hour, an additional catalyst component prepared by dissolving 0.2 part of azobisisobutyronitrile in 3.8 parts of acetic acid normal butyl ester was added, and the temperature of 100 ° C. was maintained for 2 hours. The reaction was terminated where it was kept to obtain an epoxy group-containing acrylic resin solution (B). Non-volatile content at the end of the reaction is 50.8
% (Nonvolatile content measurement condition: 50 ° C., 0.1 mmHg for 3 hours), Gardner viscosity (JIS K-5400 (199
0) 4.5.1 according to Gardner-type foam viscosity method) was S.

(3) Preparation of Thermally Latent Acid Catalyst Solution (C) Methyl isobutyl ketone 25.
0 parts, acetic acid ethyl ester 25.0 parts were charged and, after thorough mixing, zinc octylate 20.1 parts, di (2-ethylhexyl) sulfosuccinic acid 24.1 parts and N-methylmorpholine 5.8 parts. The mixture was added with stirring and stirred. afterwards,
The reaction vessel was allowed to stand for 3 hours to obtain a 50% solution (C) of the thermal latent acid catalyst.

(4) 100% of the epoxy group-containing acrylic resin solution (B) was placed in a container for producing the thermosetting clear coat coating composition (D).
Part, 5 parts of the chemically blocked acid type curing agent solution (A)
0 parts, 4.3 parts of the thermal latent acid catalyst solution (C), 0.1 parts of modaflow, 3.0 parts of xylene and 0.8 parts of normal butyl acetate were added and sufficiently stirred, and then Solvesso # 1
00 as diluent solvent and 25 in Ford Cup # 4
It was diluted so as to reach a second to obtain a thermosetting clear coat coating composition (D).

Production Example 2 Acrylic resin solution for thermosetting base coat paint (E-1
-E-5) Production A thermometer, a reflux condenser, a stirrer, and a four-necked flask equipped with a dropping funnel were charged with the respective synthetic solvents (a mixture of xylene and propylene glycol monoacetate) in the amounts shown in Table 1. The mixture was heated under stirring to maintain the reflux state. Next, under a reflux condition, a monomer and a polymerization initiator mixture (dropping components) having the composition shown in Table 1 were dropped at a constant rate from a dropping funnel over 1.5 hours. After completion of dropping, the reflux state was maintained for 1.5 hours, then cooled to 100 ° C., a polymerization initiator solution (additional catalyst) having the composition shown in Table 1 was added, and the reaction temperature of 100 ° C. was further maintained for 2 hours. By the way, by finishing the reaction,
Acrylic resin solutions for base coat paints (E-1 to E-5) having the characteristic values shown in Table 1 were obtained.

[0153]

[Table 1]

The abbreviations and trade names in Table 1 are as follows. Arcosolv PMA: trade name, Kyowa Yuka Co., Ltd., propylene glycol monomethyl ether acetate GMA: glycidyl methacrylate MMA: methyl methacrylate BA: butyl acrylate ST: styrene HEMA: 2-hydroxyethyl methacrylate praxel FM-2: trade name, Daicel Chemical Co., Ltd.
ε-caprolactone 2 mol modified HEMA Praxel FM-4: trade name, manufactured by Daicel Chemical Industries, Ltd.
ε-caprolactone 4 mol modified HEMA Perbutyl Z: trade name, manufactured by NOF CORPORATION, radical polymerization initiator Perbutyl O: trade name, manufactured by NOF Corporation, radical polymerization initiator

Production Example 3 Production of Carbon Black Millbase (F) Carbon Black TS-6B (trade name, manufactured by Degussa) 1
23.4 parts, melamine resin solution U-VAN 122 (trade name, manufactured by Mitsui Toatsu Co., Ltd.) 133.4 parts, xylene 27.3 parts,
After 27.3 parts of propylene glycol monoacetate was added and thoroughly mixed, a motor mill 250 (trade name, manufactured by Egger Japan) was used as a pigment disperser.
The pigment was dispersed for minutes to obtain carbon black millbase (F).

Production Example 4 Production of Cellulose Acetate Butyrate (CAB) Solution (G) 55 parts of ethyl acetate was added to 20 parts of CAB531-1 (trade name, manufactured by Eastman Co.) and sufficiently stirred and dissolved. After that, add 25 parts of xylene and add cellulose.
An acetate butyrate (CAB) solution (G) was obtained.

Production Example 5 Production of Internal Cross-Linking Resin Fine Particle Solution (H) To 76.2 parts of deionized water was added 1.8 parts of Lapizole B-90 (trade name, manufactured by NOF CORPORATION) as a surfactant. The mixture was heated to 80 ° C. with stirring under a nitrogen stream to dissolve rapizole B-90. Then potassium persulfate 0.0
1.2 parts of an aqueous solution of 2 parts was added, and 5 minutes after the addition, 6.0 parts of ethyl acrylate and ethylene dimethacrylate were added.
A core part monomer mixed solution of 3 parts and 1.7 parts of divinylbenzene was added dropwise over 1.5 hours. After keeping for 30 minutes, 4.1 parts of ethyl acrylate, 3.3 parts of ethylene dimethacrylate and 2.6 parts of hydroxypropyl methacrylate.
The shell part monomer mixture solution was added dropwise over 1.5 hours.
On the other hand, 1.2 hours after the start of dropping the monomer-mixed droplets in the core portion, 1.2 parts of an aqueous solution of 0.02 part of potassium persulfate was dropped over 2.5 hours simultaneously with the start of the monomer-mixed liquid. After the addition of the monomer mixture and the potassium persulfate solution, under a nitrogen stream,
Stirring was carried out at 0 ° C. for 2 hours to obtain an aqueous solution of internally crosslinked resin fine particles. After cooling, 2 parts of toluene and 3 parts of n-butanol under stirring.
After adding 8 parts and 10 parts of isopropanol in order, 26
% Sodium hydroxide (2.2 parts) was added, and the mixture was refluxed for 2 hours. Then, add 0.9 parts of a 76% formic acid aqueous solution, and add 30 parts.
After stirring for 5 minutes, 5 parts of isopropanol was added, and the mixture was left for 30 minutes and the separated water tank was removed. After adding 40 parts of ion-exchanged water to the organic layer and stirring for 30 minutes, 5 parts of isopropanol was added and left for 30 minutes to remove the aqueous layer. After performing this operation again, 40 parts of acrylic resin solution E-5 and 49 parts of methyl isobutyl ketone were added to carry out azeotropic dehydration, and only the aqueous layer was removed until the boiling point became 105 ° C. or higher. The solvent was distilled off under reduced pressure until the content became 0.1% to obtain an internal crosslinked resin particle solution (H).

Production Example 6 Production of Zinc Octylate Solution (I) To 10 parts of zinc octylate (zinc content: 18%, manufactured by Nippon Kagaku Sangyo Co., Ltd.), 26 parts of butyl acetate were added and stirred to contain zinc. A zinc octylate solution (I) having a rate of 5% was obtained.

Examples 1 to 9 Thermosetting Base Coat Coating Composition Composition Materials shown in Table 2 were weighed in a container and sufficiently stirred to prepare a thermosetting base coat coating composition (J-1 to J-9). Got

[0160]

[Table 2]

The components in Note 2 are as follows. Carbon black millbase (F): Carbon black millbase (F) produced in Production Example 3, melamine resin content: 66.7% Aluminum flakes: Showa Aluminum Co., Ltd., SAP561
-PS Melamine resin: Mitsui Toatsu Chemical Co., Ltd., Uvan 122 Isocyanate curing agent: Nippon Polyurethane Co., Ltd. Coronate EA-60B Amide wax: Kyoeisha Chemical Co., Ltd., Floren S
H-290

Example 10 Method for forming coating film An epoxy resin-based cationic electrodeposition coating composition of 20 μm was coated on a chemical conversion treated dull steel sheet and cured for 20 minutes at 170 ° C. 100 (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) was coated so as to have a dry film thickness of 40 μm, and cured at 140 ° C. for 20 minutes to obtain a coating object.
Next, toluene was added as a diluting solvent to the thermosetting base coat coating composition (J-1), and the mixture was mixed with Ford cup # 4 to 1
It was diluted for 5 seconds (20 ° C.) and air-spray coated on the above-mentioned article to be coated (dry film thickness: 15 μm). After standing for 3 minutes, the thermosetting clear coating composition (D) was applied by air spray coating so that the dry film thickness was 35 μm.
After leaving it at room temperature for 10 minutes, it was cured at 140 ° C. for 20 minutes to obtain a finished coating film. The following 8 items of coating film performance tests were performed on the finished coating film, and it was confirmed that all of them had good coating film performance. For details of the coating film performance test results,
It is described in Table 3.

The physical performance of the coating film performance was determined as follows. (1) Acid resistance-1 2 ml of 40 wt% sulfuric acid was spotted on the test piece,
After standing at 20 ° C. for 48 hours, the abnormality of the coating film was visually determined. (2) Acid resistance-2 Place 2 ml of 40 wt% sulfuric acid on the test piece in a spot shape,
After heating at 60 ° C. for 30 minutes, the abnormality of the coating film was visually determined. (3) Acid resistance-3 The test piece was immersed in 0.1 N sulfuric acid and kept at 60 ° C for 24 hours, and then the abnormality of the coating film was visually determined.

(4) Weather resistance Sunshine weather meter (JIS K-5400
(1990) 9.8.1) for 1000 hours or 3
After exposure for 000 hours, 60 degree specular gloss value (JIS
K-5400 (1990) 7.6 degree specular gloss) was measured, and the abnormality of the coating film was visually determined or compared with the gloss value before exposure. (5) Adhesiveness Adhesiveness was evaluated by a cross-cut tape method based on the method of JIS K-5400 (1990) 8.5.2. (6) Knoop hardness Based on the method of ASTM D-1474, the coating film hardness was measured by an M-type micro hardness meter manufactured by Shimadzu Corporation. The larger the number, the harder it is.

(7) Boiling resistant aqueous solution After dipping the test plate in boiling water (98 to 100 ° C.) for 3 hours, the test plate was allowed to cool at room temperature for 24 hours, and the adhesiveness was measured by the cross-cut tape method. The boiling water resistance was evaluated. (8) Gasohol-resistant ethanol and unleaded gasoline were mixed in a volume ratio of 10/90, and a test plate was immersed in the solution at 40 ° C. for 1 hour to evaluate changes in the coating surface state.

Examples 11 to 17 The thermosetting base coat coating composition (J-
Instead of 1), a thermosetting base coat coating composition (J
-2) to (J-8) were used to prepare finished coating films in the same manner as in Example 1, and the coating film performance was confirmed. As a result, it was confirmed that all of them had good coating film performance. The details of the coating film performance test results are shown in Table 3.

[0167]

[Table 3]

Example 18 An epoxy resin-based cationic electrodeposition coating composition of 20 μm was applied to a chemical conversion treated dull steel plate and cured for 20 minutes at 170 ° C. 100 (trade name: manufactured by Nippon Oil & Fats Co., Ltd.) was applied so as to have a dry film thickness of 40 μm, and cured at 140 ° C. for 20 minutes to obtain an object to be coated. Next, toluene was added to the curable base coat paint (J-1) as a diluting solvent, and the solution was added to a Ford cup # 4 for 15 seconds (2
It was diluted to 0 ° C.) and air-spray-coated on the above-mentioned article to be coated (dry film thickness: 15 μm). After standing for 3 minutes, a curable clear paint (Bellcoat No. 620
0 (trade name: manufactured by NOF CORPORATION), acrylic / melamine type) was air-spray coated so that the dry film thickness was 35 μm. Leave at room temperature for 10 minutes, then at 140 ° C for 2
It was cured for 0 minutes to obtain a finished coating film. The following three items of coating film performance tests were conducted on the finished coating film, and it was confirmed that all of them had good coating film performance. Details of the coating film performance test results are shown in Table 4.

(1) Weather resistance Sunshine weather meter [JIS K-5400
(1990) 9.8.1] for 1000 hours or 3
After exposure for 000 hours, the 60 degree specular gloss value [JIS
K-5400 (1990) 7.6 degree specular gloss] was measured, and the abnormality of the coating film was visually judged or compared with the gloss value before unexposed. (2) Adhesiveness Adhesiveness was evaluated by the cross-cut tape method based on the method of JIS K-5400 (1990) 8.5.2. (3) Moisture resistance Based on the method of JIS K-5400 (1990) 9.2.2, a moisture resistance test was conducted for 240 hours by a rotary method. The evaluation was conducted by visually observing the abnormality of the coating film immediately after the test and after 2 hours. (4) Chipping resistance Based on the diamond shot method [JP-A-56-67735], a diamond shot tester (Suga Tester Co., Ltd.)
Manufactured by the company), a 0.01 carat diamond is -2
A diamond shot test was performed at 0 ° C., a shot speed of 210 ± 10 Km / h, and 30 shots, and the total area of the peeled portion at 30 shots was evaluated.

Examples 19 to 25 J-2 to J-8 were used instead of the curable base coat paint (J-1) in Example 18, and the same procedure as in Example 18 was used to complete the coating. A film was prepared and the coating film performance was confirmed. As a result, it was confirmed that all of them had good coating film performance. Details of the coating film performance test results are shown in Table 4.

Comparative Example 1 A completed coating film was prepared in the same manner as in Example 1 except that the thermosetting base coat coating composition (J-9) was used instead of the thermosetting base coat coating (J-1) in Example 10. Then, the coating film performance was confirmed. As a result, in the thermosetting base coat coating composition (J-9), since the epoxy group was not added to the resin component composed of the polymer of the ethylenically unsaturated monomer, the boiling water resistance test and the gasohol resistance test were conducted. At the interface between the base coat and the clear coat, peeling occurred.
The details of the coating film performance test results are shown in Table 3.

Comparative Example 2 A thermosetting base coat coating composition (J-9) was used in place of the thermosetting base coat coating (J-1) in Example 18, and a finished coating film was prepared in the same manner as in Example 1. Then, the coating film performance was confirmed. As a result, the thermosetting base coat paint (J-9) does not have an epoxy group added to its main resin component, and therefore has a base coat resistance in chipping resistance.
Peeling occurred at the interface between the coat and the clear coat. Details of the coating film performance test results are shown in Table 4.

[0173]

[Table 4]

[0174]

The curable base coat coating composition of the present invention has an epoxy group in the resin component composed of a polymer of an ethylenically unsaturated monomer, so that it is a chemically blocked acid type curing agent. Securing active points of adhesion with a thermosetting clear coat coating composition consisting of a combination of a resin with an epoxy group or a curable clear coat coating composition comprising a polyol / melamine system and / or a polyol / melamine / polyisocyanate system By doing so, a coating film having excellent coating film performance can be formed. The coating film forming method and the coated article of the present invention can be easily applied to various coating film performances by combining the thermosetting base coat coating composition and the thermosetting clear coat coating composition, and performing wet-on-wet coating. Excellent coatings and coated articles can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kuniyoshi Ogura Kuniyoshi Ogura 123-2 Iwaicho, Hodogaya-ku, Yokohama-shi Kanagawa 2-204 Heights in front of the station (72) Inventor Shigeyuki Mizuno 3-52-9 Shimonagaya, Konan-ku, Yokohama-shi, Kanagawa Maison Narumi 102 (56) Reference JP-A-4-218561 (JP, A) JP-A-59-150572 (JP, A) JP-A-57-48366 (JP, A) (58) Fields investigated (Int.Cl . ⁷ , DB name) C09D 5 / 00,161 / 28,175 / 04

Claims (7)

(57) [Claims] 1. The epoxy equivalent is 500 to 300.
0 , hydroxyl value is 20 to 200, glass transition temperature is -30
Composed of a polymer of ethylenically unsaturated monomers having a weight average molecular weight of 3,000 to 150,000 at -80 ° C.
Resin component not having carboxyl group , (2) Only curing agent having two or more functional groups capable of reacting with hydroxyl group in one molecule
Curing agent comprising, (3) a Lewis acid catalyst, and (4) Ri consists coloring pigment and / or luster pigments, curing agent (2)
The compounding ratio of is relative to 100 parts by weight of the resin component of (1)
Te, curable base coating composition comprising 10 to 100 parts by weight der Rukoto. 2. A curable base coat coating composition comprising a curable base coat coating composition applied on the surface of an object to be coated, and a resin containing a chemically blocked acid type curing agent and an epoxy group on the base coat. The curable base coat coating composition according to claim 1, which is a curable base coat coating composition for use in a method for forming a coating film in which a curable clear coat coating composition comprising a combination with the above is applied in a wet-on-wet manner. 3. A curable base coat coating composition, which comprises coating a curable base coat coating composition on the surface of an object to be coated, and further using a polyol as a main resin on the base coat,
Wet-on-wet coating of a curable clear coat coating composition composed of a polyol / melamine system and / or a polyol / melamine / polyisocyanate system using a polyisocyanate compound or a block thereof as a curing agent, which is cured with an amino resin. The curable base coat coating composition according to claim 1, which is a curable base coat coating composition used in the coating film forming method. 4. A step of coating the curable base coat coating composition according to claim 1 on the surface of an object to be coated, and further a combination of an acid type curing agent chemically blocked on the base coat and a resin containing an epoxy group. A method for forming a coating film, which comprises a step of applying a curable clear coat coating composition comprising the composition on a wet-on-wet basis. 5. A step of coating the curable base coat coating composition according to claim 1 on the surface of an object to be coated, further comprising a polyol / melamine system and / or a polyol which is a main resin on this base coat and which is cured with an amino resin. A method for forming a coating film, comprising a step of applying a curable clear coat coating composition comprising a polyol / melamine / polyisocyanate system using a polyisocyanate compound or a block thereof as a curing agent in a wet-on-wet manner. . 6. A coated article obtained by the method for forming a coating film according to claim 4. 7. A coated article obtained by the method for forming a coating film according to claim 5.