JPH05269432A - Formation of coating film - Google Patents

Abstract

PURPOSE:To obtain a coating film with excellent finishing properties, recoating properties etc., by using a coating compsn. wherein specified essential ingredients are incorporated as the coating compsn. forming a colored base coat and a clear top coat. CONSTITUTION:As a coating compsn. forming a colored base coat, a coating compsn. wherein a hydroxyl group-contg. resin, an amino resin, a polyorganosiloxane contg. at least two on average silanol and/or alkoxysilane groups in a molecule and with a number-average mol.wt. of 1,000 or larger, a metal chelating compd., a metal flake powder and/or a mica powder and an org. solvent are incorporated as essential ingredients, is used. In addition, as a coating compsn. forming a clear top coat, a coating compsn. wherein a resin contg. at least one kind of group selected from silanol groups and a hydrolyzable group being directly bonded with a silicon atom, a hydroxyl group and an epoxy group, a curing catalyst and an org. solvent are incorporated as essential ingredients, is used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel coating film forming method, and more particularly to a coating film forming method having a particularly excellent finished appearance.

[0002]

2. Description of the Related Art Conventionally, there has been a demand for improving finish appearance, coating film performance and the like in top coating films, particularly for automobile exterior panels. In addition, there is a strong demand for the development of low-temperature curable coatings for the purpose of reducing energy costs and enabling the integral coating of the same coating on automobile exterior panels where steel sheet and plastic substrates are integrated. There is.

Currently, the mainstream paints for automobile top coats are thermosetting acrylic resin / melamine resin type and thermosetting polyester resin / melamine resin type.
These paints are near the limit in high smoothness, and
There is also room for improvement in the performance of various coating films. There is also a problem that the low temperature curability is not sufficient. Further, there are still problems such as a coating film being cracked by a condensate (formalin, etc.) generated during baking and environmental pollution.

The applicant of the present invention has proposed a coating composition for automobiles in Japanese Patent Application Laid-Open No. 2-160879 as a coating excellent in low temperature curability. A silicone-based coating composition obtained by blending a metal chelate compound with a copolymer having a silanol group- and / or alkoxysilane group-containing polysiloxane-based macromonomer and an oxirane group-containing vinyl monomer as monomer components. This is applied to, for example, a clear top coat for a thermosetting acrylic resin or a thermosetting polyester resin / melamine resin-based metallic base coat, and a metallic base coat is a clear top for those that have been painted and finished by a 2 coat / 1 bake system. There is a drawback that the orientation of the aluminum flake pigment is affected by the coating and a coating with an aluminum luster (giving a crisp feeling and white) cannot be obtained, and the surface gloss is inferior, and the curing of the metallic base coat is difficult. Before the start of the clear top coat Reduction starts, popping the result coating film has a drawback that cause defects such as shrinkage.

When a defect occurs in the finish coating film, a metallic base coat and a clear top coat of the same kind are usually recoated in order to repair the defect.
The one using the above silicone-based coating composition also has a problem that the adhesion between the coating films (top clear coat and metallic base coat to be recoated) is not sufficient.

[0006]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned drawbacks, the present inventors have found that a clear top coat is formed on a specific colored base coat to improve the finishability and recoatability. It has been found that an excellent coating film can be provided, and the present invention has been completed.

That is, according to the present invention, in a top coating method in which a colored base coat and a clear top coat are sequentially formed on a material and finished by a two-coat one-bake system, a coating composition for forming a colored base coat includes (1) a hydroxyl group-containing resin (2) ) Amino resin (3) Number average molecular weight 1,000 having an average of two or more silanol groups and / or alkoxysilane groups in one molecule
Using a coating composition containing the above polyorganosiloxane (4) metal chelate compound (5) metal flake powder and / or mica powder and (6) organic solvent as an essential component, as a coating composition for forming a clear top coat , (1) a resin having at least one group selected from a silanol group and a hydrolyzable group directly bonded to a silicon atom, a hydroxyl group and an epoxy group (2) a curing catalyst and (3) an organic solvent as essential components It relates to a method for forming a coating film, which comprises using a coating composition.

Next, the method of the present invention will be specifically described. Colored Base Coat The colored base coat is (1) a hydroxyl group-containing resin (2) an amino resin (3) having a number average molecular weight of 1 or more having at least two silanol groups and / or alkoxysilane groups in one molecule 1,
000 or more polyorganosiloxane (hereinafter sometimes simply referred to as “polyorganosiloxane”) (4) metal chelate compound (5) metal flake powder and / or mica powder (hereinafter simply referred to as “metal flake”) (6) Formed from a coating composition for a base coat containing an organic solvent as an essential component.

The hydroxyl group-containing resin has a hydroxyl group in the molecule and preferably has a hydroxyl value of about 20 to 200, preferably about 50 to 150. When the hydroxyl value is less than 20, the curing rate of the base coat coating becomes slower than that of the top coat coating, and the top coat coating is cured before the base coating coating is cured. It is not preferable because defects such as the above occur and the finished appearance of the coating film is deteriorated, and the curing thereof is not sufficient, so that the coating film performance (water resistance, impact resistance, etc.) is deteriorated. On the other hand, when the hydroxyl value exceeds about 200, a large amount of unreacted hydroxyl groups remain in the coating film and the coating film performance (water resistance, weather resistance, etc.) is deteriorated, which is not preferable.

As the hydroxyl group-containing resin, a resin containing a carboxyl group in the molecule can be used. In particular, the carboxyl group has the effect of increasing the reaction rate of hydroxyl groups and amino groups, hydroxyl groups and silanol groups and / or alkoxysilane groups, silanol groups and / or alkoxysilane groups, and improving the coating finish. The carboxyl group has a resin acid value of about 0 to 50, preferably about 5 to 20.

The type of the hydroxyl group-containing resin is not particularly limited, and conventionally known coating resins can be used, but resins such as hydroxyl group-containing vinyl resin, hydroxyl group-containing polyester resin and modified resins thereof are preferably used. It is desirable to do.

The hydroxyl group-containing vinyl resin is obtained, for example, by radical polymerization of the following hydroxyl group-containing polymerizable unsaturated monomer (a) and, if necessary, other polymerizable unsaturated monomer (b) ( Co) polymers can be used.

Examples of the hydroxyl group-containing polymerizable unsaturated monomer (a) include (a-1) to (a-5). (A-1) Hydroxyalkyl vinyl ether: hydroxybutyl vinyl ether and the like, (a-2) allyl alcohol and methallyl alcohol, (a-3) hydroxyalkyl ester of (meth) acrylic acid: hydroxyethyl (meth) acrylate, hydroxypropyl (Meth) acrylate, hydroxybutyl (meth) acrylate, etc., (a-4) (poly) alkylene glycol monoacrylate, ethylene glycol monoacrylate, polyethylene glycol monoacrylate, etc.
(A-5) (a-1) to (a-4) and an adduct of a lactone (for example, ε-caprolactone, γ-valerolactone), etc. (for example, Praxel FM-1, the same left FM-2,
Same as left FM-3, Same as left FA-1, Same as left FA-2, Same as left FA
-3 etc., manufactured by Daicel Chemical Co., Ltd., trade name, hydroxyethyl caprolactone-modified (meth) acrylates)

Further, other polymerizable unsaturated monomer (b)
As, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
C _1-24 alkyl or cycloalkyl esters of (meth) acrylic acid such as hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate: (meth) acrylic acid , Crotonic acid, itaconic acid,
(Anhydrous) Maleic acid, fumaric acid, carboxyl group-containing compounds such as 2-carboxyethyl (meth) acrylate: Vinyl aromatic compounds such as styrene and vinyltoluene: Perfluorobutylethyl (meth) acrylate, perfluoro Perfluoroalkyl (meth) acrylates such as isononylethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate and (meth) acrylonitriles, olefins, fluoroolefins, vinyl esters, cyclohexyl or alkyl vinyl ethers , Aryl ethers and the like.

The hydroxyl group-containing vinyl resin is produced by a conventionally known method, for example, a mixture of the above-mentioned monomer (a) and, if necessary, other monomer (b) is used as a substantially inert organic solvent. In the presence of a radical polymerization initiator in the range of about 80-22
It can be carried out by continuing the reaction at 0 ° C. for about 4 to 18 hours.

Examples of the organic solvent include aromatic hydrocarbon solvents such as xylene and toluene; ester solvents such as ethyl acetate, propyl acetate and butyl acetate; ketone solvents such as acetone and methyl ethyl ketone; ethylene glycol, cellosolve, butyl cellosolve and cellosolve acetate. And the like, such as ether type. The organic solvent may be used alone or in combination of two or more.

Further, usable radical polymerization initiators include, for example, 2,2'-azoisobutyronitrile,
2,2′-azobis (2,4-dimethylvaleronitrile and other azo initiators; benzoyl peroxide, lauryl peroxide, tert-butyl peroctoate and other peroxide initiators, and hydroxyl group-containing vinyls. The number average molecular weight of the resin is about 2,000 to 80,
000, preferably in the range of about 4,000-40,000. If the molecular weight is less than about 2,000, the melt viscosity of the base coat will be too low during baking, and the orientation of the metal flakes will change, making it difficult to obtain a metallic coating. On the other hand, if the molecular weight exceeds about 80,000, the coating work will be difficult. It is not preferable because it deteriorates the property.

As the hydroxyl group-containing polyester resin, an oil-free alkyd resin obtained by reacting a polybasic acid, a polyhydric alcohol and optionally an aromatic monobasic acid, or a polybasic acid, a polyhydric alcohol, and if necessary, An alkyd resin obtained by reacting an aliphatic monobasic acid in addition to an aromatic monobasic acid is mentioned.

The polybasic acid, polyhydric alcohol, aromatic or aliphatic monobasic acid used in the production of the above (oil-free) alkyd resin will be described below.

Examples of polybasic acids include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydroterephthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, het acid, trimellitic acid and hexa. Hydrotrimellitic acid,
Pyromellitic acid, cyclohexanetetracarboxylic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, endomethylenehexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, adipine acid,
Azelaic acid, sebacic acid, decanedicarboxylic acid, suberic acid, pimelic acid, dimer acid (a dimer of tall oil fatty acid), tetrachlorophthalic acid, naphthalenedicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4
Examples include ′ -dicarboxybiphenyl and the like, their acid anhydrides and dialkyl esters, especially dimethyl ester.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-butanediol and 1,5-pentanediol. 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyltrimethylene glycol, 3,
-Methyl-pentane-1,5-diol, 3-methyl-
4,5-pentanediol, 2,2,4-trimethyl-
1,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 2,5-hexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, dipropylene glycol, tri Ethylene glycol, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, polyalkylene oxide, bishydroxyethyl terephthalate, (hydrogenated) bisphenol A alkylene oxide adduct, glycerin, trimethylolpropane, trimethylolethane, diglycerin, penta Examples thereof include erythritol, dipentaerythritol and sorbitol. Kajura E1
Monoepoxy compounds such as 0 (manufactured by Shell Chemical Co.), α-olefin epoxide and butylene oxide can also be used as a kind of glycol.

Compounds having both carboxylic acid and hydroxyl group in the molecule can also be used. Examples of such compounds include dimethylolpropionic acid, pivalic acid, and 1
2-hydroxystearic acid, ricinoleic acid, etc. are mentioned. Lactones such as ε-caprolactone and γ-valerolactone are also cyclic ester compounds, and thus belong to the category of the above compounds.

Examples of the aromatic monobasic acid include benzoic acid and p-tert-butylbenzoic acid.

Examples of the aliphatic monobasic acid include caproic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isononanoic acid, coconut oil (fatty acid) and the like.

The above-mentioned (oil-free) alkyd resin can be produced by a conventionally known method, for example, an esterification catalyst (for example, dibutyltin dilaurate) with a mixture of the above polybasic acid, polyhydric alcohol, and if necessary, a monobasic acid. It can be carried out by carrying out an esterification reaction or a transesterification reaction in the presence of. The mixing ratio of the polybasic acid and the polyhydric alcohol is about 0.7 to 0.99 mol, preferably about 0.8 to 0.98, based on 1 mol of the polyhydric alcohol component.
It is desirable to set it in the molar range. In addition, the esterification catalyst is a total measurement of polyhydric alcohol and polybasic acid components 100
It is desirable to blend in an amount of about 0.1 to 1.0 parts by weight, preferably about 0.2 to 0.5 parts by weight, relative to parts by weight.
The reaction conditions are usually in the range of about 160 to 280 ° C., preferably about 180 to 260 ° C. for about 5 to 12 hours, preferably about 6 to 8 hours.

The number average molecular weight of the hydroxyl group-containing polyester resin can be in the range of about 500 to 10,000. When the molecular weight is less than the above range, the melt viscosity of the base coat is reduced during baking, and it is difficult to obtain a coating having a metallic feeling by changing the orientation of the metal flakes, while when it exceeds the above molecular weight range, the coating workability is generally deteriorated. It is not preferable because

As the modified resin, for example, vinyl modified alkyd resin can be used. Examples of the vinyl-modified alkyd resin include a reaction product of a hydroxyl group-containing (oil-free) alkyd resin and a carboxyl group- or isocyanate group-containing vinyl resin, a hydroxyl group- and carboxyl group-containing (oil-free) alkyd resin, and an epoxy group-containing vinyl resin. Reaction product, alkyd resin having (radical polymerizable unsaturated group) (oil-free) (for example, alkyd resin having drying oil as an essential component, alkyd resin containing hydroxyl group and carboxyl group (oil-free), reacted with glycidyl (meth) acrylate A radical polymerization reaction of a vinyl monomer (for example, the polymerizable unsaturated monomer) in the presence of an alkyd resin), the (oil-free) alkyd resin,
A vinyl-modified alkyd resin or the like is used as a dispersion stabilizer, and a vinyl monomer (for example, the above-mentioned polymerizable unsaturated monomer) is dissolved in the dispersion stabilizer in the presence of the dispersion stabilizer. However, polymer particles obtained from the monomer may be added to an insoluble organic solvent to carry out a polymerization reaction, or the like.

The amino resin is used as a cross-linking agent, and examples thereof include a methylolated amino resin obtained by the reaction of an aldehyde with an amino component such as melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, and dicyandiamide. .. Examples of the aldehyde include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.
In addition, it is also possible to use a product obtained by etherifying this methylolated amino resin with a suitable alcohol. As an example of the alcohol used for the etherification, methyl alcohol,
Examples thereof include ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, 2-ethylbutanol and 2-ethylhexanol. As the amino resin, melamine having a high degree of etherification, that is, melamine which has an average of 3 or more methyl ethers per triazine nucleus and melamine resin in which a part of its methoxy group is substituted with an alcohol having 2 or more carbon atoms is used. it can. Among them, a low molecular weight melamine having an average degree of condensation of about 2 or less and a ratio of mononuclear bodies of about 50% by weight or more is preferable from the viewpoint of high solidification. When this is used, for example, a commonly used one such as paratoluenesulfonic acid It is preferable to add a curing catalyst.

The polyorganosiloxane is used as a cross-linking agent for a hydroxyl group-containing resin together with the amino resin and also as a resin that self-crosslinks, and the average number of polyorganosiloxane is 2 or more, preferably 2 to 10 per molecule. Having a silanol group and / or an alkoxysilane group having a number average molecular weight of 1,000 or more, preferably 1,000 to 50,000.
Is a polyorganosiloxane of. This polyorganosiloxane preferably has a ladder structure portion, and can be obtained, for example, by hydrolyzing and condensing a silane compound containing a trifunctional silane represented by the following general formula (I) as an essential component. R _x Si (OR') in _4-x ··· (I) (wherein, R and R'may be the same or different,
It represents a hydrocarbon group having 1 to 13 carbon atoms, and x represents 1. ) Examples of R and R'include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group.

The silane compound to be hydrolyzed and condensed may be only the trifunctional silane of the formula (I), but if necessary, in addition to the trifunctional silane, x of the formula (I) may be used. It may contain a bifunctional or monofunctional silane having a value of 2 or 3, and in the silane compound,
The silane of the formula (I) is preferably contained in an amount of 30% by weight or more, more preferably 80% by weight or more.

Typical examples of the silane of the formula (I) include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, ethyltrimethoxysilane and the like. Is mentioned. Examples of the bifunctional or monofunctional silane which may be mixed with the silane of the formula (I) include dimethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diisobutyldimethoxysilane, diisobutyldipropoxysilane and trimethylmethoxysilane. Is mentioned.

For the hydrolytic condensation of the silane compound, a silane compound is optionally mixed with a water-soluble solvent (eg alcohol solvent, cellosolve solvent, etc.), and a mineral acid such as hydrochloric acid, sulfuric acid, phosphoric acid or formic acid is mixed. , In the presence of organic acid such as acetic acid and water, preferably at pH 6 or less, 20
It is carried out by allowing the hydrolysis and condensation reaction to proceed with stirring at about 100 ° C to 100 ° C for about 30 minutes to 20 hours. The molecular weight of the polyorganosiloxane can be appropriately adjusted depending on the amount of water used, the type and amount of catalyst, the reaction temperature, the reaction time, and the like.

In the above polyorganosiloxane resin, when the number of silanol groups and / or alkoxysilane groups is less than 2 on average in one molecule, the curing rate of the base coat coating becomes slower than that of the top coating coating. Since the topcoat coating film begins to cure before the basecoat coating film cures, the cured topcoat coating film has defects such as blemishes and the finished appearance of the coating film deteriorates.

Further, in the polyorganosiloxane resin, if the number average molecular weight is less than 1,000, the melt viscosity of the base coat is lowered during baking, the orientation of the metal flakes is changed, and a coating film having a metallic feeling cannot be obtained. There is.

The metal chelate compound is used to promote the reaction between the functional groups of the polyorganosiloxane or the reaction between the functional groups of the polyorganosiloxane and the hydroxyl group of the hydroxyl group-containing resin, and for example, aluminum, A metal chelate compound in which a chelate compound capable of forming a ketone / enol tautomer is coordinated to a metal alkoxide in which an alkoxyl group is bonded to a metal such as titanium, zirconium, calcium, barium or the like can be preferably used. Among the above, the aluminum metal chelate compound is preferable, and specifically, 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 (propionylacetonate) ) Aluminum, acetylacetonato bis (propionylacetonate) aluminum and the like.

The metal flakes give a metallic feeling to the coating film, and examples of the metal flakes include aluminum flakes, nickel flakes, copper flakes,
Examples thereof include brass flakes and chrome flakes, and examples of the mica powder include pearl mica and colored pearl mica.

Examples of the organic solvent include aromatic hydrocarbon solvents such as xylene and toluene; ester solvents such as ethyl acetate, propyl acetate and butyl acetate; ketone solvents such as acetone and methyl ethyl ketone; ethylene glycol, cellosolve, butyl cellosolve, cellosolve acetate. And the like, such as ether type. The organic solvent may be used alone or in combination of two or more. From the viewpoint of curability, those having a boiling point of about 150 ° C. or less are preferable, but the boiling point is not limited to this.

In the coating composition for a base coat, the proportion of the hydroxyl group-containing resin, amino resin and polyorganosiloxane serving as a binder is 5% by weight based on 100 parts by weight of the total amount (resin solid content) of the three components. ~
90 parts by weight, preferably 30 to 60 parts by weight, amino resin 5 to 50 parts by weight, preferably 10 to 40 parts by weight, polyorganosiloxane 1 to 40 parts by weight, preferably 5 to 30 parts by weight.
Parts by weight, more preferably 5 to 20 parts by weight.

When the compounding amount of the hydroxyl group-containing resin is less than 5 parts by weight, the adhesion to the base is deteriorated, while when it exceeds 90 parts by weight, the finish appearance of the coating film and the coating film performance (water resistance, processability, etc.) Is reduced. If the compounding ratio of the amino resin is less than 5 parts by weight, the crosslink density of the hydroxyl group-containing vinyl resin is small and the water resistance and impact resistance are significantly impaired. If the compounding amount exceeds 50 parts by weight, the mechanical properties and the adhesion to the substrate are improved. And other problems occur. Further, when the mixing ratio of the organopolysiloxane is less than 1 part by weight, the effect of accelerating the curing speed of the base coat coating is small and the finished appearance of the coating cannot be improved. It is not preferable because it deteriorates the property.

The compounding ratio of the metal chelate compound is 3 of the above hydroxyl group-containing resin, amino resin and polysiloxane.
About 0.01 to 10 parts by weight, and preferably about 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the components. If the blending ratio is less than about 0.01 parts by weight, curability and finish of the coating film are deteriorated. On the other hand, if the blending amount is more than about 10 parts by weight, the coating film tends to be colored (yellow) or has water resistance. Is reduced, which is not preferable. The mixing ratio of the metal flakes may be about 1 to 20 parts by weight based on 100 parts by weight of the total amount of the three components of the hydroxyl group-containing resin, amino resin and polysiloxane.

In addition to the above-mentioned components, the coating composition for the base coat contains, if necessary, organic pigments, inorganic pigments, pigment dispersants, polymer fine particles, ultraviolet absorbers, coating surface adjusting agents, curing catalysts, cellulose acetate ( And their derivatives),
Other additives for paints may be contained.

The pigment which may be contained in the paint is
For example, organic pigments (for example, quinacridone type such as quinacridone red, azo type such as pigment red, phthalocyanine type such as phthalocyanine blue, phthalocyanine green, etc.), inorganic pigments (for example, titanium oxide, barium sulfate,
Calcium carbonate, barita, clay, silica, etc.), carbon-based pigments (carbon black), and the like. The coating composition for the base coat may have a three-component solid content of a hydroxyl group-containing resin, an amino resin and polysiloxane of about 10 to 50% by weight.

Clear Top Coat The clear top coat is a base resin (1) containing a hydrolyzable group directly bonded to a silanol group and / or a silicon atom, a hydroxyl group and an epoxy group (hereinafter referred to as "base resin for top coat"). Abbreviated), a curing catalyst (2) and an organic solvent (3) as essential components.

The hydrolyzable group contained in the base resin for a top coat is a residue which is hydrolyzed in the presence of water to form a silanol group. For example, a C ₁ -C ₅ alkoxy group; a phenoxy group / tolyloxy group. Group, paramethoxyphenoxy group, paranitrophenoxy group, benzyloxy group and other aryloxy groups; acetoxy group, propionyloxy group, butanoyloxy group, benzoyloxy group,
Phenylacetoxy group, an acyloxy group, and -N such formyloxy group _{(R 1) 2, -ON (} R 1) 2, -ON
_{= C (R 1) 2,} -NR 2 COR 1 ( wherein, each R
₁ is the same or different and represents a C _{1 to} C ₈ alkyl group, an aryl group or an aralkyl group, and R ₂ is H or C _{1 to} C ₈
Represents an alkyl group of. ) And the like.

The base resin for the top coat is, for example, a resin containing a hydroxyl group (A), an epoxy group containing resin (B), a silanol group and / or a resin containing a hydrolyzable group directly bonded to a silicon atom (C). A resin mixture (hereinafter, abbreviated as “resin”) containing three components, an epoxy group-containing resin (B), a resin (C) containing a silanol group and / or a hydrolyzable group directly bonded to a silicon atom. A two-component resin mixture, and a resin (B)
And a resin mixture (hereinafter, abbreviated as “resin”) containing a hydroxyl group in either or both of the resin (C), a hydroxyl group, an epoxy group, a silanol group and / or a hydrolyzable group directly bonded to a silicon atom. The resin contained (hereinafter abbreviated as “resin”) and the like can be mentioned.

Resin: As the hydroxyl group-containing resin (A),
Those having an average of two or more hydroxyl groups in one molecule and having a number average molecular weight of 1,000 to 200,000, preferably 3,000 to 80,000 can be used. If the average number of hydroxyl groups is less than 2, the curability (gel fraction) will be poor, which is not preferable. From the viewpoint of finishability, water resistance, etc., the number of hydroxyl groups is preferably 400 or less on average. If the number average molecular weight is less than 1,000, the mechanical properties, finish, water resistance, etc. will be poor.
If it exceeds 50,000, the compatibility with other components will decrease,
As a result, the curing is not uniform and the finish is inferior, which is not preferable.

As the hydroxyl group-containing resin (A), conventionally known resins can be used, but it is particularly preferable to use a vinyl polymer from the viewpoints of weather resistance and finish. The hydroxyl group-containing resin (A) is obtained by polymerizing the hydroxyl group-containing polymerizable unsaturated monomer (a) and the other polymerizable unsaturated monomer (b) in the same manner as described above. The obtained one can be used.

The epoxy group-containing resin (B) has an average of 2 to 300 epoxy groups in one molecule and preferably has a number average molecular weight of 120 to 200,000, preferably 24.
0 to 80,000. If the number of epoxy groups is less than 2 on average, the curability, finish and impact resistance will be poor, which is not preferable. It is difficult to obtain a compound having a number average molecular weight of less than 120. On the other hand, when the number average molecular weight exceeds 200,000, the compatibility with other components is poor, and the resulting coating film has weather resistance and finish properties. And so on are not preferable.

Examples of the epoxy group-containing resin (B) include alicyclic polyepoxide crosslinking agents (for example,

[0050]

[Chemical 1]

Etc.), an oxirane group-containing polymerizable unsaturated monomer (c) (for example, an alicyclic vinyl monomer of the general formulas (4) to (18) described in JP-A-2-160879). A homopolymer or a copolymer with the other polymerizable unsaturated monomer (b) can be preferably used.

Examples of the resin (C) containing a silanol group and / or a hydrolyzable group directly bonded to a silicon atom include γ- (meth) acryloxypropyltrimethoxysilane and γ (meth) acryloxypropyltriethoxy. Silane, γ (meth) acryloxypropyltrisilanol, γ- (meth) acryloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-styrylethyltrimethoxysilane,
Silane compounds such as allyltriethoxysilane (d
-1); a reaction product (d-2) with the silane compound (d-1) and a trialkoxy or trihydroxysilane compound (for example, methyltrimethoxysilane, phenyltrimethoxysilane, methyltrisilanol) (for example, Japanese Patent Application Laid-Open No. HEI-2)
Homopolymers of polysiloxane macromonomers described in JP-A-160879) or copolymers with other polymerizable unsaturated monomers (b) can be preferably used.

The mixing ratio of the above resins (A), (B) and (C) is such that the total amount of these three components is 5 to 95.
% By weight, preferably 20-80% by weight, resin (B) 95
~ 5 wt%, preferably 80-20 wt%, resin (C)
The range of 0.1 to 80% by weight, preferably 1 to 20% by weight is preferable from the viewpoints of curability and coating finish.

Resin: As the epoxy group-containing resin (B) and the resin (C) having a silanol group and / or a hydrolyzable group directly bonded to a silicon atom, the same ones as described above can be used.

Further, in the resin, either or both of the resin (B) and the resin (C) have a hydroxyl group. As a method of introducing a hydroxyl group into the resin (B) and the resin (C), For example, the hydroxyl group-containing polymerizable unsaturated monomer (a) can be used as a monomer component as an essential monomer component. In this case, the number of hydroxyl groups is 1
It is preferable to contain 1 or more on average, preferably 400 or less on average in the molecule. The number average molecular weight of the resin having a hydroxyl group introduced is 1,000 to 200,000, preferably 3,000 to 80,000.

The mixing ratio of the resins (B) and (C) is such that the total amount of these two components is 5 to 95.
% By weight, preferably 20-80% by weight, resin (C) 95
The range of 5 to 5% by weight, preferably 80 to 20% by weight is preferable from the viewpoint of curability and coating finish.

The hydroxyl group-containing resin (A) may be blended with the resin, if necessary.

Resin: The resin has an average of one or more silanol groups and / or an average of 2-40 silanol groups per molecule.
Alternatively, a hydrolyzable group directly bonded to a silicon atom has an average of 1 or more, preferably 2 to 40 epoxy groups in one molecule and an average of 2 to 200 hydroxyl groups in one molecule. Also, it is preferable from the viewpoint of coating film finishing property.

The resin is, for example, the hydroxyl group-containing polymerizable unsaturated monomer (a), the oxirane group-containing polymerizable unsaturated monomer (c), the silane compound (d-1) and / or the reaction product (d). -2), and a copolymer with other polymerizable unsaturated monomer (b) can be suitably used if necessary.

The mixing ratio of the monomers (a) to (d-2) may be such that the functional group in the resin is within the above range.

The number average molecular weight of the resin is from 1,000 to
200,000, preferably 3,000-80,000
What is desirable.

The hydroxyl group-containing resin (A) may be blended with the resin, if necessary.

The base resin is, for example, a hydrocarbon solvent such as toluene or xylene, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, an ester solvent such as ethyl acetate or butyl acetate, an ether such as dioxane or ethylene glycol diethyl ether. It is used in the form of a solution type, a dispersion type, a non-aqueous dispersion type, or the like dissolved or dispersed in an organic solvent, an alcohol solvent such as butanol or propanol, or an aliphatic hydrocarbon such as pentane, hexane or heptane.

The non-aqueous dispersion type base resin composition comprises the above resin or a dispersion stabilizer, and in the presence of the dispersion stabilizer, one or more radically polymerizable unsaturated monomers and a polymerization initiator. Is dissolved in an organic solvent in which the monomer and the dispersion stabilizer are dissolved but the polymer particles obtained from the monomer are not dissolved, and a polymerization reaction is carried out to produce a non-aqueous dispersion liquid. You can When the resin used as the dispersion stabilizer is a mixture, that is, when a resin or is used, a part or all of the components of the resin mixture are used as the dispersion stabilizer to polymerize the monomers, and some components of the resin mixture are mixed. When used, a non-aqueous dispersion is obtained by blending the remaining components. As the kind of the monomer that can be used to form the polymer that becomes the particle component of the non-aqueous dispersion, all the monomers described above can be used. Since the polymer used as the particle component is preferably not soluble in the organic solvent used, it is a copolymer containing a large amount of highly polar monomers. That is, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylonitrile,
Monomers such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylamide, acrylic acid, methacrylic acid, itaconic acid, styrene, vinyltoluene, α-methylstyrene, N-methylol (meth) acrylamide It is preferable to contain a large amount of. Further, the particles of the non-aqueous dispersion may be crosslinked if necessary. As an example of a method for crosslinking the inside of the particles, it can be carried out by copolymerizing a polyfunctional monomer such as divinylbenzene or ethylene glycol dimethacrylate.

Although the dispersion polymer particles produced by the polymerization are not substantially dissolved in the organic solvent used for the non-aqueous dispersion,
The dispersion stabilizer and the radical-polymerizable unsaturated monomer include those which are good solvents. Generally, an aliphatic hydrocarbon is mainly used, and an aromatic hydrocarbon and an appropriate combination of the above alcohol-based, ether-based, ester-based, or ketone-based solvent are preferably used. Furthermore, trichlorotrifluoroethane, metaxylene hexafluoride, tetrachlorohexafluorobutane, etc. can be used if necessary.

Polymerization of the above monomers is carried out using a radical polymerization initiator. Examples of usable radical polymerization initiators include 2,2′-azoisobutyronitrile,
Azo initiators such as 2,2′-azobis (2,4-dimethylvaleronitrile); peroxide initiators such as benzoyl peroxide, lauryl peroxide, tert-butyl peroctoate, and the like. The agent is generally 0.2 per 100 parts by weight of the monomer to be polymerized.
It can be used within the range of 10 to 10 parts by weight. The composition of the dispersion stabilizer resin to be used during the above polymerization can be selected from a wide range depending on the type of the resin, but generally 3 to 3 parts by weight of the radically polymerizable unsaturated monomer is added to 100 parts by weight of the resin. About 240 parts by weight, preferably 5 to 82 parts by weight is suitable.

In the present invention, the dispersion stabilizer resin and the polymer particles may be combined.

In the resin composition of the above non-aqueous dispersion, the solid phase, which is polymer particles obtained by polymerizing the radically polymerizable unsaturated monomer, is stably dispersed in the liquid phase in which the dispersion stabilizer resin is dissolved in the organic solvent. With this dispersion, the solid content at the time of coating can be greatly increased, and since the viscosity after coating is high, a coating film having an excellent finished appearance without sagging or flowing can be formed. Furthermore, the formed coating film is a photo-chemically stable coating film in which the continuous phase of the coating film has an organic silane group, and the polymer particle component in the coating film is stabilized by the continuous phase. In addition, since the coating film is reinforced by the particle component, a coating film having excellent mechanical properties such as impact resistance can be formed.

As the curing catalyst, metal chelate compounds (for example, the same ones as described above), Lewis acids (for example, aluminum trichloride, 1-diethylaluminum trichloride, boron trifluoride, etc.), protic acids (for example, benzenesulfonic acid, p-toluenesulfonic acid, phosphoric acid, etc.), Si-
Examples thereof include compounds having an O-Al bond (eg, aluminum silicate). Among the above, metal chelate compounds, and further aluminum chelate compounds are preferable because they can form a coating film excellent in finished appearance and durability.

The mixing ratio of the curing catalyst is 0.01 to 30 parts by weight, preferably 0.1 to 100 parts by weight of the resin.
10 to 10 parts by weight. When the amount of the curing catalyst is less than 0.01 parts by weight, the curability and the finish of the coating film are deteriorated, and when it exceeds 30 parts by weight, the finishability and the water resistance of the coating film are deteriorated, which is not preferable.

If necessary, the clear coat coating composition may contain an ultraviolet absorber, an antioxidant, a light stabilizer, and various other additives for coatings.

In the method of the present invention, for example, a chemically treated steel sheet is coated with an electrodeposition paint, and an intermediate coating paint (may be omitted).
Painted with a paint and a primer suitable for various plastic materials, a paint with an intermediate paint (sometimes omitted) is applied as a material, a colored base coat paint composition is applied, and then a clear coat paint composition This can be done by painting the object. The above-mentioned electrocoating paint and intermediate coating paint differ depending on the type of paint, but usually 140-
Bake at 190 ° C for 30-90 minutes. The pigmented base and clear coat coating composition can be coated by a conventional coating method, for example, electrostatic coating or non-electrostatic coating machine. The thickness of the colored base coat is 10 to 50 μm.
A degree (after curing) is preferable. After coating the coating composition, the coating composition is left at room temperature for several minutes or forcedly dried at about 50 to 80 ° C. for several minutes, and then coated with the clear coat coating composition. The thickness of the clear coating film is preferably 20 to 100 μm (after curing). Then, the article to be coated can be heated and cured at about 120 to 180 ° C. for about 30 to 90 minutes.

[0073]

In the method of the present invention, a paint for a colored base coat finished by a two-coat one-bake method is used as a binder component, which is a polyorganosiloxane having two or more silanol groups and / or alkoxysilane groups in one molecule. It contains a metal chelate compound, and the reaction between silanol groups (or silanol groups generated by hydrolysis of alkoxysilane groups) by heating or the reaction between silanol groups and hydroxyl groups in the hydroxyl group-containing resin is in the presence of metal chelate compounds. It is carried out rapidly at relatively low temperatures. Since this reaction occurs faster than the curing reaction of the clear coat paint, the viscosity of the base coat paint increases faster than that of the clear coat paint in the early stage of baking. Therefore, it is considered that the base coating film that can withstand the shrinkage force of the coating film due to the volume change due to the curing of the clear coating composition and the volatilization of the solvent was formed, and the finished appearance of the coating film was improved.

When coating is carried out by the two-coat one-bake system, a layer (mixed layer) in which these coats are mixed is generally formed at the interface between the colored base coat and the clear top coat. In this case, the reason is not clear, but the curability in the mixed layer is lower than the curability of these single layers, and usually the coating performance such as the finished appearance and solvent resistance is reduced, but in the present invention, A coating film excellent in finished appearance and solvent resistance can be formed without such defects.

Further, when the clear base coat cured coating film was coated with the colored base coat coating composition and recoated, improvement in adhesion between the coating films was also observed.

[0076]

The present invention will be described in more detail with reference to the following examples. In the following, "parts" and "%" mean "parts by weight" and "% by weight", respectively.

Production Example of Resin for Colored Base Coat Production Example 1 30 parts of styrene and 40 parts of n-butyl methacrylate in an organic solvent of 85 parts of xylol and 15 parts of n-butanol,
10 parts of 2-ethylhexyl acrylate, 18 parts of 2-hydroxyethyl acrylate, and 2 parts of acrylic acid are reacted to produce a number average molecular weight of 6,600, a resin solid content of 50%, a hydroxyl group containing Gardner foam viscosity (25 ° C.) J. An acrylic resin solution (a-1) was obtained.

Production Example 2 30 parts of styrene and 30 parts of n-butyl methacrylate in an organic solvent of 85 parts of xylol and 15 parts of n-butanol.
Part, 2-ethylhexyl acrylate 15 parts, and 2-hydroxyethyl acrylate 25 parts of monomers are reacted to give a hydroxyl group-containing acrylic resin having a number average molecular weight of 5,000, a resin solid content of 50%, and a Gardner foam viscosity (25 ° C.) B. A solution (a-2) was obtained.

Production Example 3 48 parts (0.29 mol) of isophthalic acid, 38 parts (0.23 mol) of phthalic acid, 74 parts of hexahydrophthalic acid (0.
43 mol), 53.6 parts of trimethylolpropane (0.
4 mol), 62 parts (0.6 mol) of neopentyl glycol and 21 parts (0.1 mol) of coconut oil fatty acid are added to a reaction vessel, and coconut oil having an acid value of 8 and a hydroxyl value of 72 by condensation polymerization at 200 to 230 ° C. A modified polyester resin was obtained. 43 parts of xylene was added to 100 parts of the polyester resin to obtain a resin solution (a-3) having a resin solid content of 60% by weight and a Gardner foam viscosity (25 ° C.) Y ⁻ .

Production Example 4 Phenyltrimethoxysilane 198 parts Deionized water 54 parts 98% sulfuric acid 0.002 parts were mixed, reacted at 60 ° C. for 5 hours, methanol was removed by reduced pressure, and xylol was added to obtain a solid content. A polyorganosiloxane liquid (b-1) having an AB viscosity of 50% and a Gardner foam viscosity (25 ° C.) was obtained. The obtained polyorganosiloxane had a number average molecular weight of about 5,000 and had an average of 6 silanol groups per molecule.

Production Example 5 Methyltrimethoxysilane 136 parts Diphenyldimethoxysilane 182 parts Deionized water 90 parts 60% phosphoric acid 1 part were mixed and reacted at 60 ° C. for 10 hours, and then methanol was removed under reduced pressure to remove butyl acetate. Add 50% solids,
A polyorganosiloxane liquid (b-2) having a Gardner foam viscosity (25 ° C.) D was obtained. The obtained polyorganosiloxane had a number average molecular weight of about 15,000, and
It had an average of 10 silanol groups.

Colored base coat coating composition paints I-1 to 6 Resin solutions (a-1 to 3) obtained in Production Examples 1 to 3, Uban 20SE (Note 1), Resin solutions obtained in Production Examples 4 to 5 (B-
1-2) were mixed in the composition shown in Table 1, and then 100 parts of these mixtures (solid content) were mixed with aluminum paste 2
Add 0 parts and stir, then add Swazol 1000 (Note 2) and paint viscosity 15 seconds (Ford cup # 4/20 ° C)
Was adjusted to obtain a paint corresponding to the example. (Note 1) U-Van 20SE ... Mitsui Toatsu Chemicals, Inc., butyl etherified melamine resin solution with a solid content of about 60%, trade name. (Note 2) Swazol 1000 ... Maruzen Sekiyu KK, aromatic solvent, trade name.

Paints I-7 to 10 Mixtures shown in Table 1 were mixed and aluminum paste and Swazol 1000 were added in the same manner as Paint I-1 to obtain paints corresponding to Comparative Examples.

[0084]

[Table 1]

Production Example of Clear Coat Resin Production Example 6 γ-methacryloxypropyltrimethoxysilane 100 parts below styrene 150 parts

[0086]

[Chemical 2]

Cyclohexyl methacrylate 200 parts tert-butyl methacrylate 150 parts Hydroxybutyl acrylate 100 parts Azobisisobutyronitrile 10 parts A mixture of butanol and xylene in an equal weight mixture 1,0
The mixture was added dropwise to 00 parts and reacted at 120 ° C. to obtain a transparent copolymer having a solid content of 50% by weight and a copolymer number average molecular weight of about 20,000.

Production Example 7 400 parts of the following cyclohexyl methacrylate 150 parts of γ-methacryloxypropylmethyldimethoxysilane

[0089]

[Chemical 3]

2-Hydroxyethyl methacrylate 100 parts Azobisisobutyronitrile 10 parts a mixture of equal weight butanol and xylene 1,0.
The mixture was added dropwise to 00 parts and reacted at 120 ° C. to obtain a transparent copolymer having a solid content of 50% by weight and a copolymer number average molecular weight of about 20,000.

Production Example 8 Methyltrimethoxysilane 2720 parts γ-methacryloxypropyltrimethoxysilane 256 parts Deionized water 1134 parts 6% hydrochloric acid 2 parts Hydroquinone 1 part The mixture was reacted at 80 ° C. for 5 hours to obtain a polysiloxane macromonomer. Got The obtained polysiloxane macromonomer had a number average molecular weight of 2,000, and had one vinyl group (polymerizable unsaturated bond) and four hydroxyl groups per molecule on average.

Next, the polysiloxane macromonomer 100 parts, n-butyl methacrylate 200 parts, cyclohexyl methacrylate 300 parts

[0093]

[Chemical 4]

2-Hydroxyethyl acrylate 100 parts Mixture of azobisisobutyronitrile 10 parts with an equal weight mixture of butanol and xylene 1,0.
It is added dropwise to 00 parts and polymerized at 120 ° C. to give a transparent solid content of 50.
A weight% copolymer was obtained. The number average molecular weight of the copolymer is about 4
It was 10,000.

Coating composition for clear coat Coating composition II-1 100 parts of the resin solid content obtained in Preparation Example 6 was mixed with 1 part of tris (acetylacetonato) aluminum, and then the coating viscosity was 22 seconds with Swazol 1000. (Ford Cup N
o. 4/20 ° C.).

Coating Composition II-2 Same as Coating Composition II-1 except that the resin obtained in Production Example 7 was used in place of the resin obtained in Production Example 6 in Production Example of Coating Composition II-1. The coating composition II-2 was prepared by the method described in 1.

Coating Composition II-3 Same as Coating Composition II-1 except that in Preparation Example II-1 above, the resin obtained in Preparation Example 6 was used instead of the resin obtained in Preparation Example 6. The coating composition II-3 was prepared by the method described in 1.

Dull steel sheet (chemical conversion treatment) was coated with an epoxy resin-based cationic electrodeposition paint (25 μm), and it was heated at 170 ° C. for 30 days.
After being heat-cured for a minute, as an intermediate coat, Rugerbake AM
(Trademark product, Kansai Paint Co., Ltd., polyester resin /
Melamine resin-based automotive paint) with a dry film thickness of 30 μm
And was baked at 140 ° C. for 30 minutes. Next, the coated surface was water-polished with # 400 sandpaper, drained and dried, and the coated surface was wiped with petroleum benzine as a material.

As the coating material, the coating material for colored base coat was applied by air spray coating and left for 3 minutes, and then the coating material for clear top coat was immediately coated. The dry film thickness is 15 each
.About.20 .mu.m and 35 to 45 .mu.m. Then at room temperature 10
Let stand for 30 minutes at 140 ° C for 30 minutes (However, for recoatability, bake the first time at 160 ° C for 30 minutes and the second time at 120 ° C.
Baking was performed at 30 ° C. for 30 minutes. The coating performance and appearance are shown in Table 2.

[0100]

[Table 2]

(* 1) Appearance: The coating film was examined for cracks and blemishes. ◎ No abnormality, ○ Slightly recognized, × Many recognized. (* 2) Image clarity: Image clarity measuring device (IMAGE CLARITY METER,
It was measured by Suga Test Instruments Co., Ltd. The numbers in the table are ICM
The value is in the range of 0 to 100%, and the larger the value, the better the image clarity (image clarity), and the ICM value of 75 or more indicates that the image clarity is extremely excellent. (* 3) Metallic feeling: The metallic feeling and whiteness of the metal when viewed from the front were visually evaluated. ◎ There is a feeling of gleaming, white, there is no feeling of gleaming, and it is inferior in whiteness. × There is no feeling of gleaming and there is no whiteness. (* 4) Water resistance: The sample coated plate was immersed in warm water of 40 ° C. for 240 hours, and the blistering state of the coated surface was visually evaluated. ◎ No abnormality, △ Slightly observed, × markedly observed. (* 5) Recoatability: The same base paint and clear paint as in Examples and Comparative Examples were applied over the surface of the coating film, and 120 ° C.
It was baked for 30 minutes to obtain a coating film. Cross-cut the obtained coating film with a cutter knife and stick cellophane tape on the coated surface, and peel it off rapidly, and the adhesion between the first and second coating films (clear coating / base coating) Was evaluated.
◎ No peeling was observed, △ Slight peeling was observed, × Marked peeling was observed. (* 6) Solvent resistance: After being immersed in Nisseki Silver Gasoline (trade name, manufactured by Nippon Oil Co., Ltd.) for 1 day, the state of the coating film and the hardness of the coating film were visually examined. Coating state ◎ No abnormality, ○ Very slight streaks occur,
△ Tige spots occur, x Tige spots occur remarkably. Coating film hardness after test / Coating film pencil hardness before test

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C09D 161/20 PHK 8215-4J 163/00 PJD 8830-4J 183/06 PMU 8319-4J 201/10 PDP 7242-4J // C09D 201/06 PDL 7242-4J

Claims (1)

[Claims] 1. In a topcoat coating method in which a colored base coat and a clear top coat are sequentially formed on a material and finished by a two-coat one-bake system, a coating composition for forming a colored base coat includes (1) a hydroxyl group-containing resin (2) an amino resin (3) Number average molecular weight of 1,000 having an average of two or more silanol groups and / or alkoxysilane groups in one molecule
Using a coating composition containing the above polyorganosiloxane (4) metal chelate compound (5) metal flake powder and / or mica powder and (6) organic solvent as an essential component, as a coating composition for forming a clear top coat , (1) a resin having at least one group selected from a silanol group and a hydrolyzable group directly bonded to a silicon atom, a hydroxyl group and an epoxy group (2) a curing catalyst and (3) an organic solvent as essential components A method for forming a coating film, which comprises using a coating composition.