JPH05169023A - Formation of coating film - Google Patents

Abstract

PURPOSE:To obtain a coating film excellent in finishing property, recoating property, etc., by forming a clear topcoat on a specified colored base coat. CONSTITUTION:In the two coat-one bake overcoating, a coating composition contg. a hydroxyl-contg. vinyl resin, an amino resin, a polyorganosiloxane contg. average >=2 silanol groups and/or alkoxysilane groups and average >=1 epoxy group in one molecule and having >=1000 number average mol.wt., a metal flake powder and/or a mica powder and org. solvent as the essential components is used as the colored base coat. A coating composition contg. a resin contg, a silanol group, a group selected from the hydrolyzable groups directly bonded to silicon atom and a hydroxyl as the essential functional groups, an amino resin and org. solvent as the essential components is used as the clear topcoat. A coating film withstanding the shrinkage force due to volume change and excellent in finishing property, recoating property, etc., is obtained in this way.

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. The coating composition is a silicone coating composition prepared by blending a metal chelate compound with a copolymer having a silanol group- and / or alkoxysilane group-containing polysiloxane macromonomer and an oxirane group-containing vinyl monomer as monomer components. , This is a metallic base coat (paint mixed with aluminum flake pigment)
/ Applicable to both clear top coats, 2 coats / 1
In the case of paint finish using the bake method, the metallic base coat is affected by the clear top coat, and the orientation of the aluminum flake pigment changes, resulting in the inability to obtain a coating film with aluminum luster (there is a feeling of gleaming and white). In addition, in the case where a thermosetting acrylic resin / melamine resin-based material is used as the metallic base coat, the clear top coat starts to be cured before the curing of the metallic base coat, and as a result, the coating film is free from cracks and blemishes. However, there is a defect that such defects occur.

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, the present invention provides a coating composition for forming a colored base coat 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. (2) Amino resin (3) Polyorganosiloxane having a number average molecular weight of 1000 or more and having an average of 2 or more silanol groups and / or alkoxysilane groups in one molecule and an average of 1 or more epoxy groups (4) Metal flakes A coating composition containing powder and / or mica powder and (5) an organic solvent as an essential component is used as a coating composition for forming a clear top coat. (1) Hydrolyzability directly bonded to silanol groups and silicon atoms Resin containing at least one group selected from the group and a hydroxyl group as an essential functional group component The present invention relates to a method for forming a coating film, which comprises using a coating composition containing (2) an amino resin and (3) an organic solvent as essential components.

Next, the method of the present invention will be specifically described. Colored Base Coat The colored base coat has (1) hydroxyl group-containing vinyl resin (2) amino resin (3) having at least two silanol groups and / or alkoxysilane groups on average in one molecule and at least one epoxy group on average. Polyorganosiloxane having a number average molecular weight of 1000 or more (hereinafter, may be simply referred to as “polyorganosiloxane”) (4) Metal flake powder and / or mica powder (hereinafter, may be simply referred to as “metal flake”) ( 5) Formed from a coating composition for base coat containing an organic solvent as an essential component.

The hydroxyl group-containing vinyl 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 speed 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 deteriorates, and the curing thereof is not sufficient, so that the coating film performance (water resistance, impact resistance, etc.) decreases. 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 vinyl resin, one containing a carboxyl group in the molecule can be used. Particularly, the carboxyl group has the effect of increasing the reaction rate of the hydroxyl group and the amino group, the hydroxyl group and the silanol group and / or the alkoxysilane group, the silanol group and / or the alkoxysilane group, and improving the finish of the coating film. The carboxyl group has a resin acid value of about 0 to 50, preferably about 5 to 2
A range of 0 is good.

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, etc. (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 lactones (eg, ε-caprolactone, γ-valerolactone), and the like (eg, 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 and the like, 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 vinyltoluene: Perfluorobutylethyl (meth) acrylate, perfluoroiso Perfluoroalkyl (meth) acrylates such as nonylethyl (meth) acrylate and perfluorooctylethyl (meth) acrylate and (meth) acrylonitriles, olefins, fluoroolefins, vinyl esters, cyclohexyl or alkyl vinyl ethers, Aryl ethers and the like can be mentioned.

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, cellosolve acetate. And the like, such as ether type. The organic solvent may be used alone or in combination of two or more.

The usable radical polymerization initiators are, 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 about 4,000 to 20,000. 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.

The amino resin is used as a cross-linking agent, and examples thereof include a methylolated amino resin obtained by reacting an amino component such as melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine and dicyandiamide with an aldehyde. .. 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.

Polyorganosiloxane is used as a cross-linking agent for the hydroxyl group-containing polyester resin together with the amino resin,
It is also used as a resin that self-crosslinks, and has an average of 2 or more, preferably 2 to 10 silanol groups and / or alkoxysilane groups in one molecule and an average of 1
It is a polyorganosiloxane having one or more, preferably 1 to 30, epoxy groups. This polyorganosiloxane preferably has a ladder structure portion, and can be obtained, for example, by hydrolyzing and cocondensing a silane represented by the following general formula (I) and an epoxy group-containing silane represented by the general formula (II). it can. R ¹ _x Si (OR ² ) _4-X ... (I) (In the above formula, R ¹ and R ² may be the same or different and each represents a hydrocarbon group having 1 to 13 carbon atoms, and x is One, two
Or 3 is represented. )

[0019]

[Chemical 1] [In the above formula, R ³ and R ⁴ may be the same or different and each represents a hydrocarbon group having 1 to 13 carbon atoms, and y is 1, 2
Or 3 and G represents a group represented by the following formula (III) or (IV). ]

[Chemical 2] [In the above formulas (III) and (IV), R ⁵ has 1 carbon atom.
To 13 divalent hydrocarbon groups, and R ^{6 s} are the same or different and each represents a hydrogen atom or a methyl group. ]

In the above formula, the hydrocarbon group having 1 to 13 carbon atoms is preferably a group such as methyl, ethyl, propyl, butyl or phenyl. Of these, the hydrocarbon groups for R ² and R ³ are preferably groups such as methyl and ethyl. As the divalent hydrocarbon group having 1 to 13 carbon atoms, methylene, ethylene, propylene, butylene, pentamethylene, hexamethylene, phenylene and the like are preferable.

The mixing ratio of the silane of the formula (I) and the silane of the formula (II) in the co-condensation reaction is not particularly limited, but normally, the silane of the formula (I): the silane of the formula (II) is It is in the range of 95: 5 to 10:90 (weight ratio), and the sum of the silane in the formula (I) where x is 1 and the silane in which y is 1 in the formula (II) is 30 in the silane compounded. It is preferably at least wt%, more preferably at least 80 wt%.

Typical examples of the silane of the formula (I) include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, ethyltrimethoxysilane, Examples thereof include dimethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diisobutyldimethoxysilane, diisobutyldipropoxysilane, and trimethylmethoxysilane.

A typical example of the silane of the formula (II) is γ-
Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4
Examples include -epoxycyclohexyl) ethyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane.

The hydrolytic co-condensation reaction of the silanes of the formulas (I) and (II) is carried out by mixing these silane compounds with a water-soluble solvent (eg alcohol solvent, cellosolve solvent, etc.) if necessary, and adding hydrochloric acid. In the presence of water, a mineral acid such as sulfuric acid and phosphoric acid, or a catalyst such as organic acid such as formic acid and acetic acid, and water, preferably at pH 6 or less, with stirring at 20 ° C to 100 ° C for about 30 minutes to 20 hours. Is carried out by advancing hydrolysis and condensation reactions. The molecular weight of polyorganosiloxane depends on the amount of water used, the type of catalyst,
It can be appropriately adjusted depending on the amount, reaction temperature, reaction time and the like.

In the above polyorganosiloxane resin, when the number of silanol groups and / or alkoxysilane groups or epoxy groups is less than the above range, the curing speed of the base coat coating film becomes slower than that of the top coat coating film, and thus the base coating coating film. Since the topcoat coating film begins to cure before it is cured, defects such as tingling occur in the cured topcoat coating film, and the finished appearance of the coating film deteriorates.

Further, in the polyorganosiloxane resin, if the number average molecular weight is less than 1000, 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 feel cannot be obtained. ..

The metal flakes give a metallic feeling to the coating film. 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. The compounding amount of the metal flakes may be about 1 to 20 parts by weight with respect to 100 parts by weight of the resin solid content.

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, from the viewpoint of finishability, a boiling point of about 150 ° C. or lower is 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 serving as the binder, the amino resin and the polyorganosiloxane is 5 parts 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 amount of the hydroxyl group-containing resin is less than 5 parts by weight, the adhesion to the base is lowered, 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. When the blending ratio of the amino resin is less than 5 parts by weight, the crosslink density of the hydroxyl group-containing resin is small and the water resistance is low.
The impact resistance is remarkably impaired, and when the amount is more than 50 parts by weight, problems such as deterioration in mechanical properties and adhesion to the base occur. On the other hand, when the mixing ratio of the organopolysiloxane is less than 1 part by weight, the effect of accelerating the curing speed of the base coating film is small and the finished appearance of the coating film cannot be improved. Adhesion of is reduced.

In the base coat coating composition, in addition to the above-mentioned components, if necessary, an organic pigment, an inorganic pigment, a pigment dispersant, polymer fine particles, an ultraviolet absorber, a coating surface adjusting agent, a curing catalyst, a 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 usually have a resin solid content of about 10 to 50% by weight.

Clear Top Coat The clear top coat is a resin having a hydrolyzable group directly bonded to a silanol group and / or a silicon atom (hereinafter referred to as "hydrolyzable silyl group") and a hydroxyl group (hereinafter referred to as "resin"). , Abbreviated as "base resin for top coat"), an amino resin and an organic solvent as essential components.

The hydrolyzable group in which the topcoat base resin has hydrolyze in the presence of water is a residue which forms a silanol group, an alkoxy group of C ₁ ~ _5;
Aryloxy groups such as phenoxy group, tolyloxy group, paramethoxyphenoxy group, paranitrophenoxy group, benzyloxy group; acetoxy group, propionyloxy group, butanoyloxy group, benzoyloxy group, phenylacetoxy group, formyloxy group, etc. acyloxy group and _{-N (R 7) 2, -ON} (R 7) 2, -ON = C
_{(R 7) 2, -NR 8} COR 7 ( wherein, the R ₇ each same or different alkyl group of C ₁ ~ _8, aryl group having an aralkyl group, R ₈ is H, the C ₁ ~ ₈ It represents an alkyl group).

The base resin for topcoat used in the present invention is a resin containing at least one group selected from silanol groups and hydrolyzable silyl groups and a hydroxyl group in the same molecule as essential functional group components (hereinafter May be abbreviated as “single resin”) and a resin having at least one group selected from a silanol group and a hydrolyzable silyl group (hereinafter, this is abbreviated as “resin (or polymer) A”). ) And a resin having a hydroxyl group (hereinafter, this may be abbreviated as "resin (or polymer) B"). Examples of the type of resin include vinyl polymers, polyester resins, and polyether polyester resins. The molecular weight of these resins is about 2,000 in the case of vinyl polymer.
100,000, preferably about 4,000-80,000
It is desirable to have a number average molecular weight in the range of 0, in the case of polyester and polyether polyester systems, in the range of about 500 to 20,000, preferably about 1,000 to 5,000. If the number average molecular weight is less than the lower limit, defects such as stripes are likely to occur on the coating surface, while if the number average molecular weight exceeds the upper limit, the coating workability is poor, and scratches on the coating surface are likely to be defective. It is not preferable because it has the drawback that

In the base resin for a top coat used in the present invention, it is preferable to use a vinyl polymer having excellent weather resistance, acid resistance and scratch resistance among the above resins. The vinyl polymer will be described below.

Examples of the vinyl resin single resin include, for example, silanol group- and / or hydrolyzable silyl group-containing vinyl monomer (c), hydroxyl group-containing vinyl monomer (a), and, if necessary, A vinyl-based copolymer obtained by a copolymerization reaction with another polymerizable unsaturated monomer (b) and a vinyl-based polymer having a predetermined functional group are produced in advance, and then, A polymer obtained by reacting a silane compound having a silanol and / or a hydrolyzable silyl group (which may be a complementary reactive group) with a functional group reactive with the functional group Compound [for example, a product obtained by reacting a copolymer of glycidyl (meth) acrylate, a hydroxyl group-containing vinyl monomer (a) and another vinyl monomer (b) with γ-aminopropyltrimethoxysilane, (Meth) ac A copolymer of acid, a hydroxyl group-containing vinyl monomer (a) and another polymerizable unsaturated monomer (b) with γ-glycidoxypropyltrimethoxysilane] The manufactured product can be used.

The vinyl polymer has an average of one or more silanol groups and / or hydrolyzable silyl groups and a hydroxyl group (hydroxyl group value) in one molecule of about 30 to 300, preferably about 50.
It is desirable to have in the range of ~ 200. If the average number of silanol groups and / or hydrolyzable silyl groups is less than one in one molecule, the curability decreases and a coating film excellent in weather resistance, acid resistance, scratch resistance and the like cannot be formed, which is not preferable. Further, when the hydroxyl value is less than about 30, the curability is lowered, and it is difficult to form a coating film excellent in weather resistance, acid resistance, scratch resistance, etc. On the other hand, when the hydroxyl value is more than about 300, unreacted. A large amount of hydroxyl groups remain in the coating film, which lowers the water resistance of the coating film, which is not preferable.

As the mixed resin of vinyl polymer, for example, silanol group- and / or hydrolyzable silyl group-containing vinyl monomer (c) and, if necessary, other polymerizable unsaturated monomer (b). ) And a vinyl-based polymer obtained by (co) polymerizing and a vinyl-based polymer having a predetermined functional group, and then a group reactive with the functional group of the polymer in a complementary manner. A polymer obtained by reacting a silanol and / or a silane compound having a hydrolyzable silyl group (which may be a group which reacts complementarily) [eg glycidyl (meth) acrylate] In the copolymer with other polymerizable unsaturated monomer (b),
A product obtained by reacting γ-aminopropyltrimethoxysilane or a copolymer of (meth) acrylic acid and another polymerizable unsaturated monomer (b) was reacted with γ-glycidoxypropyltrimethoxysilane. Etc.] and the like, as well as the polymer obtained by polymerizing a hydroxyl group-containing vinyl monomer (a), the vinyl monomer (a)
And a polymer B such as a copolymer obtained by a copolymerization reaction of the above with other polymerizable unsaturated monomer (b).

The polymer A preferably has one or more silanol groups and / or hydrolyzable silyl groups on average in one molecule. If the average number of silanol groups and / or hydrolyzable silyl groups is less than one in one molecule, the curability decreases and a coating film excellent in weather resistance, acid resistance, scratch resistance and the like cannot be formed, which is not preferable.

The polymer B preferably has a hydroxyl value of about 30 or more. When the hydroxyl value is less than about 30, the curability is lowered, and it is difficult to form a coating film excellent in weather resistance, acid resistance, scratch resistance and the like. Further, when the hydroxyl value becomes too large, a large amount of unreacted hydroxyl groups remain in the coating film, which lowers the water resistance of the coating film.
It is preferably 00 or less.

The blending ratio of the polymers A and B is such that the weight ratio of polymer A: polymer B is 90:10 to 10:90, preferably 80:20 to 20:80. Among the above single resins and mixed resins, it is preferable to use a single resin which is easily cured to form a coating film excellent in finished appearance and performance. The above-mentioned monomers (a) and (b) may be the same as those mentioned above.

Examples of the vinyl monomer (c) include γ- (meth) acryloxyethyltrimethoxysilane,
γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltripropoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (Meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropylmethyldipropoxysilane, γ- (meth) acryloxybutylphenyldimethoxysilane, γ- (meth) acryloxybutylphenyldiethoxysilane, γ -(Meth) acryloxybutylphenyldipropoxysilane,
γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropyldimethylethoxysilane, γ- (meth) acryloxypropylphenylmethylmethoxysilane, γ- (meth) acryloxypropylphenylmethylethoxysilane, Acrylic silane compounds such as γ- (meth) acryloxypropyltriacetoxysilane, vinylsilane compounds such as vinyltrimethoxysilane and vinyltriethoxysilane, allylsilane compounds such as allyltriethoxy, and 2-styrylethyltrimethoxysilane. Examples thereof include styrylsilane compounds. Further, a radically polymerizable unsaturated group, a siloxane bond and silanol and / or a hydrolyzable silyl group are contained in a molecule obtained by reacting these monomers with, for example, a silane compound (eg, trimethoxysilane, triethoxysilane, etc.). Those having a group are also included.

In the base resin for a top coat used in the present invention, a resin having a carboxyl group introduced therein can also be used. As a method of introducing these groups into the resin, for example, in the production of a vinyl polymer, a carboxyl group-containing vinyl monomer may be used as the other vinyl monomer (b) component. When using these monomer components, the carboxyl group-containing vinyl monomer component is about 5 to 5 based on the vinyl polymer.
It is used in the range of 0% by weight, preferably about 10 to 40% by weight.

The amino resin used in combination with the base resin for the top coat is a methylolated amino resin similar to that described in the coating composition for a colored base coat or an etherified amino resin obtained by etherifying the amino resin with an alcohol. Resin etc. can be used. The blending amount of the amino resin is preferably about 2 to 100 parts by weight with respect to 100 parts by weight of the base resin. If the blending amount is less than 2 parts by weight, the water resistance and the like decrease, and if it exceeds 100 parts by weight, the weather resistance and the like decrease.

Examples of the organic solvent include hydrocarbon solvents such as heptane, toluene, xylene, octane and mineral spirit, ethyl acetate, n-butyl acetate,
Ester-based solvents such as isobutyl acetate, methyl cellosolve acetate and butyl carbitol acetate, ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone and diisobutyl ketone, alcohol-based solvents such as ethanol, isopropanol, n-butanol, sec-butanol and isobutanol. , Ether solvents such as n-butyl ether, dioxane, ethylene glycol monomethyl ether and ethylene glycol monoethyl ether can be used.

The clear coating composition used in the clear top coat of the present invention can be obtained by dissolving or dispersing the above base coat base resin and amino resin in an organic solvent. Further, it can be used as a non-aqueous dispersion type coating composition using this as a dispersion stabilizer. In addition to the above-mentioned base resin and organic solvent, a curing catalyst for a silanol group and / or a hydrolyzable silyl group may be added to the clear coating composition, if necessary.

Examples of the curing catalyst include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, trichloroacetic acid, phosphoric acid, mono-n-propylphosphoric acid, monoisopropylphosphoric acid, mono-n-butylphosphoric acid, monoisobutylphosphoric acid and monoisobutylphosphoric acid. -Tert-butyl phosphoric acid, monooctyl phosphoric acid,
Monoalkyl phosphoric acid such as monodecyl phosphoric acid, di-n-propyl phosphoric acid, diisopropyl phosphoric acid, di-n-butyl phosphoric acid, diisobutyl phosphoric acid, di-tert-butyl phosphoric acid, dioctyl phosphoric acid, didecyl phosphoric acid and the like, β-hydroxyethyl ( Phosphoric acid ester of (meth) acrylate, mono-n-propylphosphorous acid, monoisopropylphosphorous acid, mono-n-butylphosphorous acid, monoisobutylphosphorous acid, mono-t
ert-Butyl phosphite, monooctyl phosphite, monodecyl phosphite and other monoalkyl phosphites, di-n-propyl phosphite, diisopropyl phosphite, di-n-butyl phosphite,
Diisobutyl phosphite, di-tert-butyl phosphite, dioctyl phosphite, didecyl phosphite and other dialkyl phosphites and other acidic compounds; tetraisopropyl titanate, tetrabutyl titanate, tin octylate, dibutyltin diacetoate, dibutyltin dioctoate, dibutyl Tin-containing compounds such as tin dilaurate and dibutyltin dimaleate; butylamine, tert-butylamine, dibutylamine, hexylamine, ethylenediamine, triethylamine,
Isophorone diamine, imidazole, lithium hydroxide,
Basic compounds such as sodium hydroxide, potassium hydroxide and sodium methylate can be mentioned, and at least one of them is used. These curing catalysts are generally used in an amount of about 0.05 based on 100 parts by weight of the base coat base resin.
-20 parts by weight, preferably about 0.1-10.

When an etherified melamine resin in which a part or all of methoxy groups of hexamethoxymethylmelamine and its methoxy group are substituted with an amino resin is used as an amino resin, paratoluenesulfonic acid is used as a curing catalyst for a hydroxyl group,
Generally, a strong acid catalyst such as dodecylbenzene sulfonic acid is used, and the strong acid catalyst is neutralized (blocked) with an amine compound such as triethylamine, diethanolamine or 2-amino-2-methylpropanol. Therefore, it is used by imparting storage stability as a one-pack paint, but this neutralizing (block) strong acid catalyst
It means that it can also be a curing catalyst for alkoxysilane groups. That is, the neutralizing (blocking) strong acid catalyst becomes a common catalyst for the reaction of the resin and the reaction of the alkoxysilane at a baking temperature of 100 ° C. or higher.

If desired, the clear coating composition may further contain an ultraviolet absorber, an antioxidant, a light stabilizer, polymer fine particles, and various other additives for coatings.

The clear coating composition usually has a resin solid content of about 35 to 70% by weight. The method of the present invention is
For example, an electro-deposition paint is applied to a steel sheet that has been subjected to chemical conversion treatment, an intermediate coating (which may be omitted) and a primer suitable for various plastic materials are applied, and an intermediate coating (which may be omitted). As a material,
It can be carried out by applying a pigmented base coating composition and then applying a top clear coating composition. The above-mentioned electrodeposition coating composition and intermediate coating composition are usually baked at 140 to 190 ° C. for 30 to 90 minutes, depending on the type of coating composition. Coating of the colored base and top clear coating compositions can be carried out using conventional coating methods, for example electrostatic coating or non-electrostatic coating machines. The thickness of the colored base coat is preferably about 10 to 50 μm (after curing). 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 coating composition.
The thickness of the clear coating film is preferably 20 to 100 μm (after curing). Then, the coated object is heated at about 120 to 180 ° C. for 30 minutes.
It can be cured by heating for about 90 minutes.

[0052]

In the method of the present invention, the paint for the colored base coat finished by the two-coat one-bake method has a polyorgano having two or more silanol groups and / or alkoxysilane groups in one molecule as a binder component. Containing siloxane, the reaction between silanol groups (or silanol groups produced by hydrolysis of alkoxysilane groups) by heating and the reaction between silanol groups and hydroxyl groups in the hydroxyl group-containing resin occurs rapidly at relatively low temperatures. .. Since the reaction is carried out 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 withstands 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 is formed, and the finished appearance of the coating film is improved. Further, when the clear base coat cured coating film was coated with the colored base coating composition and re-coated, improvement in adhesion between the coating films was also observed.

[0053]

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 1 30 parts of methyl methacrylate, 53 parts of n-butyl methacrylate, 15 parts of 2-hydroxyethyl acrylate in an organic solvent of 85 parts of xylol and 15 parts of n-butanol.
Part of acrylic acid and 2 parts of acrylic acid are reacted to give a number average molecular weight of 6600, resin solid content of 50%, and Gardner foam viscosity V
To obtain a hydroxyl group-containing acrylic resin solution (A-1).

Production Example 2 Methyl methacrylate 30 parts, n-butyl methacrylate 45 parts, 2-hydroxyethyl acrylate 25 in an organic solvent of 85 parts xylol and 15 parts n-butanol.
A part of the monomers was reacted to obtain a hydroxyl group-containing acrylic resin solution (A-2) having a number average molecular weight of 5000, a resin solid content of 50%, and a Gardner foam viscosity T.

Production Example 3 182 parts of diphenyldimethoxysilane β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 186 parts Deionized water 108 parts 60% phosphoric acid 1 part After mixing and reacting at 60 ° C. for 5 hours, Methanol was removed by reduced pressure, and butyl acetate was added to the solution to give a polyorganosiloxane liquid (50% solid content, Gardner viscosity G) (b-1).
Got The resulting polyorganosiloxane has a number average molecular weight (by GPC) of about 200.
It was 0, and had an average of 10 silanol groups and an average of 7 epoxy groups per molecule.

Production Example 4 Phenyltrimethoxysilane 198 parts γ-glycidoxypropyltrimethoxysilane 236 parts Deionized water 108 parts 60% sulfuric acid 0.1 parts were mixed, reacted at 60 ° C. for 10 hours, and then depressurized to methanol. And adding xylol to obtain a solid content of 50%,
Gardner viscosity DE polyorganosiloxane liquid (low
2) was obtained. The obtained polyorganosiloxane had a number average molecular weight of about 8,000 and had an average of 10 silanol groups per molecule.

Paint composition for colored base coat Paint I-1 112 parts (56 parts by solid content) of the resin solution (a-1) obtained in Production Example 1, 40 parts by Uvan 20SE (Note 1) (24 parts by solid content) ), The resin solution (b-1) 40 obtained in Production Example 3
Parts (20 parts by solids content), 20 parts of aluminum paste and 1 part of Raybo # 3 (Note 2) were stirred and then Swazol 1000 (Note 3) / ethyl acetate = (30
/ 70) weight ratio of the mixed solvent was added to adjust the viscosity of the paint to 15 seconds (Ford cup # 4/20 ° C.) and the test was performed. (Note 1) U-Van 20SE: Mitsui Toatsu Chemicals, Inc.
Manufactured by butyl etherified melamine resin solution having a solid content of about 60%, trade name. (Note 2) Raybo # 3: Raybo Chemical Co., Ltd.
Product name: Silicone surface conditioner liquid made of about 1% active ingredient. (Note 3) Swazol 1000: Cosmo Oil Co., Ltd.
Made, petroleum-based aromatic solvent, trade name. Paint I-2 Paint I-2 was prepared in the same manner as Paint I-1, except that Resin solution (A-2) was used instead of Resin solution (A-1). Obtained. Paint I-3 A paint I-3 was prepared by the same formulation as the paint I-1, except that the resin solution (b-2) was used in place of the resin solution (b-1). Obtained. Paint I-4 Paint I-1 was prepared by the same formulation as Paint I-1, except that the resin solution (b-1) was not used.
Got 4.

Production Example 5 100 parts of styrene n-butyl acrylate 450 parts 2-ethylhexyl methacrylate 200 parts 2-hydroxyethyl methacrylate 150 parts γ-methacryloxypropyl trimethoxysilane 100 parts azobisisobutyronitrile 40 parts , In the same amount of xylene as the mixture,
The mixture was added dropwise at 0 ° C. over 3 hours and aged at the same temperature for 2 hours. The number average molecular weight of the obtained transparent polymer by GPC was 6,000.

Production Example 6 Styrene 150 parts n-butyl methacrylate 500 parts 1,4-butanediol monoacrylate 200 parts γ-methacryloxypropyl trimethoxysilane 150 parts Azobisisobutyronitrile 40 parts A mixture of xylene 500 parts , N-butanol 5
The mixture was added dropwise to 00 parts of the mixed solvent at 120 ° C. for 3 hours and then aged at the same temperature for 2 hours. The number average molecular weight of the obtained transparent polymer was 6000.

Clear Top Coat Paint Composition Paint II-1 Production Example 5 Solution (solid content 50%) 140 parts Cymel 303 (Note 1) 30 parts Nacure 5225 (Note 2) 1.5 parts Surface conditioner 0.1 Parts (manufactured by Big Chem, BYK-300 solution, having the same meanings below) UV absorber 1.0 part (Tinubin 90, manufactured by Ciba-Geigy, having similar meanings below) The above mixture was swathol # 1000. It was diluted and adjusted to a paint viscosity (same conditions as above) of 25 seconds. (Note 1) Cymel 303: full-methoxylated melamine resin manufactured by Mitsui Cyanamid Co., Ltd. (Note 2) Nacure 5225: KING INDUS
TRIES, dimethyloxazolidine neutralized product of dodecylbenzene sulfonic acid Paint II-2 Production Example 6 solution (solid content 50%) 160 parts Cymel 303 20 parts Nacure 5225 2 parts Surface conditioner 0.1 part UV absorber 1. 0 parts Prepared in the same manner as Paint II-1 using the above mixture. Paint II-3 Production Example 6 Solution (solid content 50%) 140 parts 60% U-ban 20SE 50 parts (Mitsui Toatsu's butylated melamine) Dibutyltin dilaurate 0.5 parts Surface conditioner 0.1 parts UV absorber 1 0.0 parts The same mixture as in Paint II-1 was prepared using the above mixture. Creating a painted board

Dal steel sheet (chemical conversion treatment) is coated with an epoxy resin-based cationic electrodeposition coating (25 μm), and it is heated at 170 ° C. for 30 days.
After heating and curing for a minute, as an intermediate coating, Lugerbake 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 paint, the paint for coloring base coat was applied by air spray coating and left for 3 minutes, and immediately thereafter the paint for clear top coat was applied. 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 film performance and appearance are shown in Table 1.

[0064]

[Table 1]

Test method (* 1) Appearance: The coating film was examined for cracks and spots. ◎ No abnormality, ○ Slightly recognized, × Many recognized. (* 2) Image clarity: Image clarity measuring device (IMAGE CLAR
It was measured by TYMETER manufactured by Suga Test Instruments Co., Ltd.
The numbers in the table are ICM values in the range of 0 to 100%. The larger the number, the better the image clarity (image clarity).
When the value is 75 or more, 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: It was immersed in Nisseki Silver Gasoline (trade name, manufactured by Nippon Oil Co., Ltd.) for 1 day, and the state of the coating film and the coating film hardness were examined according to the following criteria. Coating state: ◎ No abnormality, ○ Very slight tingling occurs,
△ Tige spots occur, × Tige spots occur remarkably. Coating film hardness: Shown by coating film pencil hardness after the test / coating film pencil hardness before the test.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI Technical display location C09D 161/22 PHK 8215-4J 183/06 PMU 8319-4J 201/06 PDL 6770-4J // C09D 163/00 PJD 8830-4J 8616-4D B05D 7/14 L 8616-4D 7/24 302 P 8616-4D 303 B 6904-4J C09D 5/00 PPF

Claims (1)

[Claims] 1. A top coat 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 method, as a coating composition for forming a colored base coat, (1) a hydroxyl group-containing vinyl resin (2) Amino resin (3) Polyorganosiloxane having an average number of 2 or more silanol groups and / or alkoxysilane groups and an average of 1 or more epoxy groups in one molecule and a number average molecular weight of 1000 or more (4) Metal flake powder and / or Alternatively, a coating composition containing a mica powder and (5) an organic solvent as an essential component is used to form a clear top coat, which is selected from (1) a silanol group and a hydrolyzable group directly bonded to a silicon atom. Resin containing at least one group and hydroxyl group as essential functional group components (2) Amino A coating film-forming method which comprises using a butter and (3) coating composition containing an organic solvent as essential components.