JP2001049188A - Paint composition and coating film forming method - Google Patents

Abstract

(57) Abstract: A novel coating composition using flaky particles of oxybismuth chloride and a method for forming a silky-tone coating film using the same. A coating composition comprising flaky particles of oxybismuth chloride and an organic solvent. A coating film forming method, comprising sequentially applying the coating composition (A) and the top clear coating composition (B) on an object to be coated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel coating composition using flaky particles of oxybismuth chloride and a method for forming a coating film using the same.

[0002]

2. Description of the Related Art It has been known that a paint containing an aluminum flake or a mica flake is applied to an outer panel of an automobile to form a metallic coating or a light interference coating. It is widely used because it shows glittering glitter and light coherence, and is superior in design to solid color coatings.

[0003] However, the demand for the color design of the outer panel of automobiles and home appliances has been individualized and diversified, and new demands have not been found in conventional metallic or optical interference tone coating films. There is a strong demand for the development of a paint that forms a coating film of various color designs.

An object of the present invention is to satisfy these demands, and is completely different from the conventional metallic or light interference tone coating film, and forms a novel silky-like coating film having excellent design properties. The present invention relates to the development of a paint and a coating film forming method using the same.

[0005]

DISCLOSURE OF THE INVENTION The present invention is directed to a paint for forming a novel silky-like paint film having excellent design properties, which is completely different from conventional metallic or light interference paint films. The feature of the method for forming a coating film using is that flaky particles of oxybismuth chloride are used as a glittering material exhibiting silky tone, and as a result, the object of the present invention can be achieved. The present invention has been completed.

Thus, according to the present invention, there is provided a coating composition (hereinafter referred to as "the present composition") containing flaky particles of oxybismuth chloride and an organic solvent.

The present composition is a coating composition comprising flaky particles of oxybismuth chloride and an organic solvent.

Oxybismuth chloride is a compound represented by BiOCl, and its flaky particles are used. Oxybismuth chloride itself is a known compound. Specifically, for example, oxybismuth chloride is obtained by reacting bismuth nitrate with hydrochloric acid, and its crystals can be precipitated and grown into flaky particles. The shape of the flaky particles is usually 4-octagonal, and the longitudinal direction is 5-15 μm.
m, especially 7 to 12 μm, and the thickness is preferably in the range of 0.001 to 1 μm, particularly 0.01 to 0.08 μm. Such particles exhibit a high refractive index and a high reflectivity, have a smooth surface, have a high metallic luster and a fine silky feeling. Further, it is more preferable to coat and treat the surface of the flaky powder of oxybismuth chloride with cerium hydroxide or the like, since the weather resistance is improved.

Commercial products of such flaky powder of oxybismuth chloride include, for example, Engelhard As
ia Pacific Inc. Product name "Mear
lite Radiant Pearl STL ",
"Mearlite Radiant Pearl S
UQ "and" BBT "(tentative name).

The organic solvent in the present composition is not particularly limited as long as it is a coating solvent, and examples thereof include hydrocarbon solvents, ester solvents, ketone solvents, alcohol solvents, and air solvents.
And a tellurium-based solvent.

The ratio of oxybismuth chloride to the organic solvent is, for example, 1 to 1 based on the total amount of both components.
30% by weight, especially 2-7% by weight, the latter 99-70% by weight, especially 98-93% by weight are preferred.

The present composition can be prepared by mixing and dispersing oxybismuth chloride in an organic solvent. If necessary, a coating resin, a phosphoric acid group-containing resin composition, an anti-settling agent, It is also possible to contain an electric assistant and the like.

Examples of the coating resin include polyester resins having a crosslinkable functional group such as a hydroxyl group, base resins such as alkyd resins, acrylic resins and vinyl resins, melamine resins, and polyisocyanate compounds which may be blocked. Examples of the composition include a cross-linking agent.

Further, examples of the phosphate group-containing resin composition include the following.

(P-1): An unsaturated monomer containing a phosphoric acid group and an unsaturated monomer containing a hydroxyl group are used as constituents.
A polymer containing a phosphoric acid group and a hydroxyl group in one molecule.

(P-2): Polymer particles are dispersed in a solution of a polymer dispersion stabilizer in an organic solvent, and the polymer particles are
A phosphate group-containing non-aqueous dispersion, which is a polymer particle containing a phosphate group-containing unsaturated monomer unit as a constituent.

The unsaturated monomer containing a phosphate group used for preparing the polymer (P-1) contains at least a polymerizable unsaturated bond and a phosphate group represented by the following formula (1) in one molecule. It is a compound having one by one.

Formula (1) -OPO (OH) (R ₁ ) (wherein, R ₁ is a hydroxyl group, a phenyl group, or a group having 1 to 2 carbon atoms)
It is an alkyl group of 0. ) As such a phosphate group-containing unsaturated monomer, for example, (2-
Acryloyloxyethyl) acid phosphate,
(2-methacryloyloxyethyl) acid phosphate, (2-acryloyloxypropyl) acid phosphate, (2-methacryloyloxypropyl) acid phosphate, 10-acryloyloxydecyl acid phosphate, (Meth) acryloyloxyalkyl (C2-20) acid phosphates such as 10-methacryloyloxydecyl acid phosphate
And others. Further, an equimolar addition product of glycidyl (meth) acrylate and monoalkyl (C1-20) phosphoric acid can also be used as the unsaturated monomer containing a phosphate group.

The hydroxyl group-containing unsaturated monomer is a compound having a hydroxyl group and a polymerizable unsaturated bond in one molecule, for example, hydroxyethyl (meth) acrylate,
Monoesters of glycol having 2 to 20 carbon atoms, such as hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate, and (meth) acrylic acid are exemplified.

The polymer (P-1) contains the above-mentioned unsaturated monomer containing a phosphate group and the unsaturated monomer containing a hydroxyl group as essential components, and further copolymerizes other monomers as necessary. Are included.

The other monomers are polymerizable unsaturated compounds other than the above-mentioned unsaturated monomers containing a phosphoric acid group and unsaturated monomers containing a hydroxyl group, and include, for example, (meth) acrylic acid and a compound having 1 carbon atom. Monoesters with monovalent alcohols of to 22;
Examples include styrene, acrylonitrile, vinyl acetate, vinyl chloride, (meth) acrylic acid, maleic acid, and maleic anhydride.

In the polymer (P-1), the ratio of the phosphate group-containing monomer to the hydroxyl group-containing monomer is 10 to 90%, preferably 20 to 90%, based on the total weight of both monomers. ~ 80%
And the latter is preferably 90 to 10%, particularly preferably 80 to 20%. In addition, the other monomer is a total of 100
1000 parts by weight or less, especially 10 to 500 parts by weight
Parts by weight are suitable.

The hydroxyl value of the polymer (P-1) is 5 to 15
0, especially 10 to 100 mmKOH / g, acid value based on the phosphate group is 10 to 150, especially 20 to 130 mmKOH / g.
g and the number average molecular weight are preferably from 1,000 to 100,000, particularly preferably from 3,000 to 50,000.

The polymer particles in the dispersion (P-2) are as follows:
It can be formed by polymerizing a monomer component obtained by using a phosphate group-containing unsaturated monomer and, if necessary, other monomers in combination.

Examples of the phosphate group-containing unsaturated monomer which is a constituent component of the polymer particles include a phosphate group represented by the formula (1) and a polymerizable unsaturated monomer described in the polymer (P-1). A compound having a saturated bond can be used.

The compound represented by the following formula (2) can also be used as a phosphate group-containing unsaturated monomer.

Formula (2): CH ₂ ＣCX—CO— (YO) n—OPO (OH) ₂ (wherein X is a hydrogen atom or a methyl group, and Y is an alkylene group having 2 to 4 carbon atoms) And n is an integer of 3 to 30) Specific examples of the compound represented by the formula (2) include acid phosphoxyhexa (or dodeca) (oxypropylene) monomethacrylate.

As the other monomer copolymerizable with the phosphoric acid group-containing polymerizable unsaturated monomer, a compound having at least one polymerizable unsaturated bond in one molecule can be used. specifically, the (meth) C _{1 ~ 18} alkyl esters of acrylic acid; C _{2 to 8} of the (meth) acrylic acid; C _{2 to 8} alkenyl esters of (meth) acrylic acid; (meth) acrylic acid glycidyl ester Hydroxyalkyl esters; C _3-18 alkenyloxyalkyl esters of (meth) acrylic acid; C of (meth) acrylic acid
Esters of _2-8 hydroxyalkyl esters and caprolactone; diesters of glycol and (meth) acrylic acid; vinyl aromatic compounds; α, β-ethylenically unsaturated acids; (meth) acrylic amides ; (Meth) acrylonitrile, vinyl propionate, isocyanate
Examples include triethyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, N-methyl-p-styrenesulfonamide, and γ-methacryloxypropyltrimethoxysilane.

The ratio of the phosphate group-containing polymerizable unsaturated monomer to the other copolymerizable monomer for preparing the polymer particles in the non-aqueous dispersion (P-2) is such that both monomers are used. The former is 0.1 to 100% by weight, especially 0.5 to 100% by weight, based on the total body.
It is preferably 50% by weight, more preferably 3 to 30% by weight, and the latter preferably in the range of 99.9 to 0% by weight, especially 99.5 to 50% by weight, more particularly 97 to 70% by weight.

The non-aqueous dispersion (P-2) can be prepared by polymerizing the above monomer components into particles in a solution of the polymer dispersion stabilizer in an organic solvent. A non-aqueous dispersion in which polymer particles derived from a monomer component are dispersed in an organic solvent solution is obtained.

The polymer dispersion stabilizer is for stably dispersing the polymer particles. The polymer dispersion stabilizer is compatible with the organic solvent in the dispersion, but is present together with the phosphoric acid group-containing polymerizable unsaturated monomer. Particles that are hardly compatible with polymer particles having a body unit as a constituent are used.

As such a polymer dispersion stabilizer, 1) 1
Polyester macromonomer (1a) in which a glycidyl (meth) acrylate is added to a self-condensed polyester resin of a hydroxyl group-containing fatty acid such as 2-hydroxystearic acid to introduce a polymerizable unsaturated bond, and this macromonomer (1a) A) a polymer obtained by polymerizing a polymerizable monomer to the polymer (1b), 2) the macromonomer (1a),
A polymer obtained by polymerizing a monomer containing glycidyl (meth) acrylate and further adding an ethylenically unsaturated acid to a glycidyl group in the polymer to introduce a polymerizable unsaturated bond (2a), 3) Hydroxyl-containing acrylic resin, 4) Hydroxyl-containing acrylic resin with polymerizable unsaturated bond introduced, 5)
Alkyl etherified melamine resins having a high mineral spirit tolerance, 6) oil-modified alkyd resins and oil-modified alkyd resins having polymerizable unsaturated bonds introduced thereinto, 7) cellulose acetate butyrate having polymerizable unsaturated bonds, etc. Is raised.

These dispersion stabilizers generally have a molecular weight of about 1000-1000.
It preferably has a weight average molecular weight in the range of about 50,000, especially about 3000 to about 20,000.

Among these dispersion stabilizers, the acrylic resin-based compounds described in 3) and 4) above, which are easily dissolved in low-polarity organic solvents such as aliphatic hydrocarbons and have good weather resistance, are particularly preferred. preferable.

The organic solvent used for preparing the non-aqueous dispersion (P-2) dissolves the polymer dispersion stabilizer and disperses the polymer particles without substantially dissolving it. Hydrocarbon solvents, ester solvents, ketone solvents, alcohol solvents, ether solvents and the like having a temperature of about 150 ° C. or lower.

The non-aqueous dispersion (P-2) is prepared by dissolving the above-mentioned polymer dispersion stabilizer in an organic solvent, and then dispersing a monomer component containing a phosphoric acid group-containing polymerizable unsaturated monomer. It can be prepared by polymerization. Non-aqueous dispersion (P-
In 2), the average particle size of the polymer particles derived from the monomer component containing the phosphate group-containing polymerizable unsaturated monomer is 0.1.
It is preferably from 01 to 1 μm.

The dispersion polymerization of the polymer dispersion stabilizer in an organic solvent solution can be carried out by a known radical polymerization method or the like. Is based on the total solid weight of both components, the polymer dispersion stabilizer is 0.1 to
70%, especially 5 to 50%, the monomer component is 99.9 to 30
%, Especially in the range of 95 to 50%. The ratio of the total solid content of the dispersion stabilizer and the monomer component to the organic solvent is preferably 5 to 60% for the former and 95 to 40% for the latter.

When a crosslinkable functional group such as a hydroxyl group is present in the molecule of the polymer dispersion stabilizer and the polymer particles, three-dimensional crosslinking can be carried out by adding a crosslinking agent to the non-aqueous dispersion (P-2). A coated film can be formed.

In the monomer component for preparing polymer particles, a monomer having two or more polymerizable unsaturated bonds in one molecule is used in combination with a polymerizable unsaturated monomer having a phosphate group. Alternatively, intra-particle crosslinking can be performed using a monomer having a self-crosslinking reactive group such as N-alkoxymethylated acrylamide.

In the present composition, the mixing ratio of the above-mentioned resin for paint and the resin composition containing a phosphoric acid group is as follows. Is 100 parts by weight of flaky particles of oxybismuth chloride in terms of solid content,
It is suitable that the amount is not more than 00 parts by weight, particularly 0.1 to 200 parts by weight. In particular, by blending a hydroxyl group-containing acrylic resin, a melamine resin, and a phosphate group-containing resin composition, it is possible to prevent cohesive failure within a single coating film of the present composition, and furthermore, it is possible to form a coating with other adjacent coating films. It is more preferable because the adhesion between layers can be improved.

Examples of the anti-settling agent include fatty acid amide wax, polyethylene oxide and the like, and the compounding amount thereof is based on the solid content ratio of bismuth oxychloride flaky particles.
The suitable amount is 50 parts by weight or less, particularly 1 to 30 parts by weight, more preferably 5 to 20 parts by weight, per 100 parts by weight.

The present composition can be applied to a metal or plastic outer panel of an automobile body such as a car, a truck, a motorcycle, a bus or the like, an outer panel of an electric appliance, etc., directly, or to an object to be coated thereon. An undercoat such as a cationic electrodeposition paint, and further an intermediate coat or the like can be applied after being applied in advance. Of these, it is preferable that the metal coated object is previously subjected to a chemical conversion treatment with a phosphate, a chromate, or the like. The undercoat paint and the intermediate paint are not particularly limited, and paints known per se can be used.

The composition of the present invention can be applied to these substrates (including those coated with an undercoat and an intermediate coat) by electrostatic coating, airless spray, air spray, or the like. The thickness is generally from 0.05 to 5 μm, especially from 0.1 to 5 μm, as a cured coating (sometimes containing only oxybismuth chloride or other solids such as resin compositions).
２2 μm is suitable.

The single coating film of the present composition has flaky particles of oxybismuth chloride uniformly oriented on the surface to be coated, and is completely different from the conventional coating film of metallic tone or light interference tone. It is possible to form a coated film having excellent silky-looking design properties.

The present invention also includes the following coating film forming method using the present composition.

Method (1): The composition (A) is applied to a substrate to be coated.
And a top clear paint (B).

Method (2): A method for forming a coating film characterized by sequentially applying a colored coating (C), the present composition (A) and a top clear coating (B) on an object to be coated.

The present method (3) is characterized in that a colored paint (C), a present composition (A), a base-clear paint (D) and a top clear paint (B) are successively applied on an object to be coated. Coating method.

In the present method (1), the composition (A) is applied to an object to be coated.
And a top clear paint (B).

In the present method (1), examples of the object to be coated include metal or plastic outer panels of automobile bodies such as cars, trucks, motorcycles and buses, and outer panels of electric products. These substrates may be subjected to a chemical conversion treatment with a phosphate, chromate, or the like, and further coated with a known undercoat such as a cationic electrodeposition coating, or an intermediate coating. Can be used as

As the present composition (A), the present composition characterized by containing the above-mentioned oxybismuth chloride flaky particles and an organic solvent can be used.

The top clear coating material (B) used in the present method (1) is preferably a thermosetting coating material which forms a colorless transparent or colored transparent coating film. Contains an organic solvent, and if necessary, a coloring pigment,
Paints containing a metallic pigment, an ultraviolet absorber and the like can be mentioned.

As the thermosetting resin composition, for example, acrylic resin, polyester resin, alkyd resin, fluorine resin, urethane resin, silicone resin containing a crosslinkable functional group such as a hydroxyl group, a carboxyl group, a silanol group, an epoxy group, etc. Melamine resin, urea resin, (block) polyisocyanate compound, epoxy compound or resin, carboxyl group-containing compound or resin, acid anhydride, alkoxysilane group-containing compound Alternatively, a composition comprising a crosslinking agent such as a resin can be used. Melamine resin has 1 to 1 carbon atoms
8 is a portion etherified with a monohydric alcohol or a fluorinated melamine resin, and the triazine nucleus is 1 to
Those having five are preferred. Imino group-containing melamine resins can also be used. The ratio of the base resin to the crosslinking agent is based on the total solid content of both components, and the former is 50 to 90% by weight, especially 65 to 80% by weight, and the latter is 50 to 10% by weight, particularly 4% by weight.
5-20% by weight is suitable.

Among these, an acrylic resin (base resin) containing a crosslinkable functional group such as a carboxyl group, a silanol group or an epoxy group, and an epoxy resin, which form a coating film having excellent acid resistance and scratch resistance. It is preferable to use a resin composition comprising a compound or resin, a carboxyl group-containing compound or resin, and a crosslinking agent selected from acid anhydrides and the like.

In the method (1), first, the composition (A) is applied to an object to be coated by electrostatic coating, airless spraying, air spraying.
Paint with The film thickness is 0.05 to 5 μm, especially 0.1 to 2 μm, based on the cured coating film (only flaky particles of oxybismuth chloride or may contain other solids).
m is suitable. Then, after this coating film is cured by heating, or flashed off at room temperature, for example, the solid content concentration at the time of coating is about 30 to about 80% by weight.
The top clear paint (B) adjusted as described above is applied by electrostatic coating, airless spray, air spray or the like. Its film thickness is 5 to 100 μm, preferably 20 μm, based on the cured coating film.
About 80 μm is suitable. Then 100-180
This method (1) is achieved by heating and curing at 10 ° C. for 10 to 40 minutes.

The method (2) is a method for forming a coating film characterized by sequentially applying a colored coating (C), the present composition (A) and a top clear coating (B) on an object to be coated.

Here, as the object to be coated, the present composition (A) and the top clear coating (B), those exemplified in the present method (1) can be suitably used similarly.

The coloring paint (C) is a liquid paint to be applied to an object to be coated prior to the present composition (A).
It is a paint containing a color pigment and an organic solvent.

As the resin composition, for example, a base resin such as a polyester resin, an alkyd resin, an acrylic resin, or a vinyl resin having a crosslinkable functional group such as a hydroxyl group, and a crosslinkable reaction with these functional groups, for example, a melamine resin A composition comprising a crosslinking agent such as a polyisocyanate compound which may be blocked can be suitably used. The ratio between the base resin and the crosslinking agent is preferably 50 to 90% for the former and 50 to 10% for the latter in terms of the total solid weight of both components.

Examples of the coloring pigment include inorganic pigments such as titanium oxide, zinc white, carbon black, cadmium red, molybdenum red, chrome ero, chromium oxide, Prussian bull, and cobalt bull; azo pigments and phthalocyanine pigments. Pigments for solid colors such as organic pigments such as quinacridone pigments, isoindoline pigments, sulene-based pigments, perylene pigments, and scale-like aluminum, mica, mica coated with metal oxide, mica-like iron oxide, etc. And the like for metallic pigments. As the organic solvent, for example, ordinary paint solvents such as hydrocarbons, esters, ethers, alcohols, and ketones can be used.

The above-mentioned “phosphoric acid group-containing resin composition” is blended with the colored paint (C) in order to improve the adhesion of the composition (A) to the coating film to be subsequently applied. can do. The compounding amount is 70 parts by weight or less, particularly 5 to 25 parts per 100 parts by weight of the solid content of the resin composition.
A range of parts by weight is suitable.

In addition to the above, the coloring paint (C) may further include, if necessary, an extender pigment, a curing catalyst, a coating surface regulator, an antioxidant, a flow regulator, a pigment dispersant, a silane coupling agent, and the like. They can be appropriately blended.

In the present method (2), first, a colored coating material (C) is applied to an object to be coated by electrostatic coating, airless spraying, air spraying or the like so that the film thickness of the cured coating film becomes 5 to 25 μm. Painting is preferred. It is preferable that the color tone of the surface to be coated is concealed to such an extent that the color tone cannot be visually recognized by the colored coating film. Then, depending on the thickness of the composition (A) to be coated and the content of oxybismuth chloride, etc., the silkiness is increased.
The color tone of the coating film of the colored paint (C) can be visually observed through the color coating film, and the color tone and the silky tone are both combined to provide a variety of design characteristics. An excellent coating film can be formed.

The colored coating material (C) is applied, and the coating film is left at room temperature or forcibly dried at a temperature of 100 ° C. or less (the gel fraction is 60% by weight or less, particularly 40% by weight or less), or After heating and curing at ~ 170 ° C, the present composition (A) is applied to the coating film surface.

The composition (A) is applied by electrostatic coating, airless spray, air spray or the like. The film thickness is 0.05 to 5 μm based on the cured coating film (only flaky particles of oxybismuth chloride or may contain other solids).
m, especially 0.1 to 2 μm is suitable. Then, after heating and curing the coating film, or flashing off at room temperature, for example, a top clear coating material (B) having a solid content concentration adjusted to approximately 30 to approximately 80% by weight is applied to the coated surface. )
Is applied by electrostatic coating, airless spray, air spray or the like. Its film thickness is 5-100μ based on the cured coating
m, preferably about 20 to 80 μm. Thereafter, by heating and curing at 100 to 180 ° C. for 10 to 40 minutes, the present method (2) is achieved.

The method (3) is characterized in that a color paint (C), the present composition (A), a base clear paint (D) and a top clear paint (B) are successively applied on an object to be coated. This is a method for forming a coating film.

Here, the object to be coated, the present composition (A), the top clear paint (B) and the colored paint (C) were prepared according to the method (1).
And what was illustrated by this method (2) can be used suitably similarly.

The base clear paint (D) is a paint applied to the uncured or cured surface of the present composition (A). Specifically, it is a liquid paint containing a resin composition and an organic solvent, and further, if necessary, a coloring pigment, an ultraviolet absorber and the like, and forms a colorless or colored transparent coating film. It has such transparency that the silky-tone coating film of the composition (A) can be visually recognized through the coating film of the base-clear coating material (D).

The resin composition in the base clear paint (D) is not particularly limited, and known resin compositions for thermosetting paints can be used. For example, crosslinking of a base resin such as an acrylic resin, a polyester resin, and an alkyd resin containing a crosslinkable functional group such as a hydroxyl group with a melamine resin, a urea resin, and a (block) polyisocyanate compound capable of reacting with these functional groups. A composition comprising an agent is preferred. As the melamine resin, a portion which is etherified with a monovalent alcohol having 1 to 8 carbon atoms or a fluorinated melamine resin which has 1 to 5 triazine nuclei is preferable. Imino group-containing melamine resins can also be used.
The ratio of the base resin to the crosslinking agent is 50 to 90% by weight, especially 65 to 80% by weight, and the latter is 50 to 10% by weight, particularly 45 to 20% by weight, based on the total solid content of both components.
Is suitable.

As the coloring pigment, the solid color pigments and the metallic pigments exemplified in the present method (2) can be preferably used.

Further, the base paint (D) can further be blended with the above-mentioned "phosphoric acid group-containing resin composition", whereby the adhesion between layers with another adjacent coating film is improved. It is more preferable. The compounding amount is 1 to 30 parts by weight per 100 parts by weight of the resin composition in a solid content ratio,
Particularly, 5 to 20 parts by weight is suitable.

In the present method (3), first, a colored coating material (C) is applied to an object to be coated by electrostatic coating, airless spraying, air spraying or the like so that the film thickness of the cured coating film becomes 5 to 25 μm. Painting is preferred. It is preferable that the color tone of the surface to be coated is concealed to such an extent that the color tone cannot be visually recognized by the colored coating film. Then, since the color tone of the coating film of the colored paint (C) can be visually observed through the silky-tone coating film of the present composition (A), the color tone and the silky tone can be observed. However, the combination of the two makes it possible to form a coating film with various designs and excellent design.

The colored coating material (C) is applied, and the coating film is left at room temperature or forcibly dried at a temperature of 100 ° C. or less (the gel fraction is 60% by weight or less, particularly 40% by weight or less), or After heating and curing at ~ 170 ° C, the present composition (A) is applied to the coating film surface.

The composition (A) is applied by electrostatic coating, airless spray, air spray or the like. The film thickness is 0.05 to 5 μm based on the cured coating film (only flaky particles of oxybismuth chloride or may contain other solids).
m, especially 0.1 to 2 μm is suitable. Then, after this coating film is cured by heating or flashed off at, for example, room temperature, the base surface is coated with a base clear paint (D).
To paint.

Specifically, the solid content concentration at the time of application of the base-clear paint (D) was adjusted to about 20 to about 80% by weight, and this was applied to the uncured or cured coated surface of the composition (A). , Electrostatic coating, airless spray, air spray, etc., the film thickness based on the cured coating film is 5 to 100 µm, preferably 20 to 80 µm
m. This base
For example, after the coating film of the scourer paint (D) is left at room temperature or cured by heating at 100 to 170 ° C., the solid content concentration at the time of coating is about 30 to about 80
The top clear paint (B) adjusted to weight% is applied by electrostatic coating, airless spray, air spray or the like.
The film thickness is suitably 5 to 100 μm, preferably about 20 to 80 μm, based on the cured coating film. Then 100
This method (3) is achieved by curing by heating at ~ 180 ° C for 10-40 minutes.

[0076]

According to the present invention, the following effects can be obtained.

(1) It was possible to form a film having a silky tone and excellent design, which is not seen in a conventional metallic film or light interference film.

(2) The composition (A) is added in an amount of 0.05 to 5 μm.
m, especially when applied to a thin film of about 0.1 to 2 μm, since the flaky particles of oxybismuth chloride are uniformly oriented on the surface to be coated, they were not found in conventional metallic coatings or light interference coatings. Thus, it became possible to form a silky-tone coating film having excellent denseness and smoothness.

[0079]

EXAMPLES Examples and comparative examples according to the present invention will be described. All parts and percentages are in principle based on weight. The thickness of the coating film is for the cured coating film.

1. Sample 1) Coating object A thermosetting epoxy resin-based cationic electrodeposition paint (“ELECRON 9600” manufactured by Kansai Paint Co., Ltd., trade name) was coated on a 0.8 mm-thick dull steel plate that had been subjected to zinc phosphate conversion treatment. Electrodeposited so that the cured film thickness becomes about 20 μm, and heated and cured at 170 ° C. for 30 minutes, and then applied to an intermediate coating for automobiles (thermosetting polyester resin / melamine resin-based organic solvent type coating material “TP-37 Primer”). -Surfacer "(trade name, manufactured by Kansai Paint Co., Ltd.) was air-sprayed so that the cured film thickness was about 25 μm, and was heated at 140 ° C. for 30 minutes to be cured to obtain a test object. .

2) Composition (A) a): A mixture comprising 5 parts of oxybismuth chloride flaky particles (Note 1) and 95 parts of "Swazol 1000" (Note 2).

(Note 1) Oxybismuth chloride flaky particles 4-8 octagons, 7-12 μm in the longitudinal direction, 0.0 thickness
1-0.08 μm. Product name, manufactured by ENGELHARD
"Mearlite Radiant Pearl SU
Q ".

(Note 2) "Swazol 1000" Cosmo Oil Co., Ltd., trade name, aromatic hydrocarbon solvent.

B): 5 parts of oxybismuth chloride flaky particles (Note 1), 95 parts of "Swazol 1000" (Note 2), 2.5 parts of phosphoric acid group-containing resin composition P-1 (Note 3) A mixture consisting of

(Note 3) Phosphoric acid group-containing resin composition P-1:
Acid phosphoroxyethyl methacrylate 30 parts, 2-
A monomer copolymer comprising 15 parts of hydroxyethyl acrylate, 20 parts of methyl methacrylate, 5 parts of n-butyl methacrylate, and 30 parts of 2-ethylhexyl methacrylate. Number average molecular weight 13000, hydroxyl value 72 mgK
OH / g, acid value 126 mgKOH / g.

C): 5 parts of oxybismuth chloride flaky particles (Note 1), 95 parts of "Swazol 1000" (Note 2), 2.5 parts of phosphoric acid group-containing resin composition P-1 (Note 3) A mixture comprising 3 parts of a hydroxyl group-containing acrylic resin (Note 4) and 1 part of a butyl etherified melamine resin (Note 5).

(Note 4) Hydroxyl group-containing acrylic resin: from 38% of methyl methacrylate, 17% of ethyl acrylate, 17% of n-butyl acrylate, 7% of hydroxyethyl methacrylate, 20% of lauryl methacrylate and 1% of acrylic acid Copolymer of the monomers Number average molecular weight 5000
0, hydroxyl value 54 mgKOH / g.

(Note 5) Butyl etherified melamine resin:
"U-Van 28-60" (trade name, manufactured by Mitsui Toatsu Co., Ltd.) 3) Top clear paint (B) a): Carboxyl group-containing acrylic resin (Note 6) 50
Part, epoxy group-containing acrylic resin (Note 7) 50 parts, Tinuvin 900 (manufactured by Ciba Geigy Co., trade name, ultraviolet absorber) 1 part, equivalent mixture of tetrabutylammonium bromide and monobutyl phosphoric acid 2 parts, "BYK300" (Big Chemical Co., trade name, surface conditioner) 0.1 part was mixed and dispersed in "Swazol 1000" (Note 2) to give a viscosity of 20.
Adjusted to sec / ford cup # 4/20 ° C.

(Note 6) Carboxyl group-containing acrylic resin: methanol half ester of maleic anhydride 2
0%, 4-hydroxy n-butyl acrylate 20%, n
A copolymer of a monomer component consisting of 40% of butyl acrylate and 20% of styrene. The number average molecular weight is 3,500, the acid value is 86 mgKOH / g, and the hydroxyl value is 78 mgKOH / g.

(Note 7) Acrylic resin containing epoxy group: glycidyl methacrylate 30%, 4-hydroxy n-butyl acrylate 20%, n-butyl acrylate 30%
And a copolymer of a monomer component comprising 20% of styrene.
The number average molecular weight is 3000, the epoxy group content is 2.12 mmol / g, and the hydroxyl value is 78 mgKOH / g. 4) Colored paint (C) a): 75 parts of hydroxyl group-containing acrylic resin (Note 4), 25 parts of butyl etherified melamine resin (Note 5), "CR95 titanium oxide" (trade name, manufactured by Ishihara Sangyo Co., Ltd., titanium oxide) Pigment)
100 parts were mixed and dispersed in “Swazol 1000” (Note 2), and the viscosity was adjusted to 13 seconds / ford cup # 4/20 ° C.

B): Hydroxyl group-containing acrylic resin (Note 4) 7
5 parts, butyl etherified melamine resin (Note 5) 25 parts,
20 parts of a phosphate group-containing resin composition P-1 (Note 3), 10 parts of "Green 5370" (trade name, phthalocyanine line, manufactured by Dainichi Seika Co., Ltd.), "Alpaste 7679NS"
(Toyo Aluminum Co., Ltd., trade name, aluminum frame
5 parts of “Cupaste” was mixed and dispersed in “Swazol 1000” (Note 2), and the viscosity was 13 seconds / Ford cup # 4/20.
Adjusted to ° C.

5) Base clear paint (D) a): 75 parts of a hydroxyl group-containing acrylic resin (Note 4) and 25 parts of a butyl etherified melamine resin (Note 5) were added to "Swazol 1000" (Note 2). The mixture was dispersed and adjusted to have a viscosity of 13 seconds / ford cup # 4/20 ° C.

B): Hydroxyl group-containing acrylic resin (Note 4) 7
5 parts, butyl etherified melamine resin (Note 5) 25 parts,
20 parts of the phosphoric acid group-containing resin composition P-1 (Note 3) and 0.2 parts of "Green 5370" were mixed and dispersed in "Swazol 1000" (Note 2), and the viscosity was 13 seconds / form. Do cup # 4
/ 20 ° C.

2. Examples and Comparative Examples The present composition (A) was applied to the cured intermediate coating surface of the object to be coated.
The top clear paint (B), the colored paint (C) and the base clear paint (D) were applied to form a multilayer coating film. The coating process using these paints is shown in Table 1.

[0095]

[Table 1]

Table 2 shows the performance test results of the obtained multilayer coating film. The test method of the coating film in Table 2 is as follows.

Silkiness: The presence or absence of silky soft luster was visually observed. ○: good silky feeling, △
Indicates that the silky feeling was slightly inferior, and x indicates that no silky feeling was observed.

Dense feeling: The result of visually observing the denseness of the silky feeling. ○ indicates that the compactness is good, 劣 indicates that the compactness is slightly inferior, and x indicates that the compactness is not recognized.

Adhesion: (Initial) Paint and bake the coating as described above, leave it at 20 ° C. for 1 hour, cut the coating with a cutter to reach the substrate, and measure 2 mm × 2 m
After making 100 goban eyes, adhesive tape was stuck on the surface and the tape was rapidly peeled off at 20 ° C.
The number of remaining Goban eyes was examined. ○: 1
00 pieces remaining, Δ: 99-95 pieces of Gobang-like coating remain, ×
Indicates that 94 or less gobang-like coatings remain.
(Water resistance) After coating and baking the film as described above, immersing it in warm water at 40 ° C. for 10 days, pulling it up and drying it, the test was performed in the same manner.

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[Procedure amendment]

[Submission date] August 20, 1999 (1999.8.2
0)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0095

[Correction method] Change

[Correction contents]

[0095]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 7/12 C09D 7/12 Z F term (Reference) 4D075 AE03 CB13 DB02 DC12 DC18 EA43 EC02 EC23 4J038 CG141 DA162 DD001 DD121 DG262 DG302 EA011 GA03 HA256 KA03 KA06 KA08 KA20 PA07

Claims (4)

[Claims] 1. A coating composition comprising flaky particles of oxybismuth chloride and an organic solvent. 2. The coating composition (A) according to claim 1, which is applied to an object to be coated.
And a top clear paint (B). 3. A method for forming a coating film, comprising sequentially applying a colored coating (C), the composition (A) of claim 1 and a top clear coating (B) on an object to be coated. 4. A coating characterized by successively applying a colored coating (C), the composition (A) of claim 1, a base-clear coating (D) and a top clear coating (B) on an object to be coated. Film formation method.