JP2002275425A - Ebony coating composition, method for forming coating film and multilayered coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ebony coating composition which does not cause a whitening phenomenon in the shade portion of a formed coating film, when the coating film is obliquely looked, has a high ebony property, and sufficiently develops an interfering property, to provide a method for forming a coating film, and to provide a multilayered coating film. SOLUTION: This ebony coating composition comprises a metal mixture oxide flake pigment containing two or more metal elements, carbon black pigment and a vehicle.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a jet-black paint composition, a method for forming a coating film, and a multilayer coating film obtained by the method.

[0002]

2. Description of the Related Art As a method for expressing a design of interference and jet-blackness, a method using carbon black and an interference bright pigment is known. In this method, coherence and jet-blackness are exhibited by the combined effect of carbon black and interference glittering pigments, but white blur occurs in the shade portion when the formed coating film is viewed obliquely and is called high jet-blackness. However, it is not enough.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a coating film which has high jet-blackness which does not cause white blur at a shade portion when the coating film is viewed obliquely, and which sufficiently exhibits interference. To provide a jet-black paint composition, a coating film forming method, and a multilayer coating film.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above-mentioned problems, and as a result, have reached the present invention. A jet-black paint composition containing a metal mixed oxide flake pigment comprising at least 1.2 kinds of metal elements, a carbon black pigment and a vehicle. 2. The jet-black paint composition wherein at least one of the two or more metal elements constituting the metal mixed oxide flake pigment comprising the two or more metal elements is a coloring metal element selected from the following group (A): . Group (A): Co, Ni, Fe, Mn, Cu, Cr, V,
Na, W3. The jet-black paint composition wherein the two or more metal elements other than the color-forming metal element are metal elements selected from the following color-adjustment metal elements in the group (B) or the color-forming auxiliary metal elements in the group (C). . (B) group: Ti, Sb, As, Bi, P (C) group: Al, Si, K, Ca, Mg, Ba, Zn,
Li, Zr 4. The solid content ratio of the metal mixed oxide flake pigment and the carbon black pigment is 99/1 to 70 /
30. The jet-black paint composition which is 30. 5. The jet-black paint composition described above, wherein the total content of the metal mixed oxide flake pigment and the carbon black pigment is 5 to 30% by mass based on the solid content of the paint. 6. A coating film forming method using the jet-black paint composition for forming at least one of the layers constituting the multilayer coating film. 7. On a substrate, a method for forming a multilayer coating film sequentially forming an undercoat film layer, an intermediate coat film layer, an overcoat film layer and a clear overcoat film layer, wherein the overcoat film layer is A method for forming a paint film in which a paint film layer is formed by the jet paint composition of the present invention. 8. The above-mentioned method for forming a coating film, wherein the clear top coating film layer is formed from a coating material containing a carboxyl group-containing polymer and an epoxy group-containing polymer. 9. A multilayer coating film obtained by the above coating film forming method.

[0005]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The configuration of the present invention will be described below in detail.

Jet- black paint composition The jet-black paint composition of the present invention is a paint composition containing a metal mixed oxide flake pigment composed of two or more metal elements, a carbon black pigment and a vehicle.

[0007] By using a metal mixed oxide flake pigment composed of two or more kinds of metal elements and a carbon black pigment in combination, a white blur is formed on a formed coating film in a shade portion when the coating film is viewed obliquely. High jet-blackness that does not occur is sufficiently obtained. The metal mixed oxide flake pigment composed of two or more metal elements has an average particle diameter of 10
It is a flake-like brilliant pigment having a size of ３０30 μm, preferably 10-20 μm. If the average particle diameter is less than 10 μm, it may not be possible to obtain a brilliant feeling.

[0008] At least one of the two or more metal elements constituting the mixed metal oxide flake pigment comprising the two or more metal elements is preferably a group (A): Co, Ni, F
e, a coloring metal element selected from Mn, Cu, Cr, V, Na, and W. More preferably, group (A): Mn, C
u is a coloring metal element selected from u.

Further, the above-mentioned two or more metal elements other than the above-mentioned coloring metal elements constituting the metal mixed oxide flake pigment comprising the above-mentioned two or more metal elements are preferably (B)
Group: color development adjusting metal element selected from Ti, Sb, As, Bi, P, or (C) group: Al, Si, K, Ca, M
g, Ba, Zn, Li, and Zr.

[0010] The carbon black pigment used in combination with the metal mixed oxide flake pigment comprising two or more metal elements is a black pigment commonly used in the field of paints.

In the present invention, the solid content ratio of the metal mixed oxide flake pigment composed of two or more metal elements and the carbon black pigment is 99/1 to 70/30.
When the range is more than 99/1 (when the amount of the carbon black pigment is small), the high jet blackness may be insufficient. (When the amount of the oxide flake pigment is small), the coherence may be insufficient. More preferably, it is 99/1 to 80/20.

The total content of the metal mixed oxide flake pigment composed of the two or more metal elements and the carbon black pigment is preferably 5 to 30% by mass based on the solid content of the paint. If the amount is less than 30% by mass, high jet blackness and interference may be insufficient. If the amount exceeds 30% by mass, the appearance of the coating film may be deteriorated.

On the other hand, the vehicle contained in the jet-black paint composition of the present invention disperses the above pigment, and is composed of a resin for forming a coating film and, if necessary, a crosslinking agent.

The resin for forming a coating film constituting the vehicle includes, for example, (a) an acrylic resin, (b) a polyester resin, (c) an alkyd resin, (d) a fluororesin,
(E) epoxy resin, (f) polyurethane resin, (g)
Examples thereof include polyether resins, and these can be used alone or in combination of two or more. In particular,
Acrylic resins and polyester resins are preferably used.

The acrylic resin (a) includes a copolymer of an acrylic monomer and another ethylenically unsaturated monomer. Examples of the acrylic monomer that can be used for the copolymerization include methyl, ethyl, propyl, n-butyl, i-butyl and t-acrylate of acrylic acid or methacrylic acid.
-Butyl, 2-ethylhexyl, lauryl, phenyl,
Esterified products such as benzyl, 2-hydroxyethyl and 2-hydroxypropyl, ring-opened adducts of caprolactone of acrylic acid or 2-hydroxyethyl methacrylate, glycidyl acrylate or methacrylate, acrylamide, methacrylamide and N-methylol Acrylamide, (meth) acrylic acid esters of polyhydric alcohols and the like can be mentioned. Examples of the other ethylenically unsaturated monomers copolymerizable therewith include styrene, α-methylstyrene, itaconic acid, maleic acid, and vinyl acetate.

Examples of the polyester resin (b) include saturated polyester resins and unsaturated polyester resins. Examples thereof include condensates obtained by heat-condensing a polybasic acid and a polyhydric alcohol. Examples of the polybasic acid include saturated polybasic acids and unsaturated polybasic acids.Examples of the saturated polybasic acids include phthalic anhydride, terephthalic acid, and succinic acid. For example, maleic acid, maleic anhydride, fumaric acid and the like can be mentioned.
Examples of polyhydric alcohols include dihydric alcohols and trihydric alcohols.
Examples include ethylene glycol and diethylene glycol, and examples of the trihydric alcohol include glycerin and trimethylolpropane.

The resin for forming a coating film includes a curable type and a lacquer type, and usually, a curable type is used. In the case of a type having curability, it is used as a mixture with a crosslinking agent such as an amino resin, a (block) polyisocyanate compound, an amine-based, a polyamide-based, or a polyvalent carboxylic acid, and the curing reaction proceeds at heating or at room temperature. be able to. It is also possible to use a lacquer type coating film forming resin having no curability and a curable type in combination.

When the vehicle contains a cross-linking agent, the ratio of the resin for forming a film to the cross-linking agent is 90 to 50% by mass in terms of solid content, Preferably, the coating film forming resin is 85 to 60% by mass, and the crosslinking agent is 15 to 40% by mass. If the amount of the crosslinking agent is less than 10% by mass (the amount of the resin for forming a coating film exceeds 90% by mass), the crosslinking in the coating film is insufficient. On the other hand, if the crosslinking agent exceeds 50% by mass (the
), The storage stability of the coating composition is reduced and the curing speed is increased, so that the appearance of the coating film is deteriorated.

The jet-black paint composition of the present invention may contain other glittering pigments and / or coloring pigments in addition to the metal mixed oxide flake pigment comprising two or more metal elements and the carbon black pigment. it can. Other glitter pigments include, for example, ordinary aluminum flake pigments, colored aluminum flake pigments, graphite pigments, colored mica pigments, metal titanium flake pigments, stainless flake pigments, plate-like iron oxide pigments, metal-plated glass flake pigments, metal oxides Coated with alumina flake pigment, metal oxide-coated silica flake pigment, interference mica pigment, metal oxide-coated plated glass flake pigment, hologram pigment and at least one pigment selected from the group consisting of cholesteric liquid crystal polymer flake pigments. is there. As the coloring pigment, for example, azo lake pigments, phthalocyanine pigments, indigo pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, metal complex pigments, yellow iron oxide, red iron oxide And titanium dioxide. The amount of addition of other glittering pigments and / or coloring pigments can be arbitrarily set as long as the effects of the metal mixed oxide flake pigment comprising two or more metal elements and the carbon black pigment are not hindered.

The jet-black paint composition of the present invention comprises, in addition to the above components, a polyamide wax which is a lubricating dispersion of an aliphatic amide, a polyethylene wax which is a colloidal dispersion mainly composed of polyethylene oxide, an anti-settling agent, Curing catalyst,
UV absorbers, antioxidants, leveling agents, surface conditioners such as silicone and organic polymers, anti-sagging agents, thickeners, defoamers, cross-linkable polymer particles (microgels), etc. are appropriately added and contained. be able to. These additives can improve the performance of paints and coatings by blending, for example, at a ratio of 15 parts by mass or less, respectively, to 100 parts by mass of the vehicle (based on solid content).

The jet-black paint composition of the present invention is provided in a form in which the above components are usually dissolved or dispersed in a solvent. Any solvent may be used as long as it dissolves or disperses the vehicle, and an organic solvent and / or water may be used. Examples of the organic solvent include those commonly used in the field of coatings. Examples thereof include hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, cellosolve acetate and butyl cellosolve, and alcohols. When the use of an organic solvent is regulated from the viewpoint of the environment, it is preferable to use water. In this case, an appropriate amount of a hydrophilic organic solvent may be contained.

The coating film forming method of the present invention is a method for forming a multilayer coating film on a substrate, wherein at least one of the layers constituting the multilayer coating film is formed by the above-mentioned method. This is a coating film forming method using a jet-black paint composition. Examples of the multilayer coating film include, for example, a coating film layer formed on the undercoat coating layer using the jet-black coating composition, and a jet-black coating film formed using the jet-black coating composition. An example is a layer in which a clear top coat layer is formed on the layer. Here, the multilayer coating film formed on the base material is composed of an undercoat coating layer, an intermediate coating layer, a jet-black coating layer, and a clear top-coat coating layer. And a method for forming a coating film formed from the jet-black paint composition.

The above-mentioned substrate is not limited, and metals such as iron, aluminum, copper and alloys thereof; inorganic materials such as glass, cement and concrete; polyethylene resin, polypropylene resin, ethylene-vinyl acetate Copolymer resin, polyamide resin, acrylic resin,
Resins such as vinylidene chloride resin, polycarbonate resin, polyurethane resin and epoxy resin, and plastic materials such as various FRPs; natural and synthetic materials such as wood and fiber materials (paper, cloth, etc.); and processed products thereof. .

In the method of forming a coating film of the present invention, the jet-black paint composition is applied to the above substrate directly or via an undercoat layer. It is preferable to previously apply an undercoat to the base material by chemical conversion treatment, electrodeposition coating, spray coating, powder coating, or the like.

In the case where the jet-black coating layer is formed directly on the undercoated layer without the intermediate coating, the wet-on-wet (W / W) or wet-on-dry (W / D). The above-mentioned W / W is a method of forming a lower layer coating film, drying the film by air drying or the like, and forming an upper layer coating film on an uncured or semi-cured lower layer coating film. The W / D is a method of forming an upper coating film on a lower coating film obtained by baking and curing a lower coating film.

It is also possible to apply each coating layer a plurality of times. In the case of baking the coating layer, 80 to 160
Perform baking at a temperature of ° C for a predetermined time. The dry film thickness of the jet-black coating layer is preferably 5 to 30 μm, more preferably 10 to 2 μm.
0 μm.

In the present invention, an intermediate coating film layer can be formed before the jet-black coating film layer is formed on the substrate. When an undercoat layer is formed below the intermediate coat layer, the undercoat layer is preferably formed by W / D with the undercoat layer. The intermediate coating film layer may be formed of a solvent-type paint, an aqueous paint, or a powder-type paint.
As the vehicle, pigment, and optional additives to be used for forming the intermediate coating layer, those exemplified for the jet-black paint composition can be used.

The dry film thickness of the intermediate coating film layer is 20 to 1
If the thickness is outside this range, the appearance of the coating film may be degraded. More preferably, it is 30 to 50 μm. Next, a jet-black paint layer is formed on the above-mentioned intermediate coat layer using the jet-black paint composition. This jet-black paint film layer is preferably formed by the above-mentioned intermediate paint film layer and the above W / D. The dry film thickness of the jet-black coating layer is 5 to 30.
μm is preferred, and more preferably 10 to 20 μm.

Further, at least one of the above clear top coat layers is formed as a top coat layer on the jet black coat layer. When the jet-black paint film layer contains a large amount of glitter pigment, the smoothness of the surface can be improved by applying two or more clear paints. For the formation of the clear top coat layer, it is preferable to use the above W / W. In the case of applying the clear paint a plurality of times, the clear paint may be applied and baked at the same time after the final clear paint is applied. The dry film thickness of the clear top coat layer is preferably from 20 to 100 μm, and if it is out of this range, the appearance of the coat may deteriorate. More preferably 3
0 to 50 μm.

As the clear top coat layer, a general clear paint can be used, and a so-called turbid clear coat layer having a translucent feeling may be used. Further, the clear top coat layer may be formed from a solvent type paint, an aqueous paint or a powder type paint. As the solvent-based paint or the water-based paint, a one-pack paint may be used, or a two-pack paint such as a two-pack urethane resin paint may be used. By forming a clear top coat layer on the jet-black coat layer, it is possible to improve the gloss and prevent the glitter pigment from being damaged. As the clear paint, those generally used for overcoating can be used, and a mixture of the above thermosetting resin and a crosslinking agent can be used. In particular, Tokuhei 8-1931
No. 5, when a clear coating containing a carboxyl group-containing polymer and an epoxy group-containing polymer was applied to a jet-black coating layer by acid rain prevention and W / W,
It is preferably used from the viewpoint of not disturbing the orientation of the brightener in the jet-black coating layer. In addition, these clear paints, if necessary, do not impair the transparency,
Additives such as coloring pigments, extenders, modifiers, ultraviolet absorbers, leveling agents, dispersants, and defoamers can be included.

The multi-layer coating film of the present invention is obtained by the above-mentioned method for forming a coating film, is formed on a substrate, and is formed of a layer constituting the multi-layer coating film. At least one layer is a jet-black paint layer formed using the jet-black paint composition. Preferably, the multilayer coating film is formed of an undercoat coating layer, an intermediate coating film layer, a jet-black coating film layer, and a clear top coating film layer.

[0032]

EXAMPLES Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, the compounding amount represents a mass part unless there is particular notice. The names of raw materials, paints, and equipment represent trade names unless otherwise specified.

Examples 1 to 10 and Comparative Examples 1 to 2 Preparation of Substrates Dull steel plate (length 300 mm, width 100 mm and thickness 0.8 mm) was treated with a zinc phosphate treating agent (trade name: "Surfdyne SD2000", Japan). After a chemical conversion treatment using a paint (manufactured by Nippon Paint Co., Ltd.), the dry film thickness of the cationic electrodeposition paint (trade name: “Power Top U-50”, manufactured by Nippon Paint Co., Ltd.) was 25 μm.
m was electrodeposited. Then at 160 ° C. for 30
After baking for half an hour, an intermediate coating ("Olga S-90 Sealer", manufactured by Nippon Paint Co., Ltd.) is applied by air spraying so as to have a dry film thickness of 40 [mu] m, and baked at 140 [deg.] C. for 30 minutes. A substrate was obtained.

Preparation of jet-black paint composition Acrylic resin (styrene / methyl methacrylate / ethyl methacrylate / hydroxyethyl methacrylate /
Methacrylic acid copolymer, number average molecular weight about 20,000
0, hydroxyl value 45, acid value 15, solid content 50% by mass);
The type and amount shown in Table 1 were obtained for a vehicle obtained by blending a melamine resin (trade name: “Uban 20SE”, manufactured by Mitsui Chemicals, Inc., solid content: 60% by mass) at a solid content mass ratio of 80:20. A metal mixed oxide flake pigment composed of the above two or more metal elements and a carbon black pigment in the amount shown in Table 1, and optionally other glitter pigments and / or coloring pigments in the type and amount shown in Table 1 Was blended. As a comparative example, in Comparative Example 1, an interference mica pigment was used in place of the metal mixed oxide flake pigment composed of two or more metal elements,
In Comparative Example 2, carbon black was omitted. Then, the mixture was stirred and mixed with an organic solvent (mass ratio of toluene / xylene / ethyl acetate / butyl acetate = 70/15/10/5) so as to obtain a coating proper viscosity by a stirrer to prepare a jet-black paint.

The clear coating clear paint was used the following paint. A: Acrylic resin solvent-based clear paint (trade name: "Super Lac O-130 Clear", manufactured by Nippon Paint Co., Ltd.); B: Solvent-based clear paint comprising a blend of a carboxyl group-containing polymer and an epoxy group-containing polymer (trade name) :
"Macflow O-520 Clear", manufactured by Nippon Paint Co., Ltd.).

On the surface to be coated of the base material for forming the multi-layer coating film , the above-mentioned intermediate coating film layer was dried to a thickness of 50 μm.
m, and then a jet-black paint layer shown in Table 1 was applied to form a dry film thickness of 30 μm. Next, the clear top coat layer was applied by W / W to a dry film thickness of 50 μm to form a multilayer coat. The baking condition was 140 ° C. for 20 minutes. The following evaluation items of the obtained coating film were evaluated by the following evaluation methods. Table 1 shows the results.

Evaluation method High jet-blackness: Jet-blackness when the test plate was viewed obliquely (shade portion) was visually evaluated. 3: Remarkable jet-blackness 2: Jet-blackness 1: White blurring and insufficient jet-blackness Interference: When the test specimen after coating formation is viewed from almost directly above (A), the bird's-eye angle to the test specimen When viewed at about 15 degrees (B), the color of the coating film was visually evaluated. 3... In which the colors presented in (A) and (B) are clearly different 2... In which the colors presented are different in (A) and (B) 1... Are the same

[0038]

[Table 1]

As is clear from the results in Table 1, this example shows that a multi-layer coating film was formed by the coating film forming method using the jet-black paint composition of the present invention, and high jet-blackness and interference Was obtained.

On the other hand, in the comparative example, a multilayer coating film as obtained in the above example was not obtained.

[0041]

The jet-black paint composition of the present invention contains a metal mixed oxide flake pigment comprising two or more metal elements, a carbon black pigment and a vehicle.
The multi-layer coating film formed by this paint can exhibit high jet-blackness and interference without white blur in the shade portion.

The multi-layer coating film of the present invention exhibits the high jet-blackness and interference design, so that it can be used for a vehicle outer panel such as an automobile or a motorcycle.
These parts, various container outer surfaces, coil coating, furniture, home appliance industry, communication industry, and the like are preferably used in fields requiring the above design.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 201/08 C09D 201/08 F term (Reference) 4D075 CA48 CB04 CB13 DA06 DA13 DB02 DB06 DB07 DB12 DB13 DB18 DB20 DB21 DB36 DB38 DB43 DB47 DB48 DB50 DB53 DB61 DC12 DC16 DC19 DC38 DC41 EA06 EA07 EA10 EA19 EA23 EA43 EB16 EB22 EB32 EB33 EB35 EB36 EB37 EB38 EC02 EC07 EC10 EC11 EC23 EC54 4F100 AA17B AA18B AAABAAABAABB CA13B CC00B CC00C GB41 GB48 GB81 JN01C YY00B 4J038 CC061 CD091 CF091 CG141 CG151 CG171 CH031 CH041 CH121 CH171 DB001 DB221 DD041 DD121 DF001 DG031 HA026 HA166 KA08 KA20 NA01 NA19 PA19 PB02 PB09 PC02

Claims (9)

[Claims] 1. A jet-black paint composition comprising a metal mixed oxide flake pigment comprising two or more metal elements, a carbon black pigment and a vehicle. 2. A color-forming metal element selected from the following group (A), wherein at least one of the two or more metal elements constituting the metal mixed oxide flake pigment composed of the two or more metal elements is: 1. The jet-black paint composition according to 1. Group (A): Co, Ni, Fe, Mn, Cu, Cr, V,
Na, W 3. The color-adjusting metal element other than the color-forming metal element is a metal element selected from the following color-adjustment metal elements in the group (B) or color-auxiliary metal elements in the group (C). 3. The jet-black paint composition according to 2. (B) group: Ti, Sb, As, Bi, P (C) group: Al, Si, K, Ca, Mg, Ba, Zn,
Li, Zr 4. The solid content ratio of the metal mixed oxide flake pigment and the carbon black pigment is 99/1.
The jet-black paint composition according to any one of claims 1 to 3, wherein the ratio is from 70 to 30/30. 5. The jet-blackness according to claim 1, wherein the total content of the metal mixed oxide flake pigment and the carbon black pigment is 5 to 30% by mass based on the solid content of the paint. Paint composition. 6. A method for forming a coating film using the jet-black paint composition according to any one of claims 1 to 5 for forming at least one of the layers constituting the multilayer coating film. 7. An undercoat film layer, an intermediate coat film layer,
A method for forming a multilayer coating film in which a topcoat layer and a clear topcoat layer are sequentially formed, wherein the topcoat layer is formed by the jet-black paint composition according to any one of claims 1 to 5. A coating film forming method in which a jet-black coating film layer is formed. 8. The method according to claim 7, wherein the clear top coat layer is formed from a paint containing a carboxyl group-containing polymer and an epoxy group-containing polymer. 9. A multilayer coating film obtained by the method for forming a coating film according to any one of claims 6 to 8.