JPH09310038A - Colored coating liquid excellent in light resistance and patterned coating film using the same liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a colored coating liquid capable of forming a coating film excellent in light resistance even in thin film and provide a method for forming a coating film capable of readily forming patterned coating film having good light resistance and originality. SOLUTION: This colored coating liquid is obtained by dispersing a colored pigment and at least one kind of pigment selected from transparent iron oxide pigment and fine particle zinc oxide in an amount of 5-100 pts.wt. based on 100 pts.wt. of the colored pigment into a liquid containing a resin. This method for forming a coating film comprises applying at least one kind of colored coating liquid among colored coating liquids having cyan, magenta, yellow and black colors and forming patterned coating film onto the substrate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored coating liquid such as ink or paint capable of forming a coating film having excellent light resistance, and a pattern coating having excellent weather resistance and originality using this colored coating liquid. The present invention relates to a coating film forming method capable of forming a film.

[0002]

2. Description of the Related Art Demands for coating colors on automobile bodies of automobile users (including motorcycles, which are two wheels) are diversifying year by year. There are strong demands for unique colors, patterns, and marking designs, especially for RV (recreation vehicle) vehicles. Further, in commercial vehicles such as mini buses, there is an increasing demand for differentiation by pattern painting such as company logos and product images. In order to respond to these trends, it has become an important issue to expand the range of designability by pattern painting.

In some automobile users, an original seal or patch is attached on the top coating film of the automobile body, or a colored coating liquid (ink or paint) is applied by an air spray device having a fine aperture nozzle. There are some cases where partial coating or pattern coating is attempted with a thin film of about 1 μm at most, but in both cases, the light resistance and adhesion are inferior to the existing top coating film, and discoloration, fading or sealing occurs early. There is a drawback that the difference in level between the patch and the existing topcoat film deteriorates the cosmetic appearance.

[0004]

SUMMARY OF THE INVENTION Accordingly, the present inventors
Even in the case of partial coating or pattern coating with a thin film, earnest research was conducted in order to obtain a colored coating liquid such as ink or paint capable of forming a coating film having excellent light resistance.
Further, not only for automobile users, but also for the coating film forming method capable of easily forming a patterned coating film having good light resistance and originality, which is satisfied by customers, was also earnestly studied.

As a result, a thin film can be obtained by using a coloring coating liquid prepared by dispersing a pigment component obtained by mixing a transparent iron oxide pigment and / or zinc oxide fine particles in a specific amount with the coloring pigment in a liquid containing a resin. Even in the above, it was found that a coating film having excellent light resistance can be formed, and the present invention has been completed.

Further, by applying a pattern coating film on a substrate using at least one coloring coating liquid of each of the above-mentioned coloring coating liquids of cyan, magenta, yellow and black, good light resistance can be obtained. Therefore, the inventors have found that it is possible to easily form a patterned coating film having originality, and have completed the coating film forming method of the present invention.

[0007]

That is, the present invention provides a coloring pigment, and 5 to 1 with respect to 100 parts by weight of the coloring pigment.
A colored coating liquid, characterized in that an amount of at least 100 parts by weight of at least one pigment selected from transparent iron oxide pigments and fine zinc oxide particles is dispersed in a liquid containing a resin. is there.

The present invention is also the above-mentioned colored coating liquid, which is at least one of the cyan, magenta, yellow and black colored coating liquids, and is applied onto a substrate. The present invention provides a method for forming a coating film, which comprises forming a patterned coating film.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The colored coating liquid of the present invention will be described below.

The colored coating liquid of the present invention is a coating liquid in which a color pigment and a transparent iron oxide pigment and / or fine zinc oxide particles are dispersed in a liquid containing a resin.

The liquid containing the above resin contains the resin,
And a liquid that can be used without particular limitation as long as it is a liquid capable of forming a coating film by the obtained colored coating liquid,
For example, a liquid resin alone, an organic solvent solution or an aqueous solution obtained by dissolving a resin in a solvent, an organic solvent dispersion liquid (non-aqueous dispersion type, NAD) obtained by dispersing a resin in a solvent, an aqueous dispersion liquid (emulsion), etc. The form can be mentioned.

The type of the above-mentioned resin is not particularly limited, and acrylic resin-based, alkyd resin-based, polyester resin-based,
Various resin types such as silicone resin type and fluororesin type can be used, and these resin type ones are used in combination with a curing agent such as amino resin, polyisocyanate compound, polyepoxy compound and polycarboxylic acid compound. It may be a combination. Further, the resin may be any of a thermosetting type, a lacquer curing type, an oxidation curing type and a photocuring type. In addition, when it does not cure by itself, for example, when the resin has a hydroxyl group, and a clear coating containing a polyisocyanate compound is applied onto a colored coating film containing this resin It may be a so-called soak-curing type resin in which the polyisocyanate compound of (3) diffuses to cure the resin of the colored coating film.

As the color pigment, various color pigments used for paints and inks can be used.
For example, in the case of forming a pattern coating on a white coating of an automobile, in order to produce a wide range of coating colors with a limited number of coloring coating liquids, the basic primary colors of cyan, magenta, yellow, And it is preferred to use black pigments.

The cyan pigments include cyanine blue pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, metal-free cyanine blue, indanthrene blue, navy blue, ultramarine blue and cobalt. Examples thereof include blue, and among them, phthalocyanine blue pigments such as cyanine blue pigment blue 15: 3 and cyanine blue pigment blue 15: 4 are preferable from the viewpoint of color tone and light resistance.

Examples of the magenta pigment include lake red 4R, carmine FB, dinitroaniline orange, pyrazolone orange, pyrazolone red, perinone orange, permanent red 2B, lake red R, bon maroon light, bordeaux 10B, bon maroon medium. , Thioindigo bordeaux, bon maroon L, perylene vermillion, perylene scarlet, perylene maroon, benzimidazolone orange, chrome vermillion molybdenum red, toluidine red, quinacridone red, among which quinacridone red, especially Dimethylquinacridone and dichlorquinacridone are preferable from the viewpoint of color tone and light resistance.

Examples of the yellow pigment include Fast Yellow G, Fast Yellow 10G, and Shimura Yellow 411.
9, Permanent Yellow FGL, Benzimidazolone, azo and other monoazo pigments; Disazo Yellow AAM
X, Disazo Yellow AAOT, Disazo Yellow AA
Disazo pigments such as OA, Permanent Yellow HR, and Lionol Yellow FFR; Chromophthal Yellow 3
G, Chromophthal Yellow 6G, Chromophthal Yellow GR, and other condensed azo pigments; Irgadine Yellow 3RLT
N, Irgadine Yellow 2RLT, Irgadine Yellow 2GLT, Fastgen Super Yellow GROH, Fastgen Super Yellow GRO, Sandrin Yellow 6GL, etc., Isoindolinone pigments; Anthrapyrimidine Yellow, Flavantron Yellow, Acylamino Yellow, etc. Pigments: Green Gold, Paliotre Yellow 1070, Paliotre Yellow 177
0, metal complex pigments such as Irgadine Yellow 5GT; quinophthalone yellow, isoindoline yellow, yellow lead,
Examples thereof include titanium yellow, and among these, benzimidazolone, isoindolinone pigment, isoindoline and quinophthalone yellow are preferable from the viewpoint of color tone, light resistance and the like. .

Examples of the black pigment include carbon black, pine smoke, graphite, iron black and the like, among which carbon black is preferable. .

Coloring pigments other than those mentioned above include chrome green, cobalt green, chromium oxide, cyanine green, brominated green, cobalt chrome green,
Green pigments such as titanium / nickel / cobalt / zinc greens; purple pigments such as cobalt violet, manganese violet, dioxazine violet, β-quinacridone violet; titanium white, antimony white, lead white, monobasic lead sulfate, etc. And the like.

In the colored coating liquid of the present invention, a transparent iron oxide pigment and //
Alternatively, fine particles of zinc oxide are dispersed, and the iron oxide pigment and fine particles of zinc oxide absorb light such as ultraviolet rays and contribute to improvement of light resistance of the coating film.

Examples of the transparent iron oxide pigments include fine particle transparent iron oxide yellow pigments such as Transoxide Yellow (manufactured by Hilton Davis) and Chico Trans Yellow L1916 (manufactured by BASF), Transoxide Red (manufactured by Hilton Davis) and Chico. Trans Red 2817 (BASF
Examples thereof include fine particle transparent iron oxide red pigment.

The fine zinc oxide particles may be zinc oxide pigments having an average primary particle diameter of 0.1 μm or less, and the surface thereof is surface-treated with one or more of silica, alumina and zirconia. Those that are preferred are. As a commercial product of fine-particle zinc white, for example, Finex 50
A, Finex 25A (all manufactured by Sakai Chemical Industry Co., Ltd., fine particles of zinc and white treated with silica and alumina).

The above-mentioned transparent iron oxide pigment and zinc oxide fine particles are
Each can be used alone or in combination of both, and can be used in combination with a coloring pigment.

In the colored coating liquid of the present invention, the mixing ratio of the above-mentioned color pigment and at least one pigment selected from the above-mentioned transparent iron oxide pigment and fine zinc oxide powder is 100 parts by weight of the former (color pigment) to the latter. Is used in a ratio of 5 to 100 parts by weight. When the ratio of the latter is less than 5 parts by weight, the effect of improving the light resistance is insufficient, while the ratio of the latter is 1
If it exceeds 100 parts by weight, there is almost no further effect of using it in excess of 100 parts by weight, and the color tone of the colored coating liquid deteriorates.
It may lead to increase in viscosity, deterioration of coating property, and decrease of coating film strength.

The amount of the resin in the colored coating solution of the present invention is not particularly limited as long as the coating strength of the resulting coating film is sufficient and the colored coating solution has a desired coloring power. No, but usually the color pigment / resin weight ratio is 1
It is used in the range of 0/100 to 200/100.
When the coloring pigment is an organic pigment, 15/100 to 150 /
A range of 100, preferably 20/100 to 100/100 is suitable. When the coloring pigment is an inorganic pigment other than carbon black, the range of 50/100 to 200/100, preferably 80/100 to 160/100 is suitable. 5/10 if the color pigment is carbon black
0-50 / 100, preferably 10 / 100-30 / 1
A range of 00 is suitable.

The coloring coating solution of the present invention may comprise a resin, a coloring pigment, and at least one pigment selected from transparent iron oxide pigments and fine zinc oxide particles, but usually a solvent is used for adjusting the viscosity. Be compounded. As the solvent, an organic solvent capable of dissolving or dispersing a resin, water is used. In addition to these, the colored coating liquid of the present invention contains a pigment dispersant, a neutralizing agent, a surface modifier, a surfactant, an antifoaming agent, a fluidity modifier, an ultraviolet absorber, a light stabilizer, and a curing catalyst, if necessary. And the like can be appropriately contained.

The coating film forming method of the present invention using the colored coating liquid of the present invention will be described below.

In the method for forming a coating film of the present invention, a colored coating liquid which is the above-mentioned colored coating liquid and is at least one of cyan, magenta, yellow and black colored coating liquids is applied. A patterned coating film is formed on a substrate.

The above-mentioned base material can be used without particular limitation as long as it can be an object to be coated, and examples thereof include metals such as steel plate, aluminum plate, galvanized steel plate, iron-zinc alloy plated steel plate, and the like. Chemical conversion treatment metal that has been subjected to chemical conversion treatment such as chromate treatment, zinc phosphate treatment, iron phosphate treatment, plastics such as FRP, wood, paper and other materials; these metals, chemical conversion treatment metal, plastics,
An example of the coating film forming material is a coating film formed on the surface of a material such as wood.

The coating film of the coating film-forming material may be a single-layer coating film, a two-coat coating film of undercoat-top coating, a three-coat coating film of undercoat-intermediate coating-top coating, or a single-layer coating. May be

The above coating film-forming material is used for automobiles, etc. (1) Undercoat (electrodeposition) -on a metal surface such as a steel plate
In the case where a three-coat coating film of the middle coat-top coat or a two-coat coat film of the undercoat (electrodeposition) -top coat is formed, and (2) a two-coat coat film of the undercoat-top coat is formed on the plastic surface. The following is an example of the case of the above.

In the above (1), in order to form an undercoat coating film on a metal surface which is a conductive material such as a chemical conversion treated metal surface which has been subjected to a zinc phosphate treatment, the undercoat paint is spray coated on the metal surface and rolled. It can be carried out by coating by a known method such as coating, dip coating, electrodeposition coating, etc., but it is preferable to form the undercoat coating film by electrodeposition coating using an electrodeposition coating as the primer coating. Done.

The thickness of the undercoat coating film is usually 3 to 4 as a dry film thickness.
It is suitable that it is 0 μm, preferably about 15 to 30 μm.

After undercoating is applied by electrodeposition coating or the like, it is washed with water if necessary, and then air-dried or after curing by baking or the like, an overcoat paint is applied with or without an intermediate coating film.

The intermediate coating material may be any of water-based coating material, organic solvent-based coating material and powder coating material, and the resin-based coating material may be alkyd resin-based coating, polyester resin-based coating, acrylic resin-based coating, polyurethane resin-based coating, Various resin-based paints such as vinyl resin-based paints can be used. Among them, a polyester resin is generally used.

A pigment is mixed in the intermediate coating material for the purpose of hiding the base material. Although the method of curing the intermediate coating composition is not particularly limited, it can be usually performed by baking. The intermediate coating film may have a chipping resistance function or the like. When the intermediate coating is applied in a state where the undercoat is uncured, the electrodeposition coating is simultaneously cured when the intermediate coating is baked. The thickness of the intermediate coating film is usually from 15 to 50 μm, preferably from about 20 to 40 μm, as a dry film thickness.

The topcoat paint to be applied on the undercoating film or the intermediate coating film is a paint capable of forming a good coating film having good cosmetic properties, coating film hardness and durability, and can be used as a topcoating paint for automobiles. Any material can be used without particular limitation. Examples of the form and resin type of the top coat paint include the same form and resin type as those described in the above middle coat paint.

The coating color of the topcoat paint is not particularly limited, but when a pattern coating film is formed on the topcoat coating film, the visibility of the pattern formed on the topcoat coating film, etc. From this point of view, a light color, preferably a white coating color is suitable. If the pattern coating film has a design even on a dark top coat, a dark top coat can also be used.

The thickness of the top coating film is usually 10 to 10 in terms of dry film thickness.
The thickness is 40 μm, preferably about 15 to 30 μm.

In the above (2), when a coating film is formed on a plastic substrate, plastics generally have poor adhesion of the coating film. A coating material that can improve the adhesiveness of the coating film is used, and a known material used as a primer for plastics can be used. The undercoat can be applied by a known method such as spray coating, roll coating, or dip coating. The film thickness of the undercoat coating film is usually 3 to 40 as a dry film thickness.
It is suitable that the thickness is μm, preferably about 15 to 30 μm.

As the top coat paint for plastics coated on the above-mentioned primer, the same forms and resin types as those mentioned above as the top coat paint in the case of (1) can be used. Known top coat paints for plastics used for can be suitably used. The coating color and film thickness of this top-coat paint can be the same as those in the above-mentioned top-coat paint.

In the method of the present invention, as a method of applying at least one kind of the colored coating solution of each color to form a patterned coating film on the above-mentioned substrate, brush coating, roll coating, silk screen printing Although it can be performed by a coating method such as the one described above, spray coating is preferable, and among them, a method of coating with an automatic robot having a spray device having a fine aperture nozzle (hereinafter, also referred to as “ink jet method”) is available. It is suitable.

There are two types of paint atomization in the ink jet system, an air spray type using a micro two-fluid nozzle having a mechanism for suppressing spray diffusion and an airless type using a single hole nozzle. It can be used properly depending on the size. In general, a single-hole nozzle is used to make the boundary line clear or a fine pattern is drawn, and a very small two-fluid nozzle is used to blur or paint a large area. In both cases, the coating liquid can be discharged only to a required portion by an on-demand type spray ON / OFF (ON / OFF) mechanism.

A coating head of an ink jet type coating machine has three basic colors, cyan, magenta, and yellow, or four basic coloring liquids obtained by adding black to these three colors (hereinafter,
"Basic primary color"), each has a dedicated nozzle, and further contains a coating liquid containing a bright pigment or a coloring coating liquid other than the above basic primary colors, for example, a coloring coating liquid such as white, green, or purple, or two or more kinds. When using a colored coating liquid obtained by mixing the above colored coating liquids, a nozzle for these coating liquids may be installed. A color tone in a practical range can be obtained by coating three or four basic primary colors. Therefore, when only the basic primary colors are used, the number of dedicated nozzles may be three or four.

In addition to the above-mentioned basic primary colors, if necessary, a coating liquid of a primary color or a mixed color other than the above-mentioned basic primary colors or a nozzle of a coating liquid containing a bright pigment is used in combination so that four basic primary colors can be obtained. A special color tone that cannot be produced can be produced, and the range of designability can be greatly expanded. As the bright pigment of the coating liquid containing the bright pigment, aluminum powder, copper powder, stainless steel powder, nickel powder, micaceous titanium foil, micaceous iron oxide foil, graphite and the like can be used.

The coating head equipped with these dedicated nozzles is operated in combination with an automatic coating machine that moves in a three-dimensional space, which is a fixed distance which is a close distance from the three-dimensional object, in accordance with the position data. The target patterned coating film can be formed by discharging the coating liquid from a dedicated nozzle and sequentially coating the coating liquid as needed (the order may be set appropriately). The coating time for pattern formation by the inkjet method varies depending on the type of pattern and the coating area, but when used in combination with an automatic coating machine (automatic robot), continuous coating can be performed and productivity can be improved.

The ink jet system has a great advantage that the coating efficiency of the coating is close to 100% because the coating particles are sprayed onto the object to be coated from a very short distance. It is possible to significantly reduce the running cost for supply and exhaust.

In the method of the present invention, as the pattern coating film,
Includes patterns of specific shapes, multicolored patterns, as well as two-tone finished coatings. The film thickness of the pattern coating film is not particularly limited as long as the coating color of the target pattern coating film is obtained, but it is usually about 0.5 to 20 μm as a dry film thickness. When coating with the inkjet method, the coating film thickness and the number of times of coating changes depending on the desired color, so the film thickness in a minute area is likely to differ, and the flight distance of paint particles is short, so the viscosity of the coating liquid is high. It is difficult to apply thick coating because it easily sags. Normally, the dry film thickness is 0.5.
It is a thin film of about 10 μm.

The method of the present invention may be a coating film forming method in which a pattern coating film is applied on a substrate and the pattern coating film is cured by baking or drying at room temperature to form the pattern coating film. The curing method can be appropriately selected according to the resin type of the colored coating liquid used. Alternatively, a clear coating may be applied onto the substrate after the pattern coating is applied and the pattern coating is cured, or in an uncured (including semi-cured) state.

The patterned coating film is generally a thin film, especially when it is applied by the ink jet method. Since the coating liquid needs to contain a large amount of pigment in order to obtain a sufficient coloring power with the thin film, the pattern coating film is left as it is. Then, the patterned coating film may have a low gloss and the appearance of the coated surface may be inferior, or the chemical resistance may deteriorate.
These problems can be solved by applying a clear paint on the pattern coating film.

As the clear paint, any clear paint having good weather resistance can be used without limitation, such as organic solvent type paint, water-based paint and powder paint. Various resins such as an acrylic resin, a polyester resin, an alkyd resin, a silicone resin, and a fluororesin can be used as the resin, and may be a thermosetting type or an active ray such as an ultraviolet ray or an electron beam. May be cured. As the clear coating, those used as the top clear coating for automobiles are preferably used, and among them, the acrylic resin type thermosetting clear coating is suitable.

The clear coating composition may be applied after the pattern coating film is cured. However, when the clear coating composition is a thermosetting type, the pattern coating film is air-dried and uncured. It is preferable to apply a clear paint and then heat it to bake the pattern coating film and the clear coating film at the same time from the viewpoints of interlayer adhesion between the pattern coating film and the clear coating film, reduction of heating energy amount, and the like. Further, the clear paint may contain an ultraviolet absorber and a light stabilizer in order to improve light resistance. The clear paint may be applied only on a portion having a pattern, but is preferably applied over the entire surface.

The coating film thickness of the clear coating material may be appropriately set according to the type of the clear coating material and is not particularly limited, but it is usually in the range of about 10 to 50 μm as a dry coating film thickness.

[0053]

EXAMPLES The present invention will be described in more detail below with reference to examples. Hereinafter, "parts" and "%" are based on weight.

Production of Acrylic Resin Aqueous Solution Production Example 1 Ethylene glycol monobutyl ether 60 was placed in a reaction vessel.
And 15 parts of isobutyl alcohol, and heated to 115 ° C. in a nitrogen stream. Maintained at 115 ° C., n-butyl acrylate 26 parts, methyl methacrylate 47 parts, styrene 10 parts, 2-hydroxyethyl methacrylate 10
Parts, acrylic acid 6 parts and azobisisobutyronitrile 1
Parts of the mixture were added to the reaction vessel over 3 hours. After the addition was completed, the mixture was aged at 115 ° C. for 30 minutes, a mixture of 1 part of azobisisobutyronitrile and 115 parts of ethylene glycol monobutyl ether was added over 1 hour, and the mixture was further added to 3 parts.
After aging for 0 minutes, the mixture was filtered through a 200-mesh nylon cloth at 50 ° C.

The obtained reaction product had an acid value of 48, a viscosity (Gardner foam viscometer) Z ₄ , a solid content of 55% and a glass transition point (Tg) of 45 ° C. This was neutralized with diethanolamine in an equivalent amount, and deionized water was further added to obtain an acrylic resin aqueous solution having a solid content of 50%.

Manufacturing Method of Acrylic Resin Emulsion Manufacturing Example 2 140 parts of deionized water and 30% Newcol were placed in a reaction vessel.
707SF (Nippon Emulsifier, anionic surfactant)
2.5 parts and 1 part of the following monomer mixture (1) were added, stirred and mixed in a nitrogen stream, heated to 60 ° C., and 3 parts of a 3% ammonium persulfate aqueous solution was added. Then heat to 80 ° C,
Hold, 99 parts of the following monomer mixture (1), 30% N
A monomer emulsion consisting of 2.5 parts of ewcol 707SF, 4 parts of 3% ammonium persulfate aqueous solution and 42 parts of deionized water was added to the reaction vessel using a metering pump over 4 hours. After completion of the addition, aging was carried out for 1 hour.

Next, the following monomer mixture (2) was added to the reaction vessel over 1.5 hours while maintaining the temperature at 80 ° C. After the addition was completed, the mixture was aged for 1 hour and filtered at 30 ° C. with a 200 mesh nylon cloth. did. Deionized water was further added to this, and the pH was adjusted to 7.5 with diethanolamine.
A 20% acrylic resin emulsion at 6 ° C. was obtained.

The monomer mixture (1) contains 55 parts of methyl methacrylate, 10 parts of styrene and 9 parts of n-butyl acrylate.
Part, a mixture of 5 parts of 2-hydroxyethyl acrylate and 1 part of methacrylic acid.

The monomer mixture (2) contains 5 parts of methyl methacrylate, 7 parts of n-butyl acrylate, 5 parts of 2-ethylhexyl acrylate, 3 parts of methacrylic acid and 30% Newc.
o 707SF 0.5 part mixture of 3% ammonium persulfate aqueous solution 4 parts and deionized water 30 parts.

Production of Colored Coating Liquid Example 1 Cicotrans Yellow L-1916 2 parts (manufactured by BASF, fine particle transparent iron oxide yellow pigment) Pariotor Yellow L-1820 10 parts (manufactured by BASF, yellow colored pigment) 50% solid content aqueous solution of acrylic resin obtained in Example 1 10 parts Deionized water 70 parts Total 92 parts A mixture having the above composition was dispersed in a paint shaker for 2 hours, and then the dispersion was mixed with Cymel 256 (Mitsui Cytec). 5 parts by weight, methyl etherified melamine resin solution, solid content 80%), 50 parts by weight of acrylic resin emulsion having a solid content of 20% obtained in Production Example 2, 45 parts of deionized water and 8 parts of isopropyl alcohol are mixed and stirred. Thus, a yellow colored coating liquid (Y-1) having a color pigment / resin solid content weight ratio = 10/19 was obtained. The resulting yellow colored coating liquid (Y-
The viscosity of 1) was 15 mPa · s (25 ° C.).

Comparative Example 1 The same procedure as in Example 1 was carried out except that Sicotrans Yellow L-1916 was not added, and the color pigment /
Yellow solid color coating liquid (Y:
-2) was obtained.

Example 2 In Example 1, 10 parts of Pariottle Yellow L-1
The same procedure as in Example 1 was repeated except that 10 parts of Hosta Palm Pink EB (manufactured by Hoechst, dimethylquinacridone, magenta color pigment) was used instead of 820, and the color pigment / resin solid content weight ratio = 10/19. A magenta colored coating liquid (M-1) was obtained. The obtained magenta colored coating liquid (M-
The viscosity of 1) was 12 mPa · s (25 ° C.).

COMPARATIVE EXAMPLE 2 The procedure of Example 2 was repeated except that Shicotrans Yellow L-1916 was not added, and the color pigment /
A magenta colored coating liquid (M-2) having a resin solid content weight ratio of 10/19 was obtained.

Example 3 In Example 1, 2 parts of Sicotrans Yellow L-19
Instead of 16 parts, 2 parts of Finex 25A (Sakai Chemical Co., Ltd., fine particle zinc white) is used, and instead of 10 parts of Pariotor Yellow L-1820, 10 parts of cyanine blue G
-314 (manufactured by Sanyo Dye Co., Ltd., phthalocyanine pigment) is used in the same manner as in Example 1 and a cyan color coating liquid (C-1) having a color pigment / resin solid content weight ratio = 10/19.
I got The viscosity of the obtained cyan color coating liquid (C-1) was 8 mPa · s (25 ° C.).

Comparative Example 3 The procedure of Example 3 was repeated, except that the Finex 25A was not added, and the color pigment / resin solid content weight ratio = 10/19 (c-2). ) Got.

Example 4 In Example 1, 2 parts of Sicotrans Yellow L-19
Use 2 parts of Finex 25A instead of 16,
5 instead of 10 copies of Paliotre Yellow L-1820
Part Mitsubishi carbon black MA-100 (manufactured by Mitsubishi Kasei Kogyo Co., Ltd., carbon black pigment) was used in the same manner as in Example 1, and the color pigment / resin solid content weight ratio = 5 /.
19 black colored coating liquids (B-1) were obtained. The viscosity of the obtained black colored coating liquid (B-1) was 7 mPa · s (25 ° C.).

Comparative Example 4 A black colored coating solution (B-2) having a color pigment / resin solid content weight ratio = 5/19 was carried out in the same manner as in Example 4 except that Finex 25A was not added. Got

Using the colored coating liquids obtained in Examples 1 to 4 and Comparative Examples 1 to 4, test plates were prepared by the following coating method.

Coating method (1) Preparation of object to be coated On a cold-rolled steel sheet treated with zinc phosphate, "Electron GT-1
"0" (Kansai Paint Co., Ltd., cationic electrodeposition paint) was subjected to cationic electrodeposition coating and baked to form a 20 μm-thick undercoat film. "TP-37 gray" (Kansai Paint Co., Ltd., polyester-based intermediate coating, gray color) was applied and baked on the undercoating coating so that the dry film thickness was 30 μm to form an intermediate coating. On this intermediate coating film, "Neo-Amilac White" (manufactured by Kansai Paint Co., Ltd., polyester-based top coating material, white) was applied and baked so as to have a dry film thickness of 30 [mu] m to form a top coating film. The coated plate thus obtained was used as an article to be coated.

(2) Preparation of test coated plate On the top coating film of the article to be coated obtained as described above, Example 1 was applied.
~ 4 and the respective colored coating liquids obtained in Comparative Examples 1 to 4 were applied by air spraying so that the dry coating film had a thickness of about 1 µm,
After drying for 5 minutes to remove water, "Retan PG60 clear" (Kansai Paint Co., Ltd., acrylic-urethane two-component clear top coating clear paint) is applied on it to give a dry film thickness of 35 µm. Baking was performed at 140 ° C. for 20 minutes to prepare test plates of each color.

Further, the colored coating liquids (Y) obtained in Examples 1 and 2 were used.
-1) and (M-1) are applied to each other so that the dry film thickness is 1 μm, and the total film thickness is 2 μm, and then “Retane PG60 clear” is applied thereon so that the dry film thickness is 35 μm. Then, baking was performed at 140 ° C. for 5 minutes to prepare a test plate having a red color tone. Further, instead of the colored coating liquids (Y-1) and (M-1), the colored coating liquids (Y-2) and (M-
A test plate with a red color tone, which was coated in the same manner as above except that the coating was carried out using 2) and had a dry film thickness of (Y-2) 1 μm- (M-2) 1 μm-clear coating 35 μm. It was created.

(3) Test Method The test plate obtained as described above was subjected to a 1200-hour accelerated exposure test with a sunshine weatherometer, which is an accelerated weathering tester manufactured by Suga Test Instruments Co., Ltd. The color difference (ΔE ^* ) between the initial coating film and the coating film after the test was measured with. The smaller the color difference (ΔE ^* ), the better. Further, the degree of discoloration and the change in gloss were visually examined. The evaluation was based on the following criteria. The test results are shown in Table 1 below.

Degree of discoloration ○: Discoloration is not noticeable Δ: Significant discoloration is recognized ×: Gloss change that allows significant discoloration ○: Almost no decrease in gloss is recognized Δ: Significant decrease in gloss is recognized ×: Significant gloss Decline is observed

[0074]

[Table 1]

As shown in Table 1, each of the colored coating liquids obtained in the examples showed a lesser degree of discoloration and less deterioration in gloss than the respective colored coating liquids obtained in the comparative examples, and showed good weather resistance. Further, regarding the coating film coated with the colored coating liquid, the one using each colored coating liquid obtained in the example showed better weather resistance than the one using each colored coating liquid obtained in the comparative example.

Example 5 An automatic painting machine [specifically, set with a specific pattern in a computer beforehand and operated by being controlled by the computer]
"KER420" manufactured by Kobe Steel Ltd.]
4. Using the colored coating solution obtained in 4 above, using a head having four minute diameter nozzles which are dedicated nozzles corresponding to these four colors, the above-mentioned specific pattern is formed on the top coating film of the article to be coated. Painted and dried at 80 ° C. for 5 minutes. Two types of heads were used, one having a dedicated single-hole nozzle and the other having a dedicated extremely small two-fluid nozzle, and the distance between the nozzle during coating and the surface to be coated was about 3 cm. Then, the organic solvent-diluted thermosetting acrylic resin-based clear paint "Magiclon Clear" (Kansai Paint Co., Ltd., top-coat clear paint) was applied on the top coating film and pattern by a rotary electrostatic coating machine and baked. Form a clear top coating with a thickness of about 35 μm,
A coated article having a pattern and a clear top coating film on the top coating film of the article to be coated was prepared.

Comparative Example 5 In Example 5, the coloring coating liquid used in Example 1 was used.
Coating was performed in the same manner as in Example 5 except that the colored coating liquids obtained in Comparative Examples 1 to 4 were used instead of the colored coating liquids obtained in
A coated article having a pattern and a clear top coating film on the top coating film of the article to be coated was prepared to prepare a coated article having the same appearance as in Example 5.

The coated articles obtained in Example 5 and Comparative Example 5 were
All had the desired good appearance. The same weather resistance test as described above was conducted on the same portion of the pattern in these coated articles, and the degree of discoloration and the decrease in gloss were visually examined.

In the coated article obtained in Example 5, the degree of visual discoloration and the decrease in gloss were both ◯, and Comparative Example 5
The degree of discoloration by visual inspection was
Or x, and the gloss reduction was ◯ or Δ.

[0080]

The colored coating liquid of the present invention can form a patterned coating film having excellent light resistance even in a thin film. At least 4 of cyan, magenta, yellow and black
By applying the colored coating liquids with a spray device having at least four minute nozzles for spraying each colored coating liquid of the present invention to form a patterned coating film, good light resistance and originality can be obtained. It becomes possible to easily form a patterned coating film. In addition, the performance as a comprehensive coating film can be improved by applying clear coating on the patterned coating film.

Claims (9)

[Claims] 1. A coloring pigment and at least one pigment selected from transparent iron oxide pigments and fine zinc oxide particles in an amount of 5 to 100 parts by weight per 100 parts by weight of the coloring pigment contains a resin. A colored coating liquid characterized by being dispersed in a liquid. 2. The cyan color coating liquid according to claim 1, wherein the color pigment is a phthalocyanine blue pigment. 3. The magenta colored coating liquid according to claim 1, wherein the color pigment is quinacridone red. 4. The color pigment is at least one pigment selected from benzimidazolone, isoindolinone pigment, isoindoline and quinophthalone yellow.
The yellowish colored coating liquid described. 5. The black colored coating liquid according to claim 1, wherein the color pigment is a carbon black pigment. 6. A colored coating liquid according to claim 1, which is at least one of cyan, magenta, yellow and black colored coating liquids, and is coated on a substrate. A method for forming a coating film, which comprises forming a patterned coating film on the surface. 7. The method for forming a coating film according to claim 6, wherein the colored coating liquid is applied with a spray device having a fine aperture nozzle. 8. A colored coating liquid is applied by means of a spray device having at least four fine nozzles for spraying each of the colored coating liquids of at least four colors of cyan, magenta, yellow and black, and pattern coating is performed. The coating film forming method according to claim 7, wherein a film is formed. 9. A colored coating liquid according to claim 1, which is at least one of cyan, magenta, yellow and black colored coating liquids, and is coated on a substrate. 9. The method for forming a coating film according to any one of claims 6 to 8, wherein a clear coating is applied on the patterned coating film after forming the patterned coating film on the patterned coating film.