JPS6254555B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for forming coating films with a wide range of patterns, from dot-like patterns to mesh-like patterns, by simple means. Conventional methods for forming pattern coatings include (1) applying an undercoat to a mechanically embossed base material, and after drying, applying a topcoat of a different color from the undercoat only to the raised areas; (2) silicone oil. Typical methods include adding a large amount of paint to the paint and using the repellency of the paint film, and (3) applying high viscosity paint while it remains highly viscous with poor atomization. . However, in the conventional method described above, for example, method (1), it is not possible to neatly apply the top coat only to the convex parts unless there is a considerable difference in height between the concave and convex parts, and the object to be coated is limited to flat plate-like objects. There were some drawbacks such as: In method (2), the pattern was not noticeable in solid colors, and the pattern was caused by the uneven distribution of the aluminum pigment mixed into the paint, resulting in little change. Method (3) has the disadvantage that it is not possible to obtain a uniform patterned finish with a thin film, and that it results in a thick film finish, which limits its application to cushion floors, wallpaper, etc., and also has poor painting workability. The present invention solves the problems of these conventional methods, and provides a method for forming a patterned coating film that allows various three-dimensional patterns to be obtained by simpler means without being restricted by the shape of the object to be coated. It is something. That is, the present invention applies a slurry-like paint using water as a medium to an object to be coated, and while the paint film is not dry, a slurry-like paint that is mainly composed of an organic solvent and has a solubility in water of 20% by weight (at 20°C) or less is applied. A solvent-based paint using a medium or a medium mainly consisting of an organic solvent is used, and the difference in surface tension from the slurry paint is 5 dynes/cm.
The present invention relates to a method for forming a patterned coating film, which is characterized by repeatedly applying a solvent-based coating material having a temperature higher than (20°C) and then drying the coating film. According to the method of the present invention, the difference in surface tension of each layered liquid paint, the compatibility or repellency of the medium or film-forming components between each paint, and the hue of each paint film, A wide variety of patterns can be obtained based on differences in saturation, brightness, gloss, etc., and a coated object with extremely three-dimensional effect and elegance can be obtained. The slurry paint used in the present invention contains an aqueous medium and a softening point of 5% by weight based on the aqueous medium.
~120°C, resin particles with a particle size of 4~80μ as the main component, and further contains a coloring component and, if necessary, additives such as a surfactant and a thickener. Slurry paint uses a large amount of resin particles of about 4 to 80 microns, so unlike water-based paints such as general water-soluble paints and emulsion paints, it melts once during film formation and then becomes a coating film. Therefore, even if the resin used in solvent-based paints is not compatible with slurry-based paints, the embedding effect works due to the surface tension during melting.
Two layers with strong adhesion are formed. As the resin particles, those commonly used for powder coatings can be used, including acrylic particles.
Typical examples include urethane resin, acrylic-melamine resin, epoxy resin, and polyester resin. As the coloring component, ordinary organic and inorganic coloring pigments and dyes can be used. In particular, when flaky pigments such as aluminum powder, copper powder, and mica powder are used, a pattern with metallic luster can be obtained and the aesthetic appearance is improved. Furthermore, when one component of a reactive dye that develops color through a reaction between two components is added to a slurry paint and the other component is added to the solvent-based paint, at least one of the slurry paint and the solvent-based paint is applied in a partial pattern. In this case, only the areas where the two layers are coated will develop color, and a richly varied design effect can be easily obtained. Examples of the reactive dyes include azoic dyes which form water-insoluble azo pigments through the reaction of a coupling component (priming agent) and a diazo component (developer). The laxatives include β-naphthol, naphthol AS, naphthol AS-D, naphthol AS-
OL, naphthol AS-RL, naphthol AS-PH,
Naphthol AS-E, Naphthol AS-BS, Naphthol AS-TR, Naphthol AS-BO, Naphthol AS-SW, Naphthol AS-GR, Naphthol
AS−LB, naphthol AS−BT, naphthol AS−
G, naphthol AS-SG, polycyclic aromatic oxycarboxylic acid anilides other than naphthalene, and derivatives having effects similar to these.
These primers are alkaline and water soluble and can be added to slurry paints. In addition, the color developers include Fastret B Base, Fastret KB Base, Fastret RL Base, Fastret G Base, Fastret 3GL Base, Fastret RC Base, Fast Scarlet G Base, Fast Scarlet GG Base, Fast Scarlet R.
Examples include diasonium salts obtained by diazotizing base, First Orange GC Base, First Blue BB Base, Variamine Blue B Base, First Garnet GBC Base, First Vold-GP Base, and the like. These primers or color developers can be added in an amount of 0.1 to 30% by weight in slurry paints or solvent-based paints. In this case, it is preferable that the amount of the reactive dye component in the slurry coating material and the amount of the reactive component in the solvent-based coating material be adjusted to about equimolar amounts. On the other hand, as the solvent-based paint used as the top coat, a conventionally known solvent-based paint using a medium mainly consisting of an organic solvent can be used.
The principle of the formation of the pattern of the present invention is to utilize the repelling and bleeding phenomena between the films of slurry paint and solvent-based paint in an undried state, so that the solubility of the medium used in solvent-based paint in water is 20% by weight. % (at 20°C) or less, or the difference between the surface tension of the solvent-based coating and that of the slurry coating is more than 5 dynes/cm (at 20°C).
In this range, the repelling phenomenon and the bleeding phenomenon become noticeable and a pattern appears. Therefore, it is appropriate that the medium used in the solvent-based paint is mainly a water-insoluble hydrocarbon solvent such as benzene, toluene, xylene or mineral spirits. Also, the surface tension of slurry paint is usually 35±5
dyne/cm (20℃), so for solvent-based paints it is 30
Dyne/cm (20°C) or less is appropriate. Conventional organic and inorganic coloring pigments and dyes can be used as the coloring components used in solvent-based paints, but if the coloring components are the same or similar to those used in slurry-type paints, the pattern will not stand out, so the hue and color may be different. It is appropriate to use a material with a large difference in grade such as brightness and brightness. Next, the process of forming the patterned coating film of the present invention will be explained. The slurry paint is applied to the entire surface or part of the object to be coated. This application is carried out by a conventional method such as spray coating, shower coating, flow coating, roll coating or dipping coating. In the case of partial painting, it is preferable to use a coated object that has been previously coated with a color base coat or printing. The slurry paint has a wet film thickness of 50 to 500μ.
It is preferable to apply a coating amount of about 30%. If the coating amount is less than this range, the pattern will be insufficiently formed, and if it is too large, it will be difficult to apply the coating uniformly or to dry the coating film uniformly. Subsequently, while the slurry paint film is still wet, the solvent-based paint is coated over the entire surface or part of the slurry paint film. For application of the solvent-based paint, it is suitable to apply the entire surface by spray coating or by scattering by sputter coating. The amount of solvent-based paint applied can be adjusted freely depending on the pattern to be formed, but it is usually 5 to 80 g/m ²
The degree is appropriate. Generally speaking, if the film thickness of a solvent-based paint is thinner than that of a slurry-based paint, the film of the solvent-based paint will break into each other, resulting in a small dot-like pattern; If the paint film is thicker, the solvent-based paint film will not be completely cut off and will tend to form a net-like pattern in which they are drawn together. Further, when applying slurry paints and solvent-based paints, unique patterns can be formed by combining the following painting methods. (1) Apply slurry paint to a partial pattern using a spray gun using a sputter coating, and apply colored pigments, dyes, flaky pigments, and reactive dyes (however, only one of the primer and developer is used). A solvent-based paint containing one or more of the above (contained in a slurry paint) is applied thinly and uniformly to the entire surface. By this method, the color of the slurry paint film appears almost unchanged in the outline part of the slurry paint film, and a pattern in which the colors of colored pigments, dyes, scaly pigments, reactive dyes, etc. are raised is obtained in the central part. It will be done. In addition, in the area where only the solvent-based coating film is applied, the color of the colored pigment and dye appears, but the scaly pigment (particularly mica powder) and the reactive dye are hardly or not at all noticeable, and the color of the surface of the substrate appears. Therefore, when forming a tiled pattern using this method, the color of the joints can be applied on the object in advance. (2) Apply slurry paint to the entire surface or in a pattern,
By adjusting the solvent-based paint to various sizes according to your preference and sputter painting, you can obtain a wide variety of patterns from minute dots to polka dots. This pattern is completely different from the pattern obtained by sputtering a different color paint onto a dry coating film. (3) If the slurry paint is applied in the form of narrow lines or small dots, or bubbles are formed, and then the solvent-based paint is applied over the entire surface, the solvent-based paint will be added to the slurry paint film. A unique oil droplet-like dotted or island-like pattern of paint is obtained. In this case, a more advanced design effect can be obtained by using a reactive dye for coloring. In order to form this foam, a suitable amount of a foaming agent or foaming aid such as polyacrylate (ammonium, sodium salt, etc.), polyethylene oxide, poval is mixed into the slurry paint and the foam is foamed during painting. You can take it. After this slurry paint is applied onto a substrate and foamed, a solvent-based paint with a low surface tension and, if necessary, an antifoaming agent added thereto, is applied to further reduce the surface tension. In the foaming area of a slurry paint film, the solvent-based paint with a low surface tension dissolves, the surface tension decreases, and the foam tends to defoam and spread.
The defoamed area becomes a cracked pattern with different colors and densities, or a fish-eye pattern if the foaming is small. Of course, the methods (1) to (3) above can be applied in combination as appropriate. The formed slurry paint and solvent-based paint films are then dried and deposited. For drying, it is preferable to use a conventional hot air drying oven, infrared ray drying oven, etc., and if necessary, heat drying is performed after setting, preheating, etc. In order to further impart a high-gloss appearance to the pattern formed by the above method and to improve the abrasion resistance of the surface, clear paint or color clear paint can be applied over and over again. The (color) clear paint can be applied as the final coating process for the above-mentioned solvent-based paint without drying the underlying paint film, but it is difficult to apply it without changing the previously formed pattern. Also, since the thickness of the (color) clear layer tends to be partially uneven, (color)
Care must be taken to adjust the surface tension of the clear paint to be almost the same as the tension of the painted surface. On the other hand, if the coating film is dried to at least a non-flowing state by setting, preheating, heating drying, etc., the coating film will not swell or redissolve to the extreme (color).
Any clear paint can be used.
In order to ensure sufficient adhesion between the patterned coating layer and the (color) clear layer, it is preferable to use a combination of resins constituting both coatings that have good affinity or compatibility with each other. The present invention will be explained below with reference to Examples. still,
"Parts" and "%" are expressed as "parts by weight" and "% by weight." Examples <Slurry paint> (i) Undercoat paint A Acrylic/block isocyanate resin-based white slurry paint [Slurry #1000 White: manufactured by Dainippon Toyo Co., Ltd.] (Surface tension 39 dynes/cm)
(20℃)) (ii) Undercoat B Acrylic/block isocyanate resin blue slurry paint [Slurry #1000 Light Blue: manufactured by Dainippon Toyo Co., Ltd.] (Surface tension 36 dynes/
cm (20℃)) <Solvent-based paint> (i) Top coat C Alkyd/melamine resin yellow paint [Delicon #840 Yellow; manufactured by Dainippon Toyo Co., Ltd.] was mixed with 70% xylol, 20% Solbetsuso #150, and cellosolve. It was diluted with a 10% acetate mixed solvent to a viscosity of 32 seconds (Food Cup #4) and a surface tension of 29 dynes/cm. The solubility of all media in water is 8% by weight. (ii) Top coat D Acrylic/melamine resin orange paint [Acrose #6000 Orange: Dainippon Toyo Co., Ltd.
[Made by] Xylol 50%, Solbetsuso #100 30
%, ethyl acetate 15%, butyl cellosolve 5% viscosity 26 seconds (Food cup #4),
Diluted to a surface tension of 26 dynes/cm. Note that the solubility of all media in water is 5% by weight. (iii) Top coat E Acrylic/block isocyanate resin blue paint [V Chroma #100 Blue: Manufactured by Dainippon Toyo Co., Ltd.]
was diluted with a mixed solvent of 30% xylol, 30% ethyl acetate, and 40% cellosolve acetate to a viscosity of 20 seconds (Food Cup #4) and a surface tension of 28 dynes/cm. The solubility of all media in water is 15% by weight. The gloss and color of each paint are shown in Table 1.

[Table] After spraying the slurry paint on the object to be coated, immediately spray painting a solvent-based paint.
A patterned coating was obtained by baking at 150°C for 30 minutes. The combinations of slurry paints and solvent-based paints and the film thicknesses in the wet state immediately after application are as shown in the upper row of Table 2. The gloss, color and appearance of the patterned coating film obtained were as shown in the lower row of Table 2.

[Table] Comparative Example 1 Tall oil fatty acid 456 parts, isophthalic acid 264 parts, trimellitic anhydride 87 parts, trimethylolpropane
277 parts were subjected to a dehydration condensation reaction in xylol according to a conventional method to synthesize a resin with an acid value of 58.5. The resin
To 1000 parts, 95 parts of triethylamine and 248 parts of ethylene glycol monomethyl ether acetate were added, followed by 270 parts of water and mixed with stirring. 0.2 parts of surface conditioner and 8 parts of phthalocyanine blue were added to 100 parts of the obtained resin solution, and after kneading and dispersing, water-soluble melamine resin ["Sumimar M-
30W'' (manufactured by Sumitomo Chemical Industries, Ltd.)] and 15 parts of water were also added to prepare a water-based paint. The solubility of all the media used in water is ∞
The surface tension of the water-based paint was 40 dynes/cm. A coating film was formed in the same manner as in Examples 5 and 6 except that the water-based paint was used in place of the top coat. The coating film had a uniform blue color and no pattern was formed at all.

Claims (1)

[Scope of Claims] 1. A slurry paint using water as a medium is applied to an object to be coated, and while the paint film is not dry, the paint film is mainly composed of an organic solvent and has a solubility in water of 20% by weight (at 20°C). Recoat a solvent-based paint using the following medium or a solvent-based paint using a medium mainly consisting of an organic solvent and having a surface tension difference of more than 5 dynes/cm (20°C) with the slurry paint. , and then drying the coating film. 2. The method for forming a patterned coating film according to claim 1, characterized in that the slurry-like paint contains a flaky pigment.