TW200413488A - Multicolor coating compositions and method of forming patterned surface - Google Patents

Abstract

This invention is to provide practical water-in-water type multicolor coating compositions capable of forming a coating film having excellent surface smoothness; and a method of coating with the coating compositions. One of the water-in-water type multicolor coating compositions is characterized by comprising a matte clear coating material containing a water-compatible resin and a loading pigment having a refractive index of 1.4 to 1.7 and, dispersed in the coating material, at least one kind of flat colored gel particles. The other water-in-water type multicolor coating composition is characterized by comprising a clear coating material containing a water-compatible resin and, dispersed in the coating material, at least one kind of flat colored gel particles, the flat gel particles being a gel derived from a water-compatible resin (a), a coloring pigment (b), water (c), and a reactive compound (d) capable of reacting in the presence of water. Also provided is a method of forming a patterned surface, characterized by applying a colored matte primer coating material on a building as a base to form a primer layer and then applying the water-in-water type multicolor coating composition by roll coating or brush coating to form a topcoat layer.

Description

200413488 (1) Description of the invention: [Technical field to which the invention belongs] TECHNICAL FIELD The present invention relates to a new water-based colorful pattern coating composition. L Previous 3 Background Art In the past, coatings commonly used on mats such as walls, ceilings, lintels, and other interior and exterior decorative surfaces were often referred to as matte paints. Matte paints are those specified in JISK5663 "Synthetic resin emulsion paint" to represent. This matte paint can be tinted by color to show various colors. However, the color obtained by the matte paint is a single color, and it is impossible to show a pattern mixed with a plurality of colors in one coat. In response to this, various coating compositions have been proposed which can express a variety of patterns in a single application. The conception of this kind of coating structure started from the patent of P. BUSCH 'and represented by J. C. ZOLA, a water-in-oil type colorful pattern coating which is practically used in US Patent No. 2591904 and Japanese Patent No. 231698. Here, Later, paint technicians in Japan and abroad developed various colorful pattern coatings, which can be classified into i) oil-in-water (0 / w type), oil-in-water (W / 〇), iii) oil-in-oil type (0/0 type), iv) water type (w / w type). For example, in Japanese Patent Laid-Open Publication No. 9-3022281, there is disclosed a colorful pattern coating containing enamel dispersed particles. The enamel dispersed particles are dispersed in an enamel obtained by using a copolymer having a crosslinkable functional group. Cross-linking ingredients are added after the aqueous dispersion medium. However, the 200413488 coating disclosed in the publication is an oil-in-water colorful pattern coating containing an organic solvent in the enamel dispersed particles, and a solvent odor is generated when it is dried. In addition, since the enamel dispersed particles of this publication have high hardness and almost spherical three-dimensional shape, it is difficult to form a smooth coating film. The water-based colorful pattern coating in which water-based particles are dispersed in the water-based medium can greatly improve the problem of generating such odors. Examples of such water-type colorful pattern coating in water include coatings disclosed in Patent Publication No. 2651533. The paint of this publication contains flaky gel-colored particles derived from the meanings of "polyethylene and polyethylene," and hollow particles such as hollow resin foams and inorganic hollow spheres. If the paint of this publication is used, a smoother coating film can also be formed. However, in the paint of this publication, due to the light-scattering property of the airborne material, the resulting coating film becomes white and lacks clarity. Other water-based colorful pattern coatings include coatings disclosed in Patent Publication No. 2525197. However, the color-developing particles disclosed in the bulletin are encapsulated particles, and the particles contain a liquid water-based coating. Therefore, depending on the coating secret, the capsules will be damaged and the financial skills will not work. Problems such as color bleeding from particles are likely to occur during roller coating or bristle coating. In addition, since the paint of the publication is fine in a liquid state, it also has a problem that a pattern is easily changed by a temperature or a recording pressure at the time of painting. I: Summary of the Invention 3 Disclosure of the Invention In view of this, an object of the present invention is to provide a solid water towel water-colored colorful flower material that can form a coating film with excellent smoothness and a coating method therefor. 6 200413488 The first problem of the present invention is to provide a water-based colorful pattern coating which can form smooth and sharp matte coating films. The second subject of the present invention is to provide a water-based multi-color paint which can form a certain smooth and colorful pattern even if the painting conditions such as painting equipment and painting temperature are changed. A third object of the present invention is to provide a coating method capable of forming a colorful and smooth coating film surface by roller coating or bristle coating. In order to solve the aforementioned problems, the inventors conducted an intensive review. As a result, it was found that if the flat color-developing gel particles are dispersed in a matte transparent paint containing an aqueous resin and a base pigment having a refractive index of 1.4 to 1.7, the aforementioned first problem can be solved. It was also found that a gelled substance derived from an aqueous resin (a), a color-developing pigment (b), water (c), and a reactive compound (d) capable of reacting in the presence of water was used as flat color-developing gel particles. , The second problem can be solved. That is, the present invention has the following features. 1. A water-based colorful pattern coating composition composed of at least one flat color-developing gel particle dispersed in a matte transparent coating containing an aqueous resin and a base pigment having a refractive index of 1.4 to h7. 2 · —A kind of water-based colorful pattern coating composition composed of at least one kind of flat + -shaped color-developing gel particles dispersed in a matte transparent coating containing an aqueous resin and a refractive index of 1.4 to 1/7 < In addition, the flat gelatin particles are derived from a gel of an aqueous resin (a), a chromogenic pigment (b), water (c), and a reactive compound (d) that can react in the presence of water. 3.—A kind of water-based colorful pattern coating composition, which is at least one kind of flat + 7 ϋ J Λ color-developing / turning particles dispersed in a matte transparent coating containing a water-based resin and a refractive index of 14-17 The former, and the flat color-developing gel particles are gelatinized by mixing an aqueous coating material containing a water-soluble resin ⑷, a chromogenic pigment (b) and water hydration with a reactive compound ⑷ which can react in the presence of water. By. 4. A water-based colorful pattern coating composition composed of at least one type of flat colored gel particles dispersed in a transparent coating containing an aqueous resin, and the flat colored gel particles are derived from an aqueous resin. (a), a gel of a chromogenic pigment (b), water (c), and a reactive compound (d) that can react in the presence of water. 5 · —A kind of water-based colorful pattern coating composition is formed by dispersing at least one kind of flat colored gel particles in a transparent coating containing an aqueous resin, and the flat colored gel particles are mixed by mixing An aqueous coating material containing an aqueous resin (a), a chromogenic pigment (b), and water (c) is gelled with a reactive compound (d) that can react in the presence of water. 6. The water-based colorful pattern coating composition according to any one of items 2 to 5, wherein the component (a) is an aqueous resin (a-1) having a reactive functional group, and the component (a) Reactive compound (d-1) that reacts with the aforementioned (a-1) component in the presence of water. 7. The water-based colorful pattern coating composition in water according to any one of items 2 to 5 above, wherein (d ) The component is a reactive compound (d — 2) that can self-condensate in the presence of water. 8. — A water-based colorful pattern coating composition, which is at least one type of flat colored gel particles dispersed in an aqueous resin and Refractive index I · 4 ~ 丨 · 7 of 8 200413488 Formed in a matte transparent coating of a base pigment, and the flat color-developing particles are dispersed in the form of flat particles in an aqueous dispersion medium and remixed The compound obtained by reacting the reactive compound (d-1) with the aforementioned (a-1) component in the presence of water, and the gelate is based on an aqueous resin (a-1) containing a reactive functional group, Mixing of chromogenic pigment (b) and water (c) in water-based paint can react in the presence of water. The obtained compound (d) 9. A water-based colorful pattern coating composition comprising at least one type of flat colored gel particles dispersed in a transparent paint containing an aqueous resin, and the flat shape is The colored particles are obtained by dispersing a gelatinous substance in a flat granular form in an aqueous dispersion medium, and then mixing the reactive compound (d-1) which can react with the aforementioned (a-i) component in the presence of water. The aforesaid gel compound is a reactive compound that can be reacted in the presence of water in an aqueous coating material (a-1), a chromogenic pigment (b), and water (c) that swallows a reactive luyuki group. The obtained. 10 The water-based colorful pattern coating composition according to item 8 or 9 above, wherein the component (d) is a reactive compound 1) capable of reacting with the component (a_1) in the presence of water. 11 · The water-based colorful pattern coating composition in water according to item 8 or 9 above, wherein the aforementioned hydrazone component is an inverse compound (d ~ 2) that can self-condense in the presence of water. ○ 12-a method for forming a pattern surface, It is formed on the base material of the building by color-developing primer After the undercoating ', a surface coating is formed by applying a roller coating or a bristle coating to the water towel water "color pattern coating composition" according to any one of the foregoing items.

C 9 200413488 According to the present invention, a practical water-based colorful pattern coating which can form a cold film with excellent smoothness can be obtained. Specifically, if the flat color-developing gel particles are dispersed in a matte transparent paint containing an aqueous resin and a base pigment having a refractive index of 1.4 to 1 · 7, a matte coating having excellent smoothness and sharpness can be obtained. Water-based colorful pattern paint in film. In addition, if a gelled product derived from an aqueous resin (a), a color-developing pigment (b), water (c), and a reactive compound (d) capable of reacting in the presence of water is used as the flat color-developing gel particles, Even if the coating conditions such as coating equipment and coating temperature are changed, a certain smooth colorful pattern water-based colorful pattern paint can be formed. Furthermore, if the present invention is used, a colorful and smooth coating film can be formed by roller coating or bristle coating on the above-mentioned water-based colorful pattern paint.

[Real mode; J Preferred embodiment of the invention] The present invention will be described in detail below together with the embodiment of the invention. (Transparent coating) In the composition of the present invention, a transparent coating is used as a dispersion medium. The transparent coating contains an aqueous resin as an essential component, and the degree of transparency is such that flat color-developed gel particles can be recognized by visual inspection and will not The degree of loss of clarity is sufficient. The water-based resin in the clear coating is a component that plays a role of fixing color-developing gel particles when a coating film is formed. As the water-based resin, a water-dispersible resin 10 200413488 can be used. Examples of the resin include acrylic resins, urethane resins, polyvinyl acetate resins, silicone resins, fluororesins, acrylic resins, acrylic resins, acrylic resins, and acrylic resins. , Polyvinyl alcohol, cellulose derivatives, etc., and one or more of these resins can be used. Such an aqueous resin may be one having a cross-linking property after the formation of a coating film. By having such cross-linking reactivity, coating film properties such as water resistance, weather resistance, stain resistance, and chemical resistance can be improved.时 When forming a matte coating film, the dispersing medium is preferably a matte transparent coating. The matte transparent coating can be obtained by mixing a base pigment with a refractive index of 1.4 to 1.7 in the aforementioned transparent coating. By using such a base pigment in the matte transparent coating, the sharpness of the coating film can be maintained and a matting effect can be obtained. Examples of usable base pigments include heavy calcium carbonate, marble, light calcium carbonate, white carbon, talc, kaolin, clay, clay, porcelain, diatomite, barite powder, barium sulfate, precipitated barium sulfate , Silica sand, silica powder, quartz powder, resin powder, etc. (except hollow products), these base pigments can be used alone or in combination of two or more. The refractive index is a value measured by an Abbe refractometer. The average particle diameter of the base pigment is usually 20 μm or less, and preferably 0.1 to 15 μm, and more preferably 0.5 to 8 μm. By using such a base pigment having an average particle diameter, the sharpness of the coating film can be further improved. The average particle diameter herein refers to a 50% particle diameter measured by a centrifugal precipitation type particle size distribution measuring device. The mixing ratio of the ground pigment in the matte transparent coating is usually 5 to 200 parts by weight relative to 100 parts by weight of the solid content of the water-based resin, and preferably 10 to 11 200413488 100 parts by weight. In addition, in the present invention, the term "extinction" includes, in addition to the extinction, generally referred to as "three-point brightness and five-point brightness." Specifically, the present invention can specify brightness by specular gloss. The specular gloss of the matte transparent coating is usually 40 or less, preferably 20 or less, and particularly preferably 10 or less. The brightness of the matte transparent coating can be appropriately adjusted in accordance with the type, particle diameter, and mixing ratio of the base pigment used in the matte transparent coating. Here, the "specular glossiness" is a value measured in accordance with 7.6 "mirror glossiness" of JISK5400. Specifically, the coating is applied on one side of a glass plate using a b-shaped film applicator with a gap of 15 μm, and the coated surface is placed horizontally, and dried at a temperature of 20 ° C and a relative humidity of 65% for 48 hours. The specular gloss (measurement angle of 60 degrees). (Flat-shaped colored gel particles) In the composition of the present invention, flat-shaped colored gel particles (hereinafter also referred to simply as "", "colored particles") are dispersed in the transparent coating. In the present invention, the shape of the color-developing particles is flat, whereby a smooth coating film can be formed. The "flat shape" in the present invention means that the ratio of the short diameter to the thickness is larger than that! The status person. There are no special restrictions on the short and long diameters of the color-developing particles, but they are usually 0.01 to 1 Gmm, and preferably G.1 to 5 sides, especially g.7 to 2 mm. The color-developing particles must contain at least 1 However, in order to show a colorful transformation surface, it is desirable to contain 2 different coloring particles, and the hue can be appropriately set according to the desired pattern. Colored particles ;; May also contain transparent particles. 12 200413488 The mixing ratio of the color-developing particles is usually 50 to 1,000 parts by weight relative to 100 parts by weight of the solid content of the aqueous resin contained in the transparent coating, and preferably 100 to 900 parts by weight, especially 200 to 800 parts by weight. Serve is better. The color-developing particles in the composition of the present invention are preferably gelled products derived from the aqueous resin (a), the color-developing pigment (b), water (c), and the reactive compound (d) which can react in the presence of water. Such color-developing particles have both moderate softness and strength, and can form a certain colorful pattern even if the coating conditions such as coating equipment and coating temperature are changed. In addition, spray coating is taken for granted, and pigment can be prevented from oozing out from colored particles during roller coating or bristle coating. Therefore, it can also be obtained when used for roller coating or bristle coating. Useful in water-based colorful pattern coatings. Specifically, such color-developing particles can be mixed with an aqueous coating material containing an aqueous resin (a), a color-developing pigment (b), and water (c), and a reactive compound (d) that can react in the presence of water, and It is obtained by gelatinizing an aqueous coating material and dispersing the gelled product in a clear coating material. The water-based resin (hereinafter referred to as "(a) component") in the water-based paint has a function as a color developing agent, and a water-dispersible resin and / or a water-soluble resin can be used. Specific examples include acrylic resin latex, urethane resin latex, polyvinyl acetate resin latex, silicone resin latex, fluorine resin latex, acrylic acid polyvinyl acetate resin latex, and acrylic acid urethane. Resin latex, acrylic · silicone resin latex, polyvinyl alcohol, poly (meth) acrylic acid, polyethylene oxide, water-soluble urethane, bio gum, polygalactomannan bran, alginic acid or a derivative thereof, Cellulose derivatives, gelatin, casein, albumin, etc., or by oxidation, methylation, carboxymethylation, hydroxyethyl 13 200413488 acetylation, hydroxypropylation, sulfate, phosphorylation, cationization, etc. Those resins and resins that have been chemically denatured may use one or more of these resins. The mixing amount of the component (a) in the water-based paint is usually 3 to 95% by weight, and preferably 5 to 80% by weight. As the component (a), an aqueous resin having a reactive functional group (hereinafter referred to as "(a-1)") may be used. Such (a-1) can be suitably used in combination with the component (d-1) described later. Examples of the reactive functional group in the β (a-1) component include a carboxyl group, an epoxy group, a warp group, a weanyl group, a spelling group, an amine group, and a carbamoyl group. As the color-developing pigment (hereinafter referred to as "(b) component"), those generally blended in coating materials can be used. For example, titanium oxide, zinc oxide, carbon black, lamp black, bone black, black lead, iron oxide black, copper chrome black, cobalt black, copper manganese black, red iron powder, I-light, Permanent Red, Permanent Carmine, Scallion Red, Perylene Benzophenone Red, Sigma-Dark Red, Iron Oxide Yellow, Titanium Yellow, Fast Yellow, Benzo-flavor Sigma, Yellow, Chrome Green, Cobalt Green, Phthalocyanine Green, ultramarine blue, Prussian blue, cobalt blue, phthalocyanine blue, α-quine-α-α-one ketone violet, dioxin-α-Qin violet, Ming pigment, pearl pigment, etc. One or more of these pigments can be used . The mixing amount of the component (b) in the water-based coating is usually 0.01 to 50% by weight, and preferably 0.5 to 40% by weight. From the viewpoint of improving the color stability of the color-developing particles, especially when stored at high temperature, the dispersant of the component (b) is preferably a polymer dispersant. The molecular weight of this polymer dispersant is usually 2000 ~ 100,000, and 14 200413488 is preferably 5000 ~ 50,000. Specifically, an anionic polymer dispersant, a nonionic polymer dispersant, a cationic polymer dispersant, an amphoteric polymer dispersant, etc. can be mentioned, and one or more of these dispersants can be used. Among them, two or more kinds are particularly suitable for the use of a cationic polymer dispersant in the present invention. The HLB of the polymer dispersant is preferably 3 to 15, and more preferably 5 to 10. The use of a polymer dispersant having such HLB can further improve the color stability of the color-developing particles. In addition, the so-called HLB is an abbreviation for the balance of hydrophilicity and lipophilicity, and the ratio of the hydrophilicity to the lipophilicity of the amphiphilic substance is numerically expressed. A reactive compound (hereinafter referred to as "(d) component") capable of reacting in the presence of water is a component that gels an aqueous coating material containing the components (a) to (c). In the present invention, if the (a-1) component is used as the hydrazone component, the (d) component is preferably a reactive compound that can react with the (a-1) component in the presence of water (hereinafter referred to as "(d-1 )ingredient"). As long as it can be gelled, the combination of the (a- 组合) component and the reactive functional group in the (d-1) component is not particularly limited. For example, carboxyl group and carbodiimide group, carboxyl group and Epoxy, carboxyl and azochrome, carboxyl and oxazoline, hydroxyl and isocyanate, carbonyl and hydrazine, epoxy and hydrazine, epoxy and amine, alkoxysilyl groups Interval combination. These combinations can be used singly or in combination of two or more. Specific examples of the (d-1) component include, for example, compounds containing a carbodiimide group, which are disclosed in Japanese Patent Application Laid-Open No. 10-6272, Japanese Patent Application Laid-Open No. 31-63693, Japanese Patent Application Laid-Open No. 11-60667, and the like. Disclosed, etc .; Compounds containing epoxy groups are polyethylene glycol diglycidyl ether, polyhydroxyalkane polyglycidyl ether, -15 diglycidyl polyglycidyl ether, sorbitan _ polyglycidyl ether, etc. The compound of the chromophore is 2,2-bishydroxymethylbutanol-ref. (Methenyl) propionate], 1,6 ~ hexamethylene diethyleneurea, diphenylmethane—bis—4,4 Ν, Ν—monoethyleneurea, etc .; compounds containing oxasalyl will be 2 — ethoxyl 2 — oxaline 2 — vinyl — 4 ~ fluorenyl — 2 — oxazoline, 2

1 dilute group ~ 5 monomethyl ~ 2-oxasalin, 2-isopropenyl-2-oxasalin, etc. Resin copolymerized with monomers copolymerizable with the compound, etc .; containing Isocyanuric compounds are tetramethylene diisocyanate IS, methylene monoisocyanate, isophorone diisocyanate, etc., or the equivalent of the Department of Biotechnology, and compounds containing hydrazine group. Dihydrazine acid, dihydrazine succinate, dihydrazine glutarate, dihydrazine adipic acid, dihydrazine sebacate, dihydrazine maleate and the like. As the component (d), a reactive compound capable of self-condensing in the presence of water (hereinafter referred to as "(d ~ 2) component") can also be used. When the component (d-2) is used, the component (a) is not particularly limited, and it may be an aqueous resin other than the component (a-1).

The component (d 2) is preferably a hydrolyzed condensation type reactive compound containing a sulfamethoxanyl group. Examples of such hydrolysis-type reactive compounds include: tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-sec- Butoxysilane, four t ~ butoxide stone fired, tetramethylene oxide, dimethoxydiethoxy, methyltrimethoxy stone fired, fluorenyl triethoxysilane, ethyltrimethoxysilane, ethyltrioxane Ethoxysilane, Benzyltrimethoxysilane, Dimethyldimethoxysilane, Diethyldimethoxysilane, Benzo-methoxyxanthine, T-glycidyloxypropyltrimethoxyxanthine, Shrinking Glyceryloxypropylmethyldioxosilane, τ ~ mercaptopropyltri 16 200413488 methoxysilane, r-aminopropyltriethoxysilane, N- (β-aminoethyl) -r-aminopropyltrimethyl Oxysilane, n- (β-aminoethyl) -r-aminopropylmethyldimethoxide, 9 " monomethacryloxypropyltrimethoxysilane, T-methacrylate Dimethoxysilane, fluorenyltrifluorosilane and the like or a condensate of these compounds. Also, a pyroxene compound containing a carboxyl group, a hydroxyl group, a luteinic acid group, an oxyalkylene group, or the like may be used. These compounds can be used alone or in combination of two or more. Among them, a tetraalkoxysilane compound is preferably used in the present invention. The tetraalkoxy silicon sintered compound is a compound represented by the following formula, namely: R0- (Si (OR) 2-〇) nR (however, R is an alkyl group, n ^ l), and particularly the hybrid is most suitable for use in the present invention. A tetraalkoxysilane compound having an alkyl group having 1 to 2 carbon atoms and an alkyl group having 3 to 12 carbon atoms (preferably 3 to 12). (d) The mixing amount of the component is generally 0.1 to 10% by weight, and preferably 0.3 to 6% by weight, based on the water-based paint. (d) When the component is small, the gel formation energy is insufficient. When it is applied by rollers or bristles) there is a possibility that the color-developing particles are destroyed. (D) When the amount of the color-developing particles is large, the color-developing particles become hard and it is difficult to obtain a smooth coating film. In order to promote the reaction of component (d), it is also possible to mix the catalysts of the ingredients. (Such catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc .; And other organic acids; basic catalysts such as sodium hydroxide, potassium hydroxide, ammonia, and amine compounds; organic tin compounds such as dibutyltin dilaurate, dibutyltin dioctoate, and dibutyltin diacetate; see ( Organoaluminum compounds such as acetopropionate) aluminum and monoacetopyruvate bis (ethylacetatepyruvate) aluminum; organic hydrazone compounds such as (hexadecylpyruvate) hydrazone; boric acid etc. (Manufacturing method of colorful pattern paint) In the production of the composition of the present invention, first, the component (d) is mixed with an aqueous coating material containing the components (a) to (c) to prepare a gel. In addition, in the present invention, The gelation system has nothing to do with the progress of the gelation reaction, and includes all those who start the gelation reaction by mixing the components (d).

There is no particular limitation on the pΗ of the water-based paint that forms a gel, as long as the gelation reaction can be started, but it is usually 7 to 14. By setting the pH of the water-based paint to this value, particularly when (d-2) is used as the (d) component, moderate reactivity can be obtained. The mixing of the water-based paint and the component (d) is usually carried out at normal temperature, but in order to promote the gelation reaction, heating may be performed. Next, the gelled product was added to an aqueous dispersion medium and dispersed in a flat granular shape. The timing of adding the gelled substance to the aqueous dispersion medium can be appropriately set, and can be performed immediately after mixing the aqueous coating material and the component (d), or can be performed after a certain period of time.

Here, a part or all of the transparent paint can be used as the aqueous dispersion medium. When the gelatinous substance is added to the aqueous dispersion medium, the aqueous resin may not be included in the aqueous dispersion medium, and may be mixed in a subsequent procedure. When making the shape of the color-developing particles into a flat shape, you can choose #. Lightly win the position of the propeller, sacrifice the position or position of the propeller, the rotation speed of the propeller, and the viscosity of the water-based paint. Method, viscosity of transparent coatings, etc. The particle size of the color-developing particles can also be adjusted by the same method. 18 200413488 In the present invention, the shape of the color-developing particles is flat, whereby a smooth coating film can be formed. The short and long diameters of the color-developing particles are not particularly limited, but are usually 0.01 to 10 mm, and preferably 0 1 to 5 mm, and more preferably 0 7 to 2 mm. A dispersion stabilizer can also be used when dispersing the spin gel in an aqueous dispersion medium. Examples of such dispersion stabilizers include magnesium salts, calcium salts, barium salts, aluminum salts, sodium salts, potassium salts, and borate salts. Moreover, the component for accelerating the reaction of the unreacted portion in the color-developed particles may be mixed in the aqueous dispersion medium to more surely gel. The pH of the aqueous dispersion medium is usually 7 to 10, and preferably 7 to 9, especially when the component (d-2) is used, the aqueous dispersion medium ipH should be set within this range. In the present invention, after dispersing the gelled substance in an aqueous dispersion medium, (d to l) can be further mixed, and in this case, the component (a) uses the component (a-i). With this procedure, a reaction between the (a- 丨) component and the 0-1) component can be generated on the surface of the color-developing particles, and the suitability of roller coating and bristle coating of the colorful pattern coating can be further improved. It is also possible to improve coating film physical properties such as weather resistance and water resistance. The mixing amount of the (d-1) component is usually 0 to 1% by weight relative to the color-developing particles. The mixing of the (d-1) component is usually performed at normal temperature, however, heating may be performed as required. In order to prepare the composition of the present invention containing two or more color-developing particles with different color phases, the following method may be used, gp: a method of mixing the coatings after separately producing coatings that disperse the monochromatic color-developing particles; or The method of adding at least two kinds of gelatins with different colors at the same time or in sequence to the points M and dispersing them 19 200413488. In the composition of the present invention, color-developing particles other than the flat color-developing gel particles may be mixed. Examples of such color-developing particles include crushed natural stones, color-developing aggregates, plastic pieces, rubber pieces, metal pieces, and inorganic mineral pieces. In the composition of the present invention, well-known additives for coatings can be appropriately used in addition to the aforementioned components. Examples of such additives include pigment dispersants, defoamers, thickeners, ultraviolet absorbers, antioxidants, mold inhibitors, preservatives, film-forming aids, and antifreeze agents. Moreover, as long as the sharpness of the coating film is not impaired, a color-developing pigment may be added to the transparent coating. It is also possible to use a base pigment or the like in an aqueous coating material that forms colored particles. (Coating method) The composition of the present invention can be applied to various applications such as construction, building materials, civil engineering, woodworking, plastic products, metal products, and non-ferrous metal products. Specifically, it can be used as a surface decorative material for various substrates such as concrete, plaster, edge boards, extruded forming boards, gypsum boards, Plywood boards, plywood boards, plastic boards, metal plates, glass, and magnetic tiles. The surface of these substrates can be some surface treatments (such as sealants, flat paints, fillers, etc.), or those who have formed a coating film or pasted wallpaper. In the present invention, it is preferred to form a primer layer by applying a color matting primer (hereinafter also referred to simply as "primer coating") before applying the multi-color pattern coating composition. Such an undercoating layer has a micro uneven structure on the surface. With this fine uneven structure, the coating workability of the colorful pattern coating (especially the coating workability during the roller coating or the bristle coating) can be improved, and a uniform pattern-free surface can be formed. The degree of color development in the primer is only required to hide the substrate. Specifically, the brightness of the primer in the present invention can be specified by its specular gloss. The base gloss of the primer coating is usually 40 or less, preferably 20 or less, and particularly 10 or less. If the specular gloss of the primer is high, it is difficult to apply the surface paint uniformly. The brightness of the primer coating can be appropriately adjusted in accordance with the type, particle diameter, mixing ratio, etc. of the base pigment described later. The primer can be produced by mixing an aqueous resin, a coloring pigment, and a base pigment. As the water-based resin, a water-dispersible resin and / or a water-soluble resin can be used. Examples of the resin type include acrylic resin, urethane resin, polyvinyl acetate resin, stone resin, fluororesin, propionic acid · polyvinyl acetate resin, acrylic acid · urethane resin, and propane Acid and stone resins, polyvinyl alcohol, cellulose derivatives, etc., and one or two or more of these resins can be used. Such a water-dispersible resin or a water-soluble resin may be one having a property of causing a crosslinking reaction after the coating film is formed. By having such a cross-linking reactivity, it is possible to improve coating film physical properties such as water resistance and adhesion. When a cationic aqueous resin is used, it is possible to prevent the base material from oozing out when it contains lime juice, resin, or the like. Examples of color-developing pigments include titanium oxide, oxide, carbon black, lamp black, bone black, black black, iron oxide black, copper chrome black, cobalt black, copper manganese black, red iron powder, molybdenum orange, permanent Red, permanent carmine, onion quinone red, perylene red, peracridone red, iron oxide yellow, titanium yellow, fast yellow, benzimidazolone yellow, chrome green, cobalt green, phthalocyanine green, ultramarine, Prussian blue, cobalt blue, phthalocyanine blue, acridone violet, dioxin violet, aluminum pigments, pearl pigments, etc. The primer 21 can develop a desired hue by using one or two or more of these color-developing pigments. Examples of the base pigment include heavy carbonate, marble, light calcium carbonate, white carbon, talc, kaolin, clay, clay, porcelain clay, diatomite, barite powder, barium sulfate, precipitated barium sulfate, silicon Sand, silica powder, quartz powder, resin beads, glass beads, hollow spheres, etc. One or two or more of these pigments can be used. The average particle diameter of the base pigment is usually from 0.1 to 500 μm, and preferably from 1 to 200 μm. With respect to 100 parts by weight of the solid content of the water-based resin, the mixing ratio of each component in the primer coating system is 1 to 300 parts by weight (preferably 5 to 200 parts by weight) and the base pigment. It is 5 to 300 parts by weight (preferably 10 to 200 parts by weight). In addition to the above-mentioned components in the primer coating material, known additives for coating materials may be appropriately used. Examples of such additives include pigment dispersants, defoamers, thickeners, ultraviolet absorbers, antioxidants, antifungal agents, preservatives, film-forming aids, and antifreeze agents. There are no special restrictions on the hue of the primer coating, but it is declared as a color similar to that of the color particles. By setting this hue, you can get a harmonious and beautiful result. Roller, bristles, trowel, etc. can be used when applying primer, but rollers or bristles are preferred from the standpoint of coating workability and coatability when used indoors and the like. It can also be diluted with water during painting. The coating amount of the primer coating is usually 0.05 to 0.5 kg / m2. Drying after applying the primer is usually done at room temperature, but it can also be heated. The drying time is usually 0.5 to 5 hours. After the primer is dried, colorful pattern paint can be applied. Various coating devices such as sprays, rollers, bristles, and trowels can be used when applying colorful pattern paints. In particular, if the color-developing particles are derived from the components (a) to (d) ', rollers or bristles are preferred. The right color-developing particles are from (a) to (), even if a coated surface is used with a different coating device, uniform results can be obtained. Therefore, even after spray coating, use rollers or bristles to repair It can also be achieved without a sense of incongruity. It can also be diluted with water during painting, and the mixing amount of water can be appropriately set in consideration of the type of painting equipment, the state of the painting substrate, and the temperature during painting. The coating amount of the material is usually 0e2 to h6kg / m2, and preferably 0.3 to 1.2kg / m2. In addition, the drying after coating the composition of the present invention can usually be performed at normal temperature, but it can also be heated. The drying time is usually 5 to 5 hours. The surface coating formed by colorful pattern coatings can be continuous or discontinuous. Especially when using a color-developing matting coating as the base coating, the surface coating is not necessary The undercoat layer can be completely covered to form a pattern surface without a sense of incongruity. The following examples show examples and make the features of the present invention clearer. In addition, the following raw materials are used in coating production. • Water-dispersible resin A: Acrylic Resin latex (styrene-methyl methyl propylene_decor-2-ethylhexyl acrylic vinegar copolymer, minimum film forming temperature 3 23 2004 13 488 ° C, ρΗ8.8, solid content 50 wt.% 0 / 〇) • Water Dispersive resin B: acrylic resin latex (styrene-methyl methacrylate-2-ethylhexyl acrylate copolymer, minimum film forming temperature 2 ° C, ρΗ6.2, solid content 50% by weight) • Water-dispersible resin C: Acrylic resin latex containing carboxyl group (methmethacrylate-butyl acrylate-acrylic copolymer, minimum film forming temperature 0 ° C, ρΗ8.2, solid content 50% by weight) • water Dispersive resin D: acrylic resin latex (styrene-butyl acrylate copolymer 'minimum film forming temperature Ot, solid content 50% by weight) • Water-soluble resin A: Hydroxyethyl cellulose powder • Water-soluble resin B ·· Polygalactomannan 3% by weight aqueous solution · Pigment A · Heavy calcium carbonate (refractive index 15 °, average particle diameter 8gm) • Pigment B: silica powder (refractive index 155, average particle diameter 2μιη) • Pigment c · Precipitable barium sulfate (refractive index 丨 64, average Sub-diameter 4μιη) • Pigment D: Silica powder (refractive index 155, average particle diameter 50μηι) • Pigment E: Oxidation index (refractive index 2 01, average particle diameter is similar) • Pigment F: Shixi stone powder (refraction Ratio 155, average particle diameter ⑼㈣ • White pigment liquid A: 60% by weight titanium oxide dispersion (dispersant: carboxylic acid-based dispersant, molecular weight 1800) White pigment liquid B • 60% by weight titanium oxide dispersion (dispersant: cation Polymer based on alkylene oxide adduct of molecular amine, molecular weight 15000, HLB8)) ... color pigment liquid A · iron oxide black 丨 5 wt% dispersion (dispersant: Wei acid dispersant, molecular weight 1800) 24 200413488 • Black pigment liquid B: 15% by weight of iron oxide black (dispersant: cationic polymer dispersant (alkylene oxide adduct, molecular weight 15000, HLB8)) • Reactive compound A : Butoxyl denatured product of tetramethoxysilane condensate • Reactive compound B: Tetramethoxyxanthine condensate • Reactive compound C: 2,2-Dimethylolbutanol One reference [3 — (1 —Acridine group) Propionate] • pH adjuster: Ammonia • Defoamer POLYROCKS oxygen-Xi [Test Example 1] (Production of coating colorful pattern) defoamer

Coating composition 1—A First, 200 parts by weight of water-dispersible resin A is poured into a container, and the rotation speed of the stirring blade is set to 1800 rpm. 3 parts by weight of water-soluble resin A are uniformly mixed while stirring. 20 parts by weight of pigment A, 1 part by weight of defoamer, and 250 parts by weight of water, thereby producing a transparent coating 1-A. The transparent coating 1-A had a pH of 8.0 and a specular gloss of 8. Next, inject 90 weight parts of water-dispersible resin A into other containers, and set the rotation speed of the stirring blade to 1800 rpm. While stirring, 180 weight parts of water-soluble resin B and 90 weight parts of white are evenly mixed. A pigment liquid, 5 parts by weight of an antifoaming agent, 80 parts by weight of water, and 5 parts by weight of a reactive compound A, thereby producing a white water-based paint 1-A. The aqueous coating 1-A had a pH of 9.5. Based on 474 parts by weight of the aforementioned transparent coating 1-A, 8 parts by weight are added 25 200413488

A 5 wt% aqueous solution of ammonium borate is used as a dispersion stabilizer, and the rotation speed of the stirring blade is set to 900 rpm. After being uniformly mixed, 450 parts by weight of the water-based coating 1A is slowly added while continuing to be stirred, and made By dispersing, a coating composition 1 of 0.8 to 1.2 mm in which flat white particles have been dispersed is obtained — A 〇 Coating composition 1_B In addition to using each raw material at the mixing ratio shown in Table 1, the coating composition 1 —A The same method was used to manufacture the coating, and 1.0-1.6 mm of flat gray particles having dispersed coating composition 1-B was obtained. Coating composition l_c A coating composition was produced by the same method as coating composition 1-A except that each raw material was used in the mixing ratio shown in Table 1. A coating composition having 0.8 to 1.2 mm flat black particles dispersed was obtained. 1 — C.

Coating composition 1-D Except that each raw material is used at the mixing ratio shown in Table 1, a coating is produced by the same method as coating composition 1-A to obtain a coating in which flat gray particles of 0.8 to 1.6 mm are dispersed. Composition 1-D.

Coating composition 1 —E Except for using each raw material in the mixing ratio shown in Table 1, a coating was produced by the same method as coating composition 1 -A to obtain a coating in which flat black particles of 0.8 to 1.2 mm were dispersed. Composition 1-E.

Coating composition 1-F Except that the raw materials were used in the mixing ratio shown in Table 1, the coating was manufactured by the same method as coating composition 1-A, and 0.8 to 1.4 mm flat 26 was obtained. 200413488 Flat gray particles have been obtained. Dispersed coating composition 1-F.

Coating composition 1-G Except that each raw material is used in the mixing ratio shown in Table 1, a coating is produced by the same method as coating composition 1-A to obtain a coating in which flat black particles of 0.8 to 1.2 mm have been dispersed. Composition 1-G. Coating composition 1 A coating was manufactured by the same method as coating composition 1-A except that each raw material was used in the mixing ratio shown in Table 1. A coating having flat gray particles of 1.0 to 1.8 mm dispersed was obtained. Composition 1 — Η. Coating composition 1 — 1 Except for using each raw material in the mixing ratio shown in Table 1, the coating was manufactured by the same method as coating composition 1 to A to obtain a coating in which flat black particles of 1.2 to 1.6 mm were dispersed. Composition 1-1.

Coating composition 1_J Except for using each raw material in the mixing ratio shown in Table 1, the coating was manufactured by the same method as coating composition 1-A to obtain a coating composition in which flat gray particles of 0.8 to 1.4 mm were dispersed. 1 J.

Coating composition 1-K Except that each raw material is used in the mixing ratio shown in Table 1, a coating is produced by the same method as coating composition 1-A to obtain a coating in which flat black particles of 0.8 to 1.2 mm have been dispersed. Composition 1-K.

Coating composition 1_L Except that the raw materials were used in the mixing ratio shown in Table 1, the coating was produced by the same method as coating composition 1-A, and flattened 1.0 to 1.8 mm 27 200413488 flat gray particles were dispersed. Coating composition 1-L. Coating composition 1-M Except that each raw material was used in the mixing ratio shown in Table 1, a coating was produced by the same method as coating composition 1-Α, and a coating having flat black particles of 1.0 to 1.6 mm dispersed was obtained. Composition 1-M. Coating composition 1 — NR A coating was produced by the same method as coating composition 1-A except that each raw material was used in the mixing ratio shown in Table 1. A coating having a flat gray particle size of 1.0 to 1.6 mm was obtained. Composition 1-N. Coating composition 1 A coating was produced by the same method as coating composition 1-A, except that each raw material was used at the mixing ratio shown in Table 1. A coating having 0.8 to 1.4 mm of flat black particles dispersed was obtained. Composition 1-10. 200413488 ο Two ο § • 1 * • ιβ CO f-1 s co 00 C4 00 CJ o 1 § • • 〇fH • inch to o U3 C4 • ζ rH § CQ inch. 1 • • iii co — s co o PI W 00 CJ lO 00 «§ cq s • s • \ o § o iH 9 0ί ai s Ci * \ • \ o 00 • fH s CO X iH 00 inch 8 pH • o < N • > o pH« 1C o to C9 Qin ΙΩ fH a iH ο s inch • See 10 «* S eo o tH one CO section · \ Ω 00 • S eq s • s • • \ a § ot ai W rH ο inch \ Ω co • »HS CQ 00 rH CO ΙΟ ♦ s rH o cq • • o fH • l〇o U3 N« co • -D iH ο (N ΙΟ CO • iH S co o pH rH 00 to 1 S ss • s • to so rH • inch CO M Ο ca to cc • fH § CO 00 U3 ooo § • I§ iH • 10 o • U3 0¾ pH S ο s > £) CQ • fH s CO o rH 00 Hi sos § § • • \ Ω s • 〇Φ o rH ο VO CO • rH § CO 00 od lO § iH g • • § «l〇o •« r4 1¾ fH ο Ci \ a co • »H s CO o iH od lO ιώ 00 sog • s 1 • > 〇s • I o 6 W tH ο CQ • i〇CQ rl o% 00 o od 10 oo § • • • o fH IO o \ a — P fH 〇 C4 inch 10 CO • rH oso rH od U3 comprehensive s C4 • S • s 1 U3 so rH • 0 01 o — § 05 * • U3 CO s eo 00 o 00 10 2 〇S • • o r4 • U3 o & Ω CQ • U3 rH two 8 • \ a eo • »n co o r- < rH od 10 g S s • s • • \ os S «饬 φ < 〇C0 §! 1 • • • iH s C4 00 〇00 00 s S * • device • l〇s lO • \ Ω 6 < < PQ < 1: OQ f < Bell 1 ffi plus < PQ < n vr < Sa < ja Banmo ffi ft certificate iif 1 I i 1 oil < (X) 〇Q Lin i I ii I s for fi 薮 # 1 1 φ tttts ιδ W φ 濯 € Φ s 1 Hg ιίτδ ffi jellyfish box sleep s 0. I mmnmaa Μ P < mm mm. ^ Tune _ Fu thin inlay «-rinse. ^ 31 ^, «玴 ^ 111 Feeding and wrapping 29 200413488 (Example 1-1) Using a mesh-shaped porous roller, a coating amount of 0.6 kg / m2 was applied to a slate coated with gray sealing material in advance. The paint, and the colorful pattern paint is a mixture of coating composition 1-a and coating composition i-B at a weight ratio of 50:50, and then dried at room temperature for 24 hours to observe the state of the coating film. In Example 1-1, a pattern coating film of white and gray mixed with smooth and high definition was formed, and no abnormality in the color-developed particles was observed. (Examples 1 to 2) In addition to using paint composition 丄 A k material composition 1 to B and paint composition 1 to C mixed at a weight ratio of 80:10:10, the others were implemented as colorful pattern paints. Example 1-The same coating was performed. In Examples 1 to 2, a pattern coating film of white, gray, and black mixed with smooth and high definition was formed, and no abnormality of the color-developing particles was observed. (Examples 1 to 3) Except that the coating composition 丨 -D and coating compositions 1 to E were mixed at a weight ratio of 50:50 as the colorful pattern coating, the coating was performed in the same manner as in Example 1. Installed. In Guan Example __3, a target-like coating film with mixed gray and black, smooth and clear, can be formed, and no abnormality of the color-developing particles is observed. (Examples 1 to 4) Except for using a coating composition in which a coating composition 丨-卩 and a coating composition 1 to G are mixed at a weight ratio of 50:50 as the colorful pattern coating, the other is the same as in Example 1-1. Paint it. OC · 30 In Examples 1 to 4, a pattern coating film with a mixture of gray and black, smooth and high-definition was formed. However, gray and black exuded from the colored particles. (Examples 1 to 5) The same as in Example 1-1, except that a coating composition in which coating compositions i to H and coating composition 1 to I were mixed at a weight ratio of 50:50 was used. Paint it. In Examples 1 to 5, a high-definition pattern coating film in which gray and black are mixed can be formed. However, compared with Examples 1 to 1, it becomes a pattern with a noticeable uneven structure. (Examples 1 to 6) The same as Example 1 to 1 except that paint compositions i-j and paint compositions 1 to K were mixed at a weight ratio of 50:50 as the colorful pattern paints. Paint it. In Examples 1 to 6, a gray and black mixed pattern coating film having a smooth and clear texture can be formed. However, the gray and black are exuded from the colored particles. (Examples 1 to 7) The same as Example 1 to 1 except that a coating composition mixed with a coating composition 1 to 1 and a coating composition 1 to 50 in a weight ratio of 50:50 was used. In Examples 1 to 7, a smooth pattern coating film mixed with gray and black can be formed. However, compared with the conventional examples 1-1, the result is slightly worse.

(Reference Example 1-U. 31 200413488 was performed in the same manner as in Example 1-1, except that the coating composition in which the coating composition and coating composition 1-10 were mixed at a weight ratio of 50:50 was used. Coating. In Reference Example 1-1, the coating film was all white, and a pattern coating film with high definition could not be formed. [Test Example 2] (Manufacturing of colorful pattern coating)

Coating composition 2 — A First, 200 parts by weight of water-dispersible resin A is poured into a container, and the rotation speed of the stirring blade is set to 1800 rpm. 4 parts by weight of the water-soluble resin A are uniformly mixed while stirring. 35 parts by weight of pigment B, 1 part by weight of defoaming agent, and 380 parts by weight of water, thereby producing a transparent coating 2-A. The clear coating 2-A had a pH of 8.1 and a specular gloss of 5. Next, pour 85 parts by weight of water-dispersible resin C into another container, and set the rotation speed of the stirring blade to 1800 rpm. While stirring, 250 parts by weight of water-soluble resin B and 50 parts by weight of white are evenly mixed. Pigment liquid A, 50 parts by weight of black pigment liquid A, 5 parts by weight of defoaming agent, 50 parts by weight of water, and 3 parts by weight of reactive compound C, thereby producing a white water-based paint 2-A. The pH of this water-based paint 2-A was 8.9.

With respect to 620 parts by weight of the aforementioned transparent coating 2-A, 10 parts by weight of a 5% by weight aqueous solution of ammonium borate was added as a dispersion stabilizer, and the rotation speed of the stirring blade was set to 900 rpm. Slowly add 493 parts by weight of water-based paint 2 — A while mixing and disperse it to obtain a coating composition 2 — A 〇 paint composition 2 — B 32 200413488 in which flat gray particles of 0.7 to 1.2 mm have been dispersed. The coating was manufactured by the same method as the composition 2-A except that the raw materials were used at a mixing ratio shown in Table 2 except that the composition was 2-mm in thickness from the coating of 1.6 mm. The coating composition 2 with flat black particles dispersed was obtained. b.

Coating composition 2 — C

A coating material was produced in the same manner except that each of the raw materials was used at the mixing ratio shown in Table 2 for Composition 2-A, to obtain a coating composition 2-c in which flat gray particles were dispersed. Coating composition 2 — D

Except that the raw materials were mixed and used as shown in Table 2, the coating was produced by the same method as that of the disk composition 2-A to obtain coating compositions 2 to d, which were known to have flat black particles dispersed.

Coating composition 2 —E In addition to using the raw materials at the mixing ratios shown in Table 2, the coating was produced by the same method as fish coating composition 2 -A, and 10 to 6 flat gray particles were dispersed. Coating composition 2-E. flat

Coating composition 2_F

Except that each raw material is used at the mixing ratio shown in Table 2, a coating is produced by the same method as _ Composition 2 to A to obtain ο; 1 5 坷 'coating composition 2 in which flat black particles are dispersed. F. In addition, when the coating composition 2-EA2-F is manufactured, a mixture of the water-based paint and the reactive compound c is added to the transparent paint and dispersed, and then the reactive compound c is combined.

Coating composition 2 ~ G Except for using each raw material in the mixing ratio shown in Table 2, the coating was manufactured by the same method as coating 33 200413488 m Mod 2-A to obtain a coating with flat gray particles dispersed. Composition 2-G. Coating composition 2 — Η Aside from using the raw materials in the mixing ratios shown in Table 2, the coating was manufactured by the same method as # 2 and Α to obtain a coating composition with 1 to 1.6111111 flat black particles dispersed. 2 — Η ° In addition, when coating composition 2 — G and 2 — were manufactured, the mixture of water-based paint and reactive compound A was added to Yiming Paint and dispersed, and then reactive compound C was mixed.

Coating composition 2 — I Except that each raw material was used in the mixing ratio shown in Table 2, a coating was produced by the same method as coating composition 2 —A, and 10 to 6 lac flat gray particles were dispersed. Coating composition 2 一 1.

Coating composition 2 —J Except that each raw material is used in the mixing ratio shown in Table 2, a coating is produced by the same method as that of the stock composition 2—A to obtain 0.8 to 15 paint in which flat black particles are dispersed. Composition 2 — j. Coating composition 2 — κ The coating was produced by the same method as that of coating 丄 4_1 except that each of the raw materials was used at the mixing ratio shown in Table 2. Composition 2-A was obtained. 0.8 Flat gray particles were dispersed. Coating composition 2 — κ.

Coating composition 2 — L The coating was produced by the same method as that for coating 1.6 mm, except that each of the raw materials was used at the mixing ratio shown in Table 2. Composition 2-A yielded j · 〇34 200413488 flat black particles. Dispersed coating composition 2-L.

Coating composition 2_M A coating was produced by the same method as coating composition 2-A except that each raw material was used at the mixing ratio shown in Table 2. A coating composition having flat gray particles of 0.8 to 1.5 mm dispersed was obtained. 2 — Μ. Coating composition 2 — NR A coating was produced by the same method as coating composition 2-A except that each raw material was used at the mixing ratio shown in Table 2. A coating having a flat black particle size of 1.0 to 1.6 mm was obtained. Composition 2 -N. 200413488 άτ I inch 1 • ια CO — o 00 CO 00 5 〇〇〇 1 luxury § τΗ 1 »ιο ο 1 CO od s eq i 1 • ΙΩ CO fH o § s 2 CJ 1 s cq g» s # 1 ΙΩ g 1 < 0 Q 〇〇 '• § inch \ 〇C0 • «Η o 00 w 00 o 00 10 ο ο 1 ow • 1 ο * H 9 inch ια ο < • inch w § CQ U3 00 with fH o 00 CO o iH tH 00 10 to 00 1 ss 1 s • 碓) 0 S 1 • 0 01 1 o inch • 10 00 H s CO 00 w H 00 inch 〇 o o C5 • • § tH 1 ΙΟ ο • CO od 1 M < h § 09 • 10 CO rH o% o iH CO 10 00 § < N s 1 s • • ϊΩ S • CO CD od 1 〇§ IO C0 ft s CO GO o 〇6 to § f— 4 1 1 • o rH inch 10 g \ Ω Ν t CO r4 rM 〇Oi § C9 10 03 o 00 CO o rH CO * U) ID 00 g CQ § • s 1Ω S ο »o CO fxi g inch 10 Λ rH os 00 o 00 to 8 rH i ft • o rH ΙΟ ο CQ αό rH W «〇03 inch 10 CQ rH o% o 1-4 GO 10 10 CO is 1 s ΙΩ S CO 0) od co Q 8 \ ά CO rH% CO 00 o 00 10 § pH 1 • 1 oo 10 ο • CO Γ ΟΟ * 1 O r inch \ 〇00 tH 00 2 rH 00 10 to 00 ss • s ΙΟ S • CO cn 00 »s C4 inch i〇CO rH o § 00 2 10 1 o fH os« § 1C ο 1 CO C ^ od 1 < < N o C4 inch \ Ω CO * 1 rH o 00 CQ o rH 10 • 10 00 g ca ss • 1C S 1 CO Φ 00 • Water-dispersible «fl & A Hydroponic resin A Pigment B Pigment D Pigment E Defoamer Dispersion stabilizer mirror gloss 丨 Water dispersible resin A Water-soluble resin C 丨 Water-soluble resin B White Yan Ji A White Pigment Liquid B Black Pigment Liquid A | Black Pigment Liquid B pH Adjuster Antifoam Reactive Compound A Reaction Sexual compound c WA u. F < in mm Fine St > φ __ «^ Μ > ^ * δ- * · ^ γίί-« ® to draw a beach, HGh 36 36 1313488 (Example 2 ~ i) using the net The eye-shaped porous roller is coated with a colorful pattern coating on a slate pre-coated with a gray sealant at a coating amount of 6 kg / m2, and the colorful pattern coating is mixed with a coating composition 2 — A and a coating composition For 2 -B, the state of the coating film was observed after it was allowed to dry at room temperature for 24 hours. In Example 2--, a gray-and-black mixed, smooth and high-definition coating film was formed, and no abnormality in the color-developed particles was observed. (Examples 2 to 2) Coating was carried out in the same manner as in Examples 2 to 1 except that paint composition 2_c and paint composition 2-D were mixed at a weight ratio of 50:50 as the colorful pattern paint. In 1-2, a gray and black mixed, smooth and clear pattern coating film was formed, and no abnormality in the color-developing particles was observed. (Examples 2 to 3) In addition to using a mixed coating with a weight ratio of 50:50 The composition 2-E and the coating composition 2-F were used as colorful pattern coatings, and the other coating was performed in the same manner as in Example 2-1. In the case of Example 2-3, gray and black were mixed and smooth and smooth. The high-definition pattern coating film did not observe any abnormality in the color-developing particles. (Examples 2 to 4) Except for using the coating composition 2G and the coating composition 2 in a weight ratio of 50:50, Η In addition, it is used as a colorful pattern paint, and the other coating is the same as in Example 2 to 1. In Examples 2 to 4, a gray and black mixed and smooth and clear can be formed. Observed Abnormality of particles (Examples 2 to 5) Except for using a coating composition in which coating composition 2-j and coating composition 2-J are mixed at a weight ratio of 50: 50 as a colorful pattern coating, the other examples are the same as in Example 2 — 1 The coating is performed in the same way. In Example 2-5, a mixture of gray and black can be formed, which is smooth and clear.

The degree of the pattern coating film, however, is a result of slightly inferior in sharpness compared to Example 2--. (Examples 2 to 6) The same as Example 2 to 1 except that a coating composition in which the coating composition 2-K and the coating composition 2-L were mixed at a weight ratio of 50 · 50 was used. To paint. In Example 2-6, a pattern coating film in which gray and black are mixed and smooth and high in definition can be formed, but 'gray and black exude from the color-developing particles. (Reference Example 2-1) "

The coating composition was mixed in the same manner as in Example 2-1 except that the coating composition 2—gang coating composition 2—N was mixed at a weight ratio of 5500 as a colorful pattern coating. In addition, it was impossible to form a clear f pattern coating film in Reference Example 2--all white. [Test Example 3]

(Manufacturing of colorful pattern paint) Coating composition 3 — A 200 weights are poured into the container

Star Part Water Dispersible Resin A, and set the rotation speed of the stirring blade S75 38 200413488 to 1800 rpm. While stirring, mix 3 parts by weight of water-soluble resin A, 1 part by weight of defoamer, and 250 parts by weight. Part of the water, thereby producing a clear coating 3-A. The clear coating 3 -A had a pH of 8 · 1. Next, inject 90 weight parts of water-dispersible resin A into other containers, and set the rotation speed of the stirring blade to 1800 rpm. While stirring, 180 weight parts of water-soluble resin B and 90 weight parts of white are evenly mixed. Pigment liquid, 5 parts by weight of defoamer and 80 parts by weight of water, thereby producing a white paralyzed water-based paint 3-A. The water-based paint 3-A had a pH of 9.5. With respect to 454 parts by weight of the aforementioned transparent coating 3-A, 8 parts by weight of an aqueous solution of 5% by weight of ammonium borate was added as a dispersion stabilizer, and the rotation speed of the stirring blade was set to 900 rpm. Slowly add 445 parts by weight of a mixture of water-based paint 3 — A and 5 parts by weight of reactive compound A and disperse them, thereby obtaining a coating composition 3 in which flat white particles of 0.8 to 1.2 mm have been dispersed — A. Coating composition 3 — B ^ Except that each raw material was used in the mixing ratio shown in Table 3, a coating was produced by the same method as coating composition 3-A, and flat gray particles of 1.0 to 1.6 mm were dispersed. Coating composition 3-B. ·

Coating composition 3 — C Except that the raw materials were used in the mixing ratios shown in Table 3, the coating was produced by the same method as coating composition 3-A to obtain a coating in which flat black particles of 0.8 to 1.2 mm were dispersed. Composition 3-C.

Coating composition 3 — D 39 200413488 Except that the raw materials were used in the mixing ratio shown in Table 3, the coating was manufactured by the same method as coating composition 3 — A, and flat gray particles of 0.8 to 1.6 mm were dispersed. Coating composition 3-D. -

Coating composition 3-E A coating was produced by the same method as coating composition 3-A, except that the raw materials were used in the mixing ratios shown in Table 3. A coating having a flat black particle size of 0.8 to 1.2 mm was obtained. Composition 3-E. Coating composition 3 —F # Except that the raw materials were used in the mixing ratio shown in Table 3, the coating was produced by the same method as coating composition 3-A, and 1.0 to 1.8 mm of flat gray particles were dispersed. Coating composition 3-F.

Coating composition 3 — G Except that the raw materials were used in the mixing ratio shown in Table 3, a coating was produced by the same method as coating composition 3-A to obtain a coating in which flat black particles of 1.2 to 1.6 mm were dispersed. Composition 3-G. Coating composition 3 —Η · Except that the raw materials were used at the mixing ratios shown in Table 3, the coating was produced by the same method as coating composition 3-A, and 0.8 to 1.5 mm of flat gray particles were dispersed. Coating composition 3 — Η. _ Coating composition 3_1 Except that the raw materials are used in the mixing ratio shown in Table 3, the coating is produced by the same method as coating composition 3-AA, and a coating composition with flat black particles of 1.0 to 1.6 mm dispersed is obtained. Object 3 — I.

Coating composition 3 —J 40 200413488 Except that the raw materials were used in the mixing ratio shown in Table 3, the coating was manufactured by the same method as coating composition 3-A, and flat gray particles of 12 to 1.8 mm were obtained. Dispersed coating composition 3-J.

Coating composition 3 — K Except that the raw materials were used at the mixing ratios shown in Table 3, the coating was produced by the same method as coating composition 3 — A, and coating composition 3 with flat black particles dispersed— K. In addition, when manufacturing coating compositions 3-J and 3-K, a mixture of a water-based coating and a reactive compound C is added to a transparent coating and dispersed, and then the reactive compound C is mixed.

Coating composition 3 — L Except that each raw material was used at the mixing ratio shown in Table 3, the coating was produced by the same method as coating composition 3-A, and flat gray particles of 0.8 to 1.6 mm were obtained. Dispersed coating composition 3-L. Coating composition 3-M Except that each raw material was used in the mixing ratio shown in Table 3, a coating was produced by the same method as coating composition 3-AA, and 0.8-L4mm flat black particles were dispersed. Coating composition 3—M. In addition, when manufacturing the coating compositions 3-L and 3-M, a mixture of a water-based paint and a reactive compound A is added to a transparent paint and dispersed, and then the reactive compound C is mixed.

Coating composition 3 — N Except that the raw materials are used at the mixing ratios shown in Table 3, the coating is produced by the same method as coating composition 3-A, and a flat 41 200413488 of 0.8 to 1.4 mm is obtained. Coating composition 3-N with gray particles dispersed. Coating composition 3 — 〇 Except that the raw materials were used in the mixing ratio shown in Table 3, the coating was manufactured by the same method as coating composition 3 — A to obtain a coating in which flat black particles of 0.8 to 1.2 mm were dispersed. Composition 3-〇.

42 200413488 Table 3-1 3 · Α 3 · Β 3-C 3-D 3 · Ε 3-F 3, G Water-dispersible resin A 200 200 200 200 200 200 200 Water-soluble thieves A 3 4 4 4 4 4 4 Transparent defoamer 1 1 1 1 1 1 1 1 Coating water 250 380 380 380 380 380 380 Dispersing stabilizer 8 10 8 10 8 10 8 pH 8.1 8.2 8.2 8.2 8.2 8.2 8.2 8.2 Water dispersing formula A 90 85 100 85 100 85 100 Water-dispersible resin C---• •--Water-soluble resin B 180 250 200 250 200 250 200 White Yan 90 90---50 • White Touch_B---50-•-Water-based Black Touch Na-50 100-• 50 100 Black Contact B-• 50 100 • Coating pH adjuster--4-4 • 4 Antifoam 5 5 5 5 5 5 5 Water 80 50 70 50 70 50 70 Reactive Compound A 5 10 25 10 25--Antibodies Compound B---• Y 10 25 Reactive Compound C--•---• pH 9.5 9.2 11,5 9.0 11.2 9.1 11.2 Anti-Teng Compound C----• •-Except for pH , The number of axes 値 are all parts by weight.

43 200413488 Table 3-2 3 · Η 3-1 3-J 3 · Κ Η 3 · Μ 3 · Ν 3-0 Water-dispersible resin A 200 200 200 200 200 200 200 200 Water-soluble resin A 4 4 4 4 4 4 4 4 Transparent defoamer 1 1 1 1 1 1 1 1 1 Coating water 380 380 380 380 380 380 380 380 Dispersing stabilizer 10 8 10 8 10 8 10 8 pH 8.2 8.2 8.2 8.2 8, 2 8.2 8.2 8.2 Water dispersibility Resin A • • •-85 100 85 100 Water-dispersible resin C 85 100 85 100 • • •-Ice-soluble resin B 250 200 250 200 250 200 250 200 White trip_A 50 • White touch_ 50-50 • 50- --Xianji 50 100 Water-based black tincture 50 100 50 100 50 100 •-Coating mm---• • 4 • 4 Antifoam 5 5 5 5 5 5 5 5 Water 50 70 50 70 50 70 50 70 Reactive compounds A •-•-10 25--Reactive compound B-Reactive compound C 3 3 3 3 •-pH 8.9 8.7 8.9 8.7 9.2 11.5 9.0 11.4 saasecBBaes Reactive compound C-• 3 1 3 1-In addition to pH, in the table Several parts by weight.

44 200413488 (Example 3 ~ i) Using a mesh-like porous roller, a multi-layer pattern paint is applied to a slab pre-sealed with a sealing compound at a coating amount of 0,6 kg / m2, and the multi-pure sample coating is 50: The coating composition 3-A and the coating composition 3-B were mixed in a weight ratio of 50, and the state of the coating film was observed after drying at room temperature for 24 hours. In Example 3-1, a white and gray mixed, smooth and high-definition pattern coating film was formed, and no abnormality in the color-developed particles was observed. (Example 2-3) Except that paint composition 3-A, paint composition 3-B, and paint composition 3-c were mixed at a weight ratio of 80:10:10 as the colorful pattern paint, Example 3-Coating was performed in the same manner. In Example 3-2, a pattern coating film of white, gray, and black mixed with a smooth and sharp texture was formed, and no abnormality in the color-developed particles was observed. (Examples 3 to 3) The coating was carried out in the same manner as in Example 3 to 1 except that paint composition 3_D and paint compositions 3 to E were mixed at a weight ratio of 50:50 as the colorful pattern paint. In Examples 3 to 3, a patterned coating film of mixed gray and black, smooth and clear, was formed, and no abnormality in the color-developed particles was observed. (Examples 3 to 4) The same as Examples 3 to 1 except that a paint composition in which paint composition 3-F and paint composition 3-G were mixed at a weight ratio of 50: 50 was used. Paint it. 45 200413488 Yu Guan Example 3-4 towels can form a gray and black mixed high-definition pattern coating film. However, compared with Example 34, it has a slightly more pronounced uneven structure. (Examples 3 to 5) The same procedure as in Example 3 to 1 was carried out except that paint composition 3—H and k material composition 3 I were mixed at a weight ratio of 50 · 50 as the colorful pattern paint. Painting. In Examples 3-5, a pattern of mixed gray and black, smooth and sharp southern patterns can be formed, and no abnormality in the color-developing particles was observed. (Examples 3 to 6) The same procedure as in Example 3 to 1 was performed, except that the paint composition 3—j and the paint composition 3-K were mixed at a weight ratio of 5G: 5G. Tu Nong. In Example 3-6, a pattern coating film 'A' mixed with gray and black, smooth and high-definition was formed, and no abnormality in the color-developed particles was observed. (Examples 3-7) The coating was performed in the same manner as in Example 3-1 except that the coating composition 3-M should be mixed with the coating composition 3-M in a weight ratio of 50:50 as the colorful pattern coating. Yiyu_3-7 towels can form gray and black silk, and a smooth and high-resolution pattern coating film '. No abnormality in the color-developing particles was observed. (Reference Example 3-1) In addition to using a paint composition in which the paint composition 3_brilliant paint composition 3-0 is mixed at a weight ratio of 50:50 as a colorful pattern paint, its D D: == 46 200413488 Example 3-1 was painted in the same manner. However, gray and black exuded from the colored particles. [Test Example 4] (Manufacture of primer coating)

Primer 4-A with 200 parts by weight of water-dispersible resin D, 40 parts by weight of white pigment liquid A, 30 parts by weight of black pigment liquid A, 28 parts by weight of pigment F, and 1 part by weight are evenly mixed with a mixer. A part of the antifoaming agent was used to produce a gray primer 4A. The specular gloss of this primer 4-A was 3.0.

Primer 4 —B For 200 parts by weight of water-dispersible resin D, uniformly mix 20 parts by weight of white pigment liquid A, 15 parts by weight of black pigment liquid A, 5 parts by weight of pigment F, and 1 part by weight with a mixer. Part of the defoamer, thereby producing a gray primer 4 -B. The specular gloss of this primer 4 -B was 35.

Primer 4-C: 200 parts by weight of water-dispersible resin D, uniformly mix 20 parts by weight of white pigment liquid A, 10 parts by weight of black pigment liquid A, and 1 part by weight of a defoamer with a mixer. As a result, a gray primer 4-C was manufactured. The primer 4-C had a specular gloss of 75. (Manufacturing of colorful pattern paint)

Coating composition 4—A First, pour 200 parts by weight of water-dispersible resin A into the container, set the rotation speed of the mixing blade to 1800 rpm, and mix 3 parts by weight of water-soluble resin A evenly while stirring. , 20 parts by weight of pigment B, 47 parts by weight of 200413488 parts of defoamer and 250 parts by weight of water, thereby producing a transparent coating 4 -A. The clear paint 4-A had a pH of 8.2 and a specular gloss of 7. Next, inject 90 weight parts of water-dispersible resin A into other containers, and set the rotation speed of the stirring blade to 1800 rpm. While stirring, 180 weight parts of water-soluble resin B and 90 weight parts of white are evenly mixed. Pigment liquid A, 5 parts by weight of a defoaming agent, 80 parts by weight of water, and 5 parts by weight of a reactive compound A, thereby producing a white water-based paint 4A. The water-based coating 4-A had a pH of 9.5. _

With respect to 474 parts by weight of the aforementioned transparent coating 4-A, 8 parts by weight of an aqueous solution of 5% by weight of ammonium borate was added as a dispersion stabilizer, and the rotation speed of the stirring blade was set to 900 rpm. After being uniformly mixed, the surface was continuously disturbed. 450 parts by weight of water-based coating material 4-A was slowly added and dispersed while mixing, thereby obtaining a coating composition 4-A of 0.8 to 1.4 mm in which flat white particles were dispersed. In addition to coating composition 4-B, The mixing ratios shown in Table 4 were used to manufacture the coating composition by using the same method as the coating instrument composition 4-A except that the raw materials were used to obtain a coating composition 4-B in which flat gray particles of 1.0 to 1.6 mm were dispersed. .

Coating composition 4-C Except that the raw materials were used at the mixing ratios shown in Table 4, the coating composition was manufactured by the same method as coating composition 4-A, and 0.8 to 1.2 mm flat black particles were dispersed. Coating composition 4 -C.

Coating composition 4 — D Except that the raw materials were used in the mixing ratio shown in Table 4, the coating composition was manufactured by the same method as that of the coating 〇 Ο Γ 48 200413488 Composition 4 A, and a flatness of 0.8 to 1.4 mm was obtained. The coating composition 4-D in the form of gray particles has been dispersed.

Coating composition 4 —E Except for using each raw material in the mixing ratio shown in Table 4, a coating composition was manufactured by the same method as coating composition 4A, and 0.8 to 1.2 mm flat black particles were dispersed. Coating composition 4 -E.

Coating composition 4 —F Except that the raw materials were used in the mixing ratio shown in Table 4, the coating composition was produced by the same method as coating composition 4A, and flat gray particles of 1.0 mm to 1.8 mm were obtained. Dispersed coating composition 4-F.

Coating composition 4-G Except that each raw material was used at the mixing ratio shown in Table 4, a coating composition was produced by the same method as coating composition 4-A, and flat black particles of 1.2 to 1.6 mm were dispersed. Coating composition 4 -G. Coating composition 4 —Η Except that the raw materials were used at the mixing ratios shown in Table 4, the coating composition was produced by the same method as coating composition 4 — A, and 0.8 to 1.4 mm flat gray particles were dispersed. Of coating composition 4

Coating composition 4-1 except that each raw material was used in the mixing ratio shown in Table 4, a coating composition was manufactured by the same method as coating composition 4-AA, and 0.8 to 1.2 mm flat black particles were dispersed. Of coating composition 4-1.

Coating composition 4 -J Except that the raw materials were used at the mixing ratio shown in Table 4, the coating composition was produced by the same method as Coating 49 200413488 Composition 4-A, and a flat gray color of 1.0 to 1.8 mm was obtained. Coating composition 4—J with dispersed particles.

Coating composition 4 —K Except that the raw materials were used in the mixing ratios shown in Table 4, the coating composition was manufactured by the same method as Coating _ composition 4 -A, and flat black particles of 1.0 to 1.6 mm have been obtained. Dispersed coating composition 4-K.

Coating composition 4 —L Except that the raw materials were used in the mixing ratio shown in Table 4, the coating composition was produced by the same method as coating · Composition 4—A to obtain flat gray particles of 1.2 to 2.0 mm. Dispersed coating composition 4-L. Coating composition 4 except that the raw materials were used in the mixing ratios shown in Table 4, the coating composition was produced by the same method as coating composition 4-A, and flat black particles of 1.0 to 1.6 mm were dispersed. Coating composition 4 -M. • 0 0 · 50 200413488 4 Table 4-M 200 1 1 fH § CO «00 co 〇 ο Η» o § «P inch U3 o Bu Ω * iq rH p» 4 4-L 200 inch 1 1 rH o CO CO 2 οό co 00 UD 00 1 o g S 1 to o iO o H 1 < price 4-K 200 inch 1 ΙΟ C0 rH § CO 00 iH 00 〇 I o §-o H inch UD o to N ♦ 10 S 1〇CQ inch 1 W m rH o 00 00 2 fH cd U3 00 tg C4 gs 1 10 s 〇rH 1 0Ϊ 6 Η XI * 〇§ 1〇C0 r * 4 o CO CO 00 rH 00 U3 1 oo iH o § • o H 1 ID o io CQ 1 00 CD W § cq inch \ 〇00 fH o § o fH 00 > 〇1 U3 00 g cq gg 1 10 s 〇rH 蜃 inch < ό 〇ο § inch 10 CQ iH% CO α 15 U3 ο ιΗ os «o iH inch \ ao • 10 cq S ο (Μ inch 10 C0 rH s OT 2 IS ια 1Λ 00 § CQ ss 1 10 s • o iH CD W 1 inch 10 C0 iH o 00 CO + 10 Ο ο os • o inch 10 o 1 • inch · rH rH Q ο «inch \ 〇C0 tH s CO + 10 ΙΟ 00 s 05 § s% IG s 1 ko φ 〇ο § 10 00 rH o 00 co Γ1! l〇ο ο o 〇q • o inch 10 o 10 09 1 i〇d § < N inch 10 C0 1 H § CQ o r-4 rH 00 10 10 00 § 3 ss 1 Ω g 〇rH 1 ① · < Ο 0¾ C0 〇IN 1 iH § cq 00 co ο ① s rH s 1 1 \ C § ΪΪΩ σί Water-dispersible resin A Water-soluble nitrile A Pigment B Pigment ι > I Foaming agent ¾ Dispersing stabilizer w A Mirror gloss water-dispersible grease A water-dispersible resin B water-tank resin B < 1 • Π3 c! S fll pH adjuster defoamer reactive compound A reactive compound BW β | mm ^ __ moth_1! ^ ® ^ 揪, ^ 3Iid, M paper tray 51 4 (Consistent Example 4 ~ i) Using a wool roller to coat the slate with a coating amount of 0.3kg / m2 " A. "After drying at room temperature for 2 hours, a multicolor pattern coating is applied at a coating amount of 6kg / m using a mesh-shaped porous roller, and the multicolor pattern coating is a mixture of coating composition 4A and coating composition at a 50:50 weight-to-weight ratio. In the case of object 4-B, although the state of the color-developing particles of the colorful pattern paint was observed here, no special abnormality was seen. Next, the state of the coating film was observed after drying at room temperature for 24 hours. Example 4 The coating film formed in —1 is a pattern of white and gray mixed and smooth, and it is a spotless and uniform result. (Performance Example 4-2) In addition to using a mixed paint composition with a weight ratio of 80:10:10 Objects 4 to 8. Coatings of coating composition 4—B and coating composition 4—c were used as colorful pattern coatings, and other coatings were applied in the same manner as in Example 4-1. No observation was made in Example 4-2. The color-developing particles are abnormal. In addition, the resulting coating film is a white, gray and black mixed and smooth pattern, and is a result of hot spots and uniformity. (Example 4-3) Except for the use of a weight of 50:50 Ratio mixing coating composition 4-D and coating The coating of the material composition 4-E was painted in the same manner as in Example 4-1 except that it was a colorful pattern coating. + The coating formed in Example 4-3 _ gray and black mixed and smooth pattern, but ' Gray and black ooze from the color-developing particles. 52 ο α (Examples 4 to 4) * A paint in which the paint composition 4_f and the soil material composition 4 to G are mixed at a weight ratio of 50 · 50 is used as the exterior of the colorful pattern paint The other coating was performed in the same manner as in Example 4-1. In Example 4-, no abnormality of the color-developing particles was observed. Moreover, the pattern of the formed coating film was similar to the color mixed with black, however, compared with Example 4-1 is a pattern with obvious uneven structure. (Example 4-5), except that a coating material mixed with coating composition 4_H and coating composition 4 ~ 1 in a weight ratio of 50 · 50 is used as a colorful pattern coating The others are painted in the same manner as in Example 4 to 1. V In Example 4-5, the coating film formed was a pattern of gray and black mixed and smooth, however, gray and black exuded from the color-developing particles. (Example 4-6) In addition to using primer 4 B was used as the base coating, and the coating was performed in the same manner as in Examples 4 to 1. The coating film formed in Examples 4 to 6 was a pattern in which gray and black were mixed and smoothed. In the case of pattern coating, the color-developing particles are slightly unevenly applied, and spots are formed on a part of the coating film. (Examples 4 to 7) In addition to using a coating composition mixed at a weight ratio of 50:50 4—j and the paint composition 4—K are used as colorful pattern paints, and the other coatings are applied in the same manner as in Example 4-1. 53 200413488 The coating film formed in Example 4-7 is a mixture of gray and black. And smooth _ pattern, however, compared with the embodiment 4-1, the result is slightly worse. (Reference Example 4-1) In addition to using primer paint 4-B as the primer paint, and a paint mixture of paint composition 4-L and paint composition 4-M in a weight ratio of 50:50 was used as the colorful pattern Except for the paint, the coating was performed in the same manner as in Example 4-1. _ In Reference Example 4-1, when the multi-color pattern coating was applied by roller, the color-developed particles were unevenly applied, and significant spots were formed in the formation of the coating film. (Reference Example 4-2) The coating was performed in the same manner as in Example 4-1, except that the primer 4-C was used as the primer. In Reference Example 4-2, when the multi-color pattern coating was applied by roller, the color-developed particles were unevenly applied, and significant spots were formed when the coating film was formed. [Test Example 5] (Manufacture of primer coating)

Primer 5 — A For 200 parts by weight of water-dispersible resin D, uniformly mix 40 parts by weight of white pigment liquid A, 30 parts by weight of black pigment liquid A, 28 parts by weight of pigment F, and 1 weight by using a mixer. Part of the defoamer, thereby producing a gray primer 5-A. The primer 5—A had a specular gloss of 3.0. Ό Ci; 54 200413488

Primer 5 — B Based on 200 parts by weight of water-dispersible resin D, 20 parts by weight of white pigment liquid A, 15 parts by weight of black pigment liquid A, 5 parts by weight of pigment F, and 1 part by weight are evenly mixed with a mixer. Part of the defoamer, thereby producing a gray primer 5-B. The primer 5-B had a mirror gloss of 35.

Primer 5 — C For 200 parts by weight of water-dispersible resin D, 20 parts by weight of white pigment liquid A, 10 parts by weight of black pigment liquid A, and 1 part by weight of antifoaming agent are evenly mixed with a mixer. As a result, a gray primer 5-C was produced. This primer 5—C had a specular gloss of 75. (Manufacturing of colorful pattern paint)

Coating composition 5_A First, 200 parts by weight of water-dispersible resin A is poured into a container, and the rotation speed of the mixing paddle is set to 1800 ηρπ. While mixing, 4 parts by weight of the water-soluble resin A is uniformly mixed. 35 parts by weight of pigment B, 1 part by weight of defoamer, and 380 parts by weight of water, thereby producing a transparent coating 5A. The clear coating 5-A had a pH of 8.1 and a specular gloss of 5. Next, pour 85 parts by weight of water-dispersible resin C into another container, and set the rotation speed of the stirring blade to 1800 rpm. While stirring, 250 parts by weight of water-soluble resin B and 50 parts by weight of white are evenly mixed. Pigment liquid A, 50 parts by weight of black pigment liquid A, 5 parts by weight of defoamer, 50 parts by weight of water, and 3 parts by weight of reactive compound C, thereby producing a white water-based paint 5A. The pH of this water-based paint 5-A was 8.9. With respect to 620 parts by weight of the aforementioned transparent coating 5-A, 10 parts by weight of 55 200413488 ammonium borate 5% by weight aqueous solution was added as a dispersion stabilizer, and the rotation speed of the stirring blade was set to 900 rpm, and the mixture was mixed evenly on the other side. 493 parts by weight of water-based paint 5-A was slowly added and dispersed while continuously stirring, thereby obtaining a paint composition 5-A in which flat gray particles of 0.7 to 1.2 mm were dispersed.

Coating composition 5 — B Except that the raw materials were used in the mixing ratio shown in Table 5, the coating was produced by the same method as coating composition 5 — A to obtain a coating in which flat black particles of 0.8 to 1.6 mm were dispersed. Composition 5-B.

Coating composition 5-C Except that each raw material was used in the mixing ratio shown in Table 5, a coating was produced by the same method as coating composition 5-A, and a coating with flat gray particles of 1.0 to 1.6 mm dispersed was obtained. Composition 5-C.

Coating composition 5 — D Except that each raw material was used in the mixing ratio shown in Table 5, a coating was produced by the same method as coating composition 5-A to obtain a coating in which flat black particles of 0.8 to 1.4 mm were dispersed. Composition 5-D.

Coating composition 5 — E Except that the raw materials were used in the mixing ratios shown in Table 5, the coating was produced by the same method as coating composition 5 -A to obtain a coating in which flat gray particles of 1.0 to 1.6 mm were dispersed. Composition 5 -E.

Coating composition 5_F Except that the raw materials are used in the mixing ratio shown in Table 5, the coating is manufactured by the same method as coating composition 5-A, and 0.8 to 1.5 mm flat 56 200413488 flat black particles have been dispersed. Coating composition 5-F. In the production of coating compositions 5-E and 5-F, a mixture of a water-based coating and a reactive compound C is added to a transparent coating and dispersed, and then the reactive compound C is mixed.

Coating composition 5 — G Except that each raw material was used at the mixing ratio shown in Table 5, a coating was produced by the same method as coating composition 5 — A, and flat gray particles of 0.8 to 1.4 mm were dispersed. Coating composition 5-G. Coating composition 5 — Η A coating was produced by the same method as coating composition 5 — A except that the raw materials were used in the mixing ratios shown in Table 5. A coating with flat black particles of 10 to 1.6 mm dispersed was obtained. Composition 5 — Η. In addition, when the coating compositions 5 -G and 5-were produced, a transparent coating was added with a mixture of a water-based coating and a reactive compound A and dispersed, and then the reactive compound C was mixed. Coating composition 5 ~ 1 Except for using each raw material at the mixing ratio shown in Table 5, the coating was manufactured by the same method as coating composition 5-A, and flat gray particles of 1.0 to 1.6 mm were dispersed. Coating composition 5-I.

Coating composition 5 ~ J Except that each raw material was used in the mixing ratio shown in Table 5, the coating was produced by the same method as coating composition 5-A, and flat black particles of 0.8 to 5111111 were obtained. Dispersed coating composition 5-J.

Coating composition 5 — K 57 Except that the raw materials were used in the mixing ratios shown in Table 5, a coating was produced by the same method as coating composition 5-A, and 0.8 to 1.4 mm of flat gray particles were dispersed. Coating composition 5-K.

Coating composition 5 —L Except that the raw materials were used at the mixing ratios shown in Table 5, the coating was produced by the same method as coating composition 5 — A to obtain a coating in which flat black particles of 1.0 to 1.6 mm were dispersed. Composition 5-L. Coating composition 5 — Μ Except that the raw materials were used in the mixing ratio shown in Table 5, a coating was produced by the same method as coating composition 5-Α, and a coating with flat gray particles of 1.0 to 1.8 mm dispersed was obtained. Composition 5 -M. Coating composition 5 — NR A coating was produced by the same method as coating composition 5-A except that each raw material was used at the mixing ratio shown in Table 5, and a coating with flat black particles of 1.2 to 1.8 mm dispersed was obtained. Composition 5-N. 200413488 5 Table Η S (Ν yjf 1 1 § CO 00 ο 〇6 ο ιΗ os • * ο ιΗ ft 1 U5 ot CO t- od S FREE § (Ν 1 1 1—4 s CO o FREE 2, VO 00 s CQ g 隹 s 1 1 10 s CO od * 10 g 09 inch ΙΩ c〇1 rH o § 00 ο 〇6 λΩ ο I 〇 • 1 o 1 inch: i〇o «1 Xi · fH iH • Μ 10 Ο § \ Ω CO 1 iH swo rH 00) Ω to »ssis» 1 > 〇s 9 1 o trophy # 〇 § inch Qin 10 CO fH o 00 CO 00 rH 00 inch 1 o rH o § • 1 § rH «ref. o 1 CO od 1 Η ιό Ο § inch% to CO tH s CO o rH 〇6 inch »ID 00 gsts» • 10 o \ 0 1 CO 0) 00 IW ΙΟ Ο ο CQ inch \ Ω CO • iH o English 00 ο αό ΙΟ 1 〇rH o N • 1 8 rH inch to? ιο cq% CO r4 tH rH 0 ύ ο inch • ΙΟ CO 1 rH o § o iH ιΗ 00 Ί LO CO 〇k〇 (NJ § 1 S 1 10 so 1 o Q eg ύ ο § CO 1 «» 4 o Dad 00 ο 00. 〇fH 〇〇 (N 1 1 O rH 1 ιο o 1 CO t- od rH Μ to 8 1C CQ I rH s CO o fH ιΗ 〇6 10 隹 to 00 § 0¾ § 1 § 1 10 § »CO ω αό« Q ιό ο S inch US CO • iH o 8 00 ο 〇6 10 fo rH o N ref < o iH 1 ID o 1 dry * Ο ΙΟ ο 10 CO 1 rH s CO o fH rH 00 10 1 10 00 o 10 N s 1 § 1 \ as 1 »« ιό ο inch \ a CO 1 fH § CO 00 ο οό 10 curtain o rH o 1 o »H • t» 〇ot CO t- od a < ί ΙΩ ο S inch lCOCO • rH Φ 00 o rH γΗ 〇ό 10 »\ a 00 gs View o to 1 1 10 s CO CD oo »Water-dispersible resin A Water-soluble resin A Pigment B Pigment D Antifoam dispersant stabilizer W P. Mirror gloss water-dispersible resin A Water-dispersible resin c Water-soluble resin B White pigment liquid A White pigment liquid B Black pigment liquid A Black pigment liquid B pH adjuster Antifoaming agent Reactive compound A Reactive compound c X β I Reactive compound c mm * * Rose 3 «® Bi, Hdxi 59 200413488 (Examples 5 to 1) The slate was coated with a primer 5 — A 0 using a wool roller at a coating amount of 0.3 kg / m 2 after drying at room temperature for 2 hours, and then a coating amount of 0.6 kg / m2 is coated with colorful pattern paint, and the colorful pattern paint is a mixture of coating composition 5 -A and coating composition 5 -B in a weight ratio of 50:50. Although this observation state of the color particles of the multicolored pattern paint, but there is no particular see the anomalies. Next, it was allowed to dry at room temperature for 24 hours, and the state of the coating film was observed. The coating film formed in Example 5-1 was a white and gray mixed and smooth pattern, and it was a spotless and uniform result. (Example 5-2) Except that a coating material in which a coating composition $ a c and a coating composition 5-D was mixed at a weight ratio of 50 · 50 was used as a colorful pattern coating, the coating was performed in the same manner as in Example 5-1. Installed. No abnormality was observed in the color-developing particles in Examples 5-2. In addition, the formed coating film was a white, gray and black mixed and smooth pattern, and it was a spotless and uniform result. (Example 5-3) The coating was performed in the same manner as in Example 5-1, except that a coating material in which the coating composition 5_E and the coating composition 5-F were mixed at a weight ratio of 50:50 was used as the colorful pattern coating. Installed. No abnormality was observed in the colored particles in Examples 5 to 3. In addition, the formed coating film is a white, gray and black mixed and smooth pattern, and it is a uniform result without specks, q 60 200413488. (Examples 5 to 4) In addition to using the paint composition 5-G and the "paint composition 5-" paint mixed in a weight ratio of 50: 50 as a colorful pattern paint, other and practical _ Example 5 -1 Paint in the same way. No abnormality was observed in the color-developing particles in Examples 5 to 4. In addition, the formed coating film was a white, gray and black mixed and smooth pattern, and it was a spotless and uniform result. · (Example 5-5) The same procedure as in Example 5-1 was carried out except that a paint in which paint composition 5-1 and paint composition 5j were mixed at a weight ratio of 50:50 was used as a colorful pattern paint. Painting. The coating film formed in Examples 5-5 was a pattern in which gray and black were mixed and smoothed. However, compared with Example 5-1, the result was slightly inferior in sharpness. (Examples 5-6) # The coating was carried out in the same manner as in Example 5-1, except that a primer coating 5B was used as the primer coating. The coating film formed in Examples 5 to 6 is a pattern in which gray and black are mixed and smooth-however, when the multi-color pattern coating is applied by roller, it becomes-a state where the colored particles are slightly unevenly applied, In addition, spots may be formed on a part of the coating film. (Example 5-7) The same procedure as in Example 5-1 was carried out except that a paint in which paint composition 5-K and 200413488 paint composition 5 ~ L were mixed at a weight ratio of 50:50 was used as a colorful pattern paint. Painting. The coating film formed in Examples 4 to 7 was a pattern in which gray and black were mixed and smoothed. However, gray and black exuded from the colored particles. (Reference Example 5 — 1)

Except for using the primer 5-B as the primer, and using a paint mixed with the coating composition 5-M and the coating composition 5 ~ N in a weight ratio of 50: 50 as the colorful pattern paint, the other examples 5-1 Apply the same. In Reference Examples 5 to 1, when the multi-color pattern coating was applied by roller, the color-developed particles were unevenly applied, and the spots on the coating film were formed. (Reference Example 5-2) The coating was performed in the same manner as in Example 5-1 except that the primer 5-C was used as the primer. In Reference Example 5-2, when the multi-color pattern coating was applied by a roller, the color-developed particles became uneven, and significant spots were formed in the formation of the coating film. Industrial Applicability The water-based colorful pattern coating composition of the present invention can form a matte coating film having excellent smoothness and sharpness. χ, the water-based colorful pattern coating composition of the present invention can be changed into a smooth and colorful pattern even if the coating conditions such as silk appliances and coating temperature are changed. X, according to the present invention, by applying roll coating or brushing to the 7jc t water-based colorful pattern coating composition 62 200413488 wool coating, a colorful and smooth coating surface can be formed. I: Schematic description 3 (none)

63

Claims (1)

200413488 Scope of patent application: 1. A water-based colorful pattern coating composition, which is at least one flat color-developing gel particle dispersed in a matte transparent coating containing an aqueous resin and a base pigment with a refractive index of 1.4 to 1.7 And the former. 5 2 · —A kind of water-based colorful pattern coating composition formed by at least one flat color-developing gel particle dispersed in a matte transparent coating containing an aqueous resin and a ground pigment with a refractive index of 1.4 to 1.7, and The flat color-developing gel particles are derived from a gelled product of an aqueous resin (a), a color-developing pigment (b), water (c), and a reactive compound (d) capable of reacting in the presence of water. 10 3. —A kind of water-based colorful pattern coating composition formed by at least one flat color-developing gel particle dispersed in a matte transparent coating containing an aqueous resin and a base pigment having a refractive index of 1.4 to 1.7, and The flat color-developing gel particles are obtained by mixing an aqueous coating material containing a water-soluble resin (a), a color-developing pigment (b), and water (c) with a reactive compound (d) capable of reacting in the presence of water. Geller. 4. A water-based colorful pattern coating composition, which is formed by dispersing at least one type of flat colored gel particles in a transparent coating containing an aqueous resin, and the flat colored gel particles are derived from an aqueous resin ( a) A gelled product of a chromogenic pigment (b), water (c) and a reactive compound (d) 20 which can react in the presence of water. 5 · —A kind of water-based colorful pattern coating composition is formed by dispersing at least one kind of flat colored gel particles in a transparent coating containing an aqueous resin, and the flat colored gel particles are mixed by mixing Aqueous resins (a), chromogenic pigments (b), and water (c) are water-soluble paints that react with the reactive compound (d) in the presence of water and cause gelation. 6. If the water-based colorful pattern coating composition in water according to item 2 of the patent application, wherein the aforementioned rhenium component is an aqueous resin having a reactive functional group ^ -1), the aforementioned rhenium component can be reacted in the presence of water by the aforementioned components 5 should be a reactive compound (d-1). 7. The water-based colorful pattern coating composition in water according to item 3 of the patent application, wherein the component (a) is an aqueous resin having a reactive functional group (0-1), and the component (d) is water-soluble. A reactive compound (d-1) which reacts with the aforementioned (a- 丨) component in the presence. 10 8 · The water-based colorful pattern coating composition in water according to item 4 of the patent application, wherein the component (a) is an aqueous resin having a reactive functional group (0-1), and the component (d) may exist in water. Reactive compound (d-1) that reacts with the aforementioned (a-u component). 9. For example, the water-based colorful pattern coating composition 15 in the scope of the patent application No. 5 in which the component (a) is reactive Functional group water-based resin (a-1), the aforementioned component (d) is a reactive compound (d-1) which can react with the aforementioned component (a_1) in the presence of water. A water-based colorful pattern coating composition in which the aforementioned (d) component is a reactive compound 20 (d-2) that can self-condensate in the presence of water. 11. · Aqueous water-type colorful pattern in item 3 of the scope of patent application A coating composition in which the aforementioned (d) component is a reactive compound (d-2) capable of self-condensing in the presence of water. 12 · The water-based colorful pattern coating composition in water according to item 4 of the patent application composition 65 13 The aforementioned (d) component is a reactive compound capable of self-condensation in the presence of water (d — 2). • The water-based colorful pattern coating composition in water according to item 5 of the patent application, wherein the aforementioned (d) component is a reactive compound (d ~ 2) capable of self-condensing in the presence of water. A water-based colorful pattern coating composition is formed by dispersing at least one flat color-developing gel particle in a matte transparent paint containing an aqueous resin and a base pigment having a refractive index of 1.4 to 1.7, and the flat color develops The particles are obtained by dispersing the gelatin in the form of flat granules in an aqueous dispersion medium, and then mixing the reaction ratio compound (d ~ i) which can react with the aforementioned (a-1) component in the presence of water. The gel compound is mixed with a reactive compound (d) which can react in the presence of water in an aqueous coating material containing an aqueous resin (a-1) having a reactive functional group, a chromogenic pigment (b), and water (c). 15 · —A water-based colorful pattern coating composition composed of at least one kind of flat colored gel particles dispersed in a transparent coating containing an aqueous resin, and the flat colored particles The gelatinous substance is dispersed in flat particles In the medium, a reactive compound (d ~ i) which can be reacted with the aforementioned (a__1) component in the presence of water is further mixed, and the gelled substance is an aqueous resin containing a reactive functional group ( a_ i), a chromogenic pigment (b) and water (c) are obtained by mixing a reactive compound (d) which can react in the presence of water. 16. The water type in water as in item 14 of the scope of patent application A colorful pattern coating composition in which the aforementioned (d) component is a reactive compound (d — 1) capable of reacting with the aforementioned component 200413488 in the presence of water. '17. For example, the water-based colorful pattern in water in item 15 of the scope of patent application is heavy The material composition, wherein the component (d) is a reactive compound (d-1) capable of reacting with the component (a-i) in the presence of water. 5 18. The water-based colorful pattern coating composition in water according to item 14 of the patent application, wherein the component (d) is a reactive compound (d-2) capable of self-condensing in the presence of water. 19. 10 20. For example, the water-based colorful pattern coating group in the scope of the patent application item No. 15 in which the aforementioned hydrazone component is a reactive compound (d-2) capable of self-condensing in the presence of water. -The method of forming the pattern surface is to form a primer layer on the base material of the building by using the _ color primer coating, and then apply the water pattern colorful pattern in any of the items i to 19 in the scope of patent application The coating composition is subjected to roller coating or bristle coating to form a surface coating. 67 200413488 (1) Designated representative map: (1) The designated representative map in this case is: (No). (2) Brief description of the representative symbols of the components in this representative diagram: (none) 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: