JP4909054B2 - Multi-pattern coating film forming method and composite coating film - Google Patents

Description

  The present invention relates to a method for forming a multicolored paint film using a multicolor paint and a composite paint film.

  For example, a multi-pattern paint is well known as a paint in which granular gel is stably dispersed in a dispersion medium. The multicolored paint is a paint that can produce various patterns of two or more colors with a single painting, and is mainly used for painting buildings and the like.

  As a coating method using a multicolored paint, Patent Document 1 includes as main components a polymer obtained by polymerizing at least one monomer selected from vinyltoluene, butadiene, styrene, and an acrylic monomer, a pigment, and an organic solvent. After coating and drying a multicolored paint containing at least one kind of enamel-dispersed particles obtained by mixing and dispersing the composition to enamel and dispersing it in an aqueous dispersion medium, the concealment rate of the dried coating film is on it. A multi-pattern paint finishing method is described in which a clear paint that is 0.5 or less is applied.

  According to such a paint finishing method, it is possible to maintain the initial coating state without causing deterioration of the coating film over time or cracking between the pattern particles even in outdoor use, and a deep finish appearance by clear coating However, since the multicolored coating film is formed by fusing the pattern particles, it cannot be denied that it is insufficient for long-term durability.

  Patent Document 2 discloses a natural stone-like paint composition comprising, as main components, a pattern color-forming dispersed phase particle having a specific particle size distribution composed of a plurality of colors and a transparent dispersion medium capable of dispersing the dispersed phase particle in a particle state. A natural stone-like coating method characterized by coating an object on an undercoat layer is described. According to such a coating method, it is possible to form a layered coating film having a natural stone tone and full of volume without requiring special skills such as a special coating machine or a skilled coating specialist. In order to respond to diversified user preferences, it is necessary to develop a coating system that exhibits unique design and satisfies long-term durability.

JP-A-9-57186 JP 2003-154308 A

  An object of the present invention is to provide a multi-pattern coating film forming method suitable for forming a composite coating film having a unique finished appearance and excellent in durability over a long period of time.

As a result of intensive studies on the above-mentioned problems, the present inventors have adjusted the water absorption rate of the colored coating film provided under the specific multi-color coating film so as to be within a specific range, thereby improving the durability of the formed composite coating film. As a result, the present invention has been found.
That is, the present invention
1. After the colored coating (I) having a water absorption of 20% or less is applied to the surface to be coated, the colored coating is formed, and then the multicolored coating (II) is applied on the coated surface. A method for forming a multicolored pattern coating film for forming a multicolored pattern coating film, wherein the multicolored pattern paint (II) is obtained by granulating the colored paint (a1) and a coating material forming component (B). comprise becomes, Ri color difference ΔE is near the range of 15 or more with colored coating film formed from at least one coloring paint particles (a) and the colored coating (I), colored paint particles (a) and the coating Both the film-forming component (B) contain a resin having a reactive functional group (x), and the colored coating particle (A) and / or the coating film-forming component (B) can react with the reactive functional group (x). multicolor coating film forming method characterized that you containing a crosslinking agent having a reactive functional group (y),
2. The method for forming a multicolor pattern coating film according to item 1, wherein the colored paint (I) contains an ultraviolet absorber and / or a light stabilizer,
3. Item 1 wherein the colored paint (I) contains a reactive functional group (m) and the multicolored paint (II) contains a reactive functional group (n) capable of reacting with the reactive functional group (m) The method for forming a multicolor pattern coating film according to Item 2,
4). Both the colored paint (I) and the multicolored paint (II) contain a resin having a reactive functional group (m), and the colored paint (I) and / or the multicolored paint (II) has a reactive functional group (m). The method for forming a multicolor pattern coating film according to any one of 1 to 3, comprising a crosslinking agent having a reactive functional group (n) capable of reacting with
5. The multicolored paint film according to any one of items 1 to 4, wherein the multicolor paint (II) is applied so that the concealment ratio of the formed paint film is within a range of 10 to 70%. Forming method,
6). 6. A composite coating film obtained by the multicolor pattern coating film forming method according to any one of items 1 to 5 ;
About.

  According to the method of the present invention, a composite coating film having good durability can be formed by providing a colored coating film having a specific water absorption rate under the multicolored coating film, and the color tone of the colored coating film is Reflected in the multicolored paint film, it can have a deep and unique appearance that cannot be achieved with the multicolored paint film alone.

  The coated surface applied to the method for forming a multicolored pattern coating film of the present invention is not particularly limited, and examples thereof include gypsum board, concrete wall, mortar wall, slate board, PC board, ALC board, cement calcium silicate board. Surfaces of base materials such as wood, stone, plastic moldings, metal workpieces, acrylic resins, acrylic urethane resins, polyurethane resins, fluororesins, acrylic silicon resins, acetic acid provided on these substrates Examples include vinyl resin and epoxy resin coating surfaces, wallpaper surfaces made of materials such as polyvinyl chloride, polyolefin, paper, and cloth. Various sealers and undercoats can be applied to these various substrate surfaces. Pre-painted surfaces are also included.

  The colored paint (I) used in the method of the present invention is a paint having a formed coating film with a water absorption of 20% or less, and the water absorption is preferably within the range of 0.1 to 15%.

  If the water absorption rate of the formed coating film exceeds 20%, the durability of the composite coating film obtained by coating the later-described multicolored paint (II) on the colored coating film formed by the colored coating composition (I) is inferior. It is not preferable.

  In the present specification, the water absorption is measured as follows.

  A sample is uniformly coated on a polypropylene plate (300 × 100 × 5 mm) so as to have a dry film thickness of 40 μm, and dried for 7 days under conditions of an air temperature of 23 ° C. and a relative humidity of 60% to obtain a coating film. Thereafter, a free coating film is arbitrarily cut out in a 3 cm square from the coating film, submerged in deionized water at 20 ° C. for 24 hours, wiped off water droplets on the surface, and immediately weighed. Measure.

Water absorption (%) = [(B−A) / A] × 100
However, A: Mass (g) of the free coating film before submersion
B: Mass (g) of the free coating film after submersion.

  The colored paint (I) is a paint containing a color pigment and a resin component, and it is important that the water absorption rate of the formed coating film is in the above range, and the material and the like can be arbitrarily selected.

  Examples of the color pigment include white pigments such as titanium oxide; black pigments such as carbon black, acetylene black, lamp black, bone black, graphite, iron black, and aniline black; yellow iron oxide, titanium yellow, monoazo yellow, and condensed azo. Yellow pigments such as yellow, azomethine yellow, bismuth vanadate, benzimidazolone, isoindolinone, isoindoline, quinophthalone, benzidine yellow, permanent yellow; orange pigments such as permanent orange; red iron oxide, naphthol AS azo red, ansanthrone , Anthraquinonyl red, perylene maroon, quinacridone red pigment, diketopyrrolopyrrole, watching red, permanent red and other red pigments; cobalt purple, quinacridone violet, dioxadi Violet pigments such as violet; like green pigment such as phthalocyanine green; cobalt blue, phthalocyanine blue, blue pigments such as vat blue.

  The colored paint (I) may contain extender pigments as necessary. Examples of such extender pigments include barita powder, precipitated barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, white carbon, diatomaceous earth, talc, magnesium carbonate, alumina white, gloss white, silica sand, and quartz powder. .

  These color pigments and extender pigments can be used alone or in combination of two or more.

  As the resin component contained in the colored paint (I), those known as conventionally known binder components can be used without limitation, and may be a crosslinked type or a non-crosslinked type, or an organic solvent type. Or water based. The resin type is not particularly limited. Specifically, for example, acrylic resin, polyolefin resin, silicon resin, polyurethane resin, epoxy resin, phenol resin, polyester resin, alkyd resin, polycarbonate These resins can be used, and these can be used alone or in combination of two or more. These resins may be modified like, for example, urethane-modified acrylic resin, or may be graft-polymerized.

  The resin component contained in the colored paint (I) is an aqueous resin, which is suitable from the viewpoint of adhesion between the two when a later-described multicolored paint is aqueous.

  When the aqueous resin is in the form of dispersed particles, the aqueous resin can be a single layer or a multilayer such as a core / shell type. Further, the aqueous resin can be a resin having an anionic group, for example, a carboxyl group as a hydrophilic group. In this case, the resin may be neutralized, and as a neutralizing agent that can be used in this case Can be exemplified by amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, dimethylaminoethanol, 2-methyl-2-amino-1-propanol, ammonia, and the like. It can be used alone or in combination of two or more.

  The aqueous resin is preferably an acrylic resin from the viewpoints of durability and weather resistance of the colored coating film formed from the colored paint (I).

  Examples of such acrylic resins include resins obtained by copolymerizing polymerizable unsaturated monomers. Examples of such polymerizable unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) ) Acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, etc. Linear or branched alkyl (meth) acrylate; Cyclohexyl (meth) acrylate, cycloaliphatic alkyl (meth) acrylate such as isobornyl (meth) acrylate; Aralkyl (meth) acrylate, such as benzyl (meth) acrylate Alkoxyalkoxy (meth) acrylates such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate; perfluoroalkyl (meth) acrylates; N, such as N, N-diethylaminoethyl (meth) acrylate; N-dialkylaminoalkyl (meth) acrylate; (meth) acrylamide; (meth) acrylonitrile; vinyl ester compounds such as vinyl acetate and vinyl propionate; vinyl aromatic compounds such as styrene and α-methylstyrene; allyl (meth) acrylate , Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylol pro Pantri (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tetra (Meth) acrylate, glycerol di (meth) acrylate, 1,1,1-trishydroxymethylethane di (meth) acrylate, 1,1,1-trishydroxymethylethanetri (meth) acrylate, 1,1,1- Polyvinyl compounds having at least two polymerizable unsaturated groups in one molecule such as trishydroxymethylpropane tri (meth) acrylate, triallyl isocyanurate, diallyl terephthalate, divinylbenzene; 2-hydroxyethyl (meth) acrylate -Hydroxyalkyl (meth) acrylates such as 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate, allyl alcohol, and ε-caprolactone of the above hydroxyalkyl (meth) acrylate Modified products, hydroxyl group-containing polymerizable unsaturated monomers such as polyoxyethylene chain-containing (meth) acrylates whose molecular ends are hydroxyl groups; carboxyl groups such as (meth) acrylic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate, etc. Polymerizable unsaturated monomer; (meth) acrolein, formylstyrene, vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, etc.), acetoacetoxyethyl (meth) Carbonyl group-containing polymerizable unsaturated monomers such as acrylate, acetoacetoxyallyl ester, diacetone (meth) acrylamide; glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate , 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, epoxy group-containing polymerizable unsaturated monomers such as allyl glycidyl ether; isocyanate ethyl (meth) acrylate, m-iso Isocyanate group-containing polymerizable unsaturated monomers such as propenyl-α, α-dimethylbenzyl isocyanate; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltri Alkoxysilyl group-containing polymerizable unsaturated monomers such as methoxysilane and γ-methacryloyloxypropyltriethoxysilane; epoxy group-containing polymerizable unsaturated monomers or reaction products of hydroxyl group-containing polymerizable unsaturated monomers and unsaturated fatty acids; Examples thereof include oxidatively curable group-containing polymerizable unsaturated monomers such as cyclopentenyloxyethyl (meth) acrylate, dicyclopentenyloxypropyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and the like. It can be used in combination of more than one species.

  The polymerization method of the monomer is not particularly limited. For example, according to a general emulsion polymerization method, an acrylic resin can be easily produced by (co) polymerizing the monomer in the presence of an emulsifier. Can do.

  As the emulsifier used in the production of the acrylic resin, known emulsifiers can be used. Examples of applicable emulsifiers include anionic emulsifiers, nonionic emulsifiers and amphoteric emulsifiers. Can do.

  Examples of the anionic emulsifier include diammonium dodecyl diphenyl ether disulfonate, sodium dodecyl diphenyl ether disulfonate, calcium dodecyl diphenyl ether disulfonate, alkyl diphenyl ether disulfonate such as sodium alkyl diphenyl ether disulfonate; sodium dodecyl benzene sulfonate, dodecyl benzene sulfonic acid Alkyl benzene sulfonates such as ammonium; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; aliphatic carboxylates such as fatty acid sodium and potassium oleate; sulfate salts containing polyoxyalkylene units (for example, polyoxyethylene alkyl) Sodium ether sulfate, polyoxyethylene alkyl ether sulfate Polyoxyethylene alkyl ether sulfates such as ammonium; polyoxyethylene alkylphenyl ether sulfate sodium, polyoxyethylene alkylphenyl ether sulfates such as ammonium polyoxyethylene alkylphenyl ether sulfate; polyoxyethylene polycyclic sodium phenyl ether sulfate; Polyoxyethylene polycyclic phenyl ether sulfates such as polyoxyethylene polycyclic phenyl ether ammonium sulfate); Naphthalene sulfonic acid formalin condensate such as sodium naphthalene sulfonic acid formalin condensate salt; Sodium dialkyl sulfosuccinate, monoalkyl succinate Alkyl succinate sulfonates such as disodium sulfonate, and the like. Others can be used in combination of two or more.

  Examples of nonionic emulsifiers include polyoxyalkylene unit-containing ether compounds (for example, polyoxyalkylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene tridecyl ether, polyoxyethylene oleyl ether). Polyoxyalkylene alkyl phenyl ether compounds such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyoxyalkylene polycyclic phenyl ether compounds such as polyoxyethylene polycyclic phenyl ether); polyoxyethylene monolaurate Polyoxyalkylene alkyl ester compounds such as polyoxyethylene monostearate and polyoxyethylene monooleate; Polyoxyalkylene alkylamine compounds such as reoxyethylene alkylamine; sorbitan compounds such as sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, etc. These can be used alone or in combination of two or more.

  Examples of amphoteric emulsifiers include dimethylalkyl betaines, dimethylalkyl lauryl betaines, and alkyl glycines.

  As the emulsifier, a reactive emulsifier containing both a polymerizable unsaturated group and an anionic group or a nonionic group in the molecule can also be used.

  The usage-amount of the said emulsifier is 0.5-6 mass% normally on the basis of the total mass of a polymerizable unsaturated monomer, Preferably it can exist in the range of 1-4 mass%.

  Moreover, it is suitable that the colored paint (I) further contains an ultraviolet absorber and / or a light stabilizer.

  Thereby, durability of the composite coating film obtained by the coating film formation method of this invention can be improved more effectively.

  Examples of ultraviolet absorbers include salicylic acid derivatives such as phenyl salicylate, p-octylphenyl salicylate, 4-t-butylphenyl salicylate; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2,2'-dihydroxy- 4,4'-dimethoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, sodium 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2, , 2 ', 4,4'-tetrahydro Xylbenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, resorcinol monobenzoate, 2,4-dibenzoyl resorcinol, 4,6-dibenzoyl resorcinol, hydroxy Benzophenones such as dodecylbenzophenone and 2,2'-dihydroxy-4 (3-methacryloxy-2-hydroxypropoxy) benzophenone; benzotriazoles such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole And other compounds such as oxalic anilide and cyanoacrylate.

  As the light stabilizer, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl)- 5-chlorobenzotriazole, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6- Tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate 1- (2-hydroxyethyl) -4-hydroxy-2 , 2,6,6-tetramethylpiperidine polycondensate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, bis- (2,2 ′, 6, 6'-tetramethyl-4-pi Lysinyl) Sebate - DOO, 4-benzoyloxy -2,2', 6,6'-tetramethyl piperidine, and the like.

  The ultraviolet absorbers and / or light stabilizers may be used alone, or may be appropriately selected and used in combination.

  The use ratio of the ultraviolet absorber is 0.1 to 5.0% by mass, preferably 0.2 to 2.0% by mass, based on the resin solid content contained in the colored paint (I). The proportion of the light stabilizer used is 0.1 to 5.0% by mass, preferably 0.2 to 3.0% by mass, based on the resin solid content contained in the colored paint (I). It is preferable to be within.

  The colored paint (I) includes an antifoaming agent, a curing catalyst, a pigment dispersant, a surfactant, a film-forming aid, a viscosity modifier, a neutralizing agent, an antiseptic, an antifungal agent, an antifreezing agent, and a formaldehyde adsorbent. Paint additives such as can be included as required.

  The colored paint (I) can be applied using a coating means known per se, for example, using a coating device such as a roller, air spray, airless spray, lysine gun, universal gun, brush, or iron. Can do. Moreover, when using a roller, a wool roller, a sand-bone roller, etc. can be used.

The coating amount of the colored paint (I) can be changed depending on the composition of the colored paint used and the state of the multicolored paint film described later as long as the water absorption is within the above range. 500 g / ^{m 2,} it is desirable that preferably is adjusted to the range of 20~350g / ^{m 2.}

  The formed coating film can be dried by any of heat drying, forced drying or room temperature drying depending on the type of paint used.

  In the method of the present invention, the multicolor paint (II) is applied on the colored coating film formed by the colored paint (I).

  The multicolored paint (II) used in the method of the present invention contains colored paint particles (A) obtained by granulating the colored paint (a1) and a coating film forming component (B). ) Has a color difference ΔE with the colored coating film formed from the colored paint (I) in the range of 15 or more.

  If the color difference ΔE between the colored coatings formed from the colored coating particles (A) and the colored coating (I) is less than 15, the color tone of the colored coating as the undercoat is not reflected in the multicolored coating, A deep and unique appearance cannot be exhibited, which is not preferable.

  In the method of the present invention, a preferred range of the color difference ΔE between the colored coating films respectively formed from the colored paint particles (A) and the colored paint (I) can be exemplified by a range of 15-60.

In this specification, the color difference ΔE is obtained by applying a colored paint (I) or a colored paint (a1) to a tin plate with an applicator having a gap of 150 μm, and drying for 48 hours under conditions of an air temperature of 23 ° C. and a relative humidity of 60%. 300 "(Minolta, color difference meter) was measured in the L ^* a ^* b ^* color system, and the sample surface was randomly selected and measured under standard light source (D65) irradiation. Average value. The color difference ΔE means ΔE ^* ab, and ΔE ^* ab = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2 , and the color difference between the two colors is expressed as L ^* Calculated from the value of a ^* b ^* .

  In the present specification, the colored paint (a1) is used as a sample for measuring the color difference of the colored paint particles (A).

  In the multicolored paint (II), the blending ratio of the colored paint particles having a color difference ΔE of 15 or more with respect to the colored coating film formed from the colored paint (I) is 25% by mass or more, particularly 40 to 40%. It is suitable from the point of the finishing property of the composite coating film formed by the method of this invention that it exists in the range of 99 mass%.

  In the multicolored paint (II), the colored paint (a1) for producing the colored paint particles (A) may be water-based or solvent-based, but it must be water-based. Is suitable.

  As the aqueous resin used when the colored paint (a1) is water-based, a resin that can be dissolved or dispersed in water is used. There is no particular limitation on the type of the resin, and specifically, for example, it can be appropriately selected from the resins listed in the resin included in the colored paint (I).

  In the method of the present invention, the specific colored paint particles (A) and the coating film-forming component (B) are formed on the colored paint film having a specific range of water absorption formed by coating the colored paint (I). The paint containing the multicolor pattern paint (II) is applied, and the water absorption rate of the color coating film formed from the color paint (I) and the color difference between the color paint film and the color paint particles (A) satisfy the above relationship. Although it will not be restrict | limited especially if it is a thing, Colored paint (I) contains a reactive functional group (m), and reaction which can react a multi-colored paint (II) with a reactive functional group (m) It is desirable that it contains a functional functional group (n).

  This improves the adhesion between the colored coating film formed from the colored paint (I) and the multicolored paint film formed from the multicolored paint (II), and the durability of the composite coating film formed by the method of the present invention. Can be improved.

  The combination of the reactive functional group (m) and the reactive functional group (n) is not particularly limited as long as the combination can react with each other under the drying condition of the coating film. Specifically, For example, hydroxyl group and isocyanate group, hydroxyl group and alkyl ether group, hydroxyl group and imino group, carboxyl group and epoxy group, amino group and epoxy group, amide group and epoxy group, carbonyl group and hydrazine group, carbonyl group and hydrazide group, carbonyl group And a combination of a carbonyl group and a bisacetyldihydrazone group. Particularly, a combination of a carbonyl group and a hydrazide group is preferable because it can form a one-component crosslinking at room temperature.

  As a combination of the colored paint (I) and the colorful pattern paint (II), both the colored paint (I) and the colorful pattern paint (II) contain a resin having a reactive functional group (m). ) And / or the multicolored paint (II) may contain a crosslinking agent having a reactive functional group (n) capable of reacting with the reactive functional group (m).

  In the method of the present invention, from the viewpoints of water resistance, weather resistance of the composite coating film formed, storage stability of each coating material, and room temperature one-component crosslinking, etc. ) Both contain a carbonyl group-containing aqueous resin, and the colored paint (I) and / or the multicolor paint (II) preferably contains a hydrazine derivative.

  Examples of the hydrazine derivative for reacting with the carbonyl group used for such purposes include hydrazine, hydrazine hydrate, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid Dihydrazide of saturated aliphatic carboxylic acid having 2 to 18 carbon atoms such as dihydrazide; dihydrazide of monoolefinically unsaturated dicarboxylic acid such as maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide; phthalic acid, terephthalic acid or isophthalic acid dihydrazide Pyromellitic acid dihydrazide, trihydrazide or tetrahydrazide; nitrilotriacetic acid trihydrazide, citric acid trihydrazide, 1,2,4-benzenetrihydrazide; ethylenediamine Traacetic acid tetrahydrazide, 1,4,5,8-naphthoic acid tetrahydrazide; polyhydrazide obtained by reacting a low polymer having a carboxylic acid lower alkyl ester group with hydrazine or hydrazine hydrate (hydrazine hydride), etc .; carbonic acid Dihydrazide, bissemicarbazide; obtained by excessively reacting a diisocyanate such as hexamethylene diisocyanate and isophorone diisocyanate and a polyisocyanate compound derived therefrom with N, N-substituted hydrazine such as N, N-dimethylhydrazine and the hydrazides exemplified above. Polyfunctional semicarbazide; the isocyanate group in the reaction product of the polyisocyanate compound and an active hydrogen compound containing a hydrophilic group such as polyether polyols and polyethylene glycol monoalkyl ether Water-based polyfunctional semicarbazide obtained by excessively reacting the indicated dihydrazide; a mixture of the polyfunctional semicarbazide and water-based polyfunctional semicarbazide; and bisacetyldihydrazone, etc., each of which is used alone or in combination of two or more. can do.

  Coloring pigments and dyes can be used as the colorant that can be contained in the colored paint (a1). As a coloring pigment, it can select suitably from what was illustrated by description of the said colored coating material (I), and can be used individually or in combination of 2 or more types.

  On the other hand, examples of the dye include azo dyes such as monoazo dyes, polyazo dyes, metal complex azo dyes, pyrazolone azo dyes, stilbene azo dyes and thiazole azo dyes; anthraquino dyes such as anthraquinone derivatives and anthrone derivatives; indigo derivatives and thioindigo derivatives Indigoid dyes such as: phthalocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes; quinoneimine dyes such as azine dyes, oxazine dyes, thiazine dyes; polymethine (or cyanine) dyes, adimethine dyes, etc. Methine dyes; quinoline dyes; nitro dyes; nitrone dyes; benzoquinone and naphthyquinone dyes; naphthalimide dyes; perinone dyes, and the like. Together it can be used. These colorants can be used alone or in combination of two or more according to the intended color.

  In the colored paint (a1), an extender can be used together with the colorant. As an extender, it can select suitably from what was listed by description of the said colored paint (I), and can be used individually or in combination of 2 or more types.

  The blending amount of the colorant is usually 0.01 to 500 masses based on the mass of the resin contained in the color paint (a1) from the viewpoints of colorability, specific gravity, durability and the like due to the color paint particles (A). %, Preferably 0.05 to 400% by mass.

  The colored paint (a1) may further comprise, if necessary, a specific gravity adjusting material such as balloon particles, an antifoaming agent, a curing catalyst, a pigment dispersant, an aromatic, a deodorizing agent, an antibacterial agent, a neutralizing agent, and a surfactant. , Aqueous water repellent, dispersant, antiseptic, antifungal agent, antifreeze agent, UV absorber, light stabilizer, film-forming aid, zinc whisker, formaldehyde adsorbent, antimony trioxide, antimony pentoxide, water Flame retardants such as aluminum oxide can be contained.

  The granulation of the colored paint (a1) can be performed using a conventionally known technique and is not limited. For example, a liquid composition containing the colored paint (a1) and a water-soluble polysaccharide is dissolved in water. The colored paint (a1) is encapsulated in a polysaccharide metal salt gel by contacting with an aqueous medium containing a monovalent or polyvalent metal ion capable of forming a water-insoluble or hardly soluble salt with the functional polysaccharide. Colored paint particles can be formed.

  The water-soluble polysaccharide is a polysaccharide capable of changing to a water-insoluble or sparingly soluble gel when contacted with a monovalent or polyvalent metal ion in an aqueous medium, generally about 3,000 to about 3,000. Those having a number average molecular weight in the range of 2,000,000 and exhibiting a water solubility of about 10 g / L (25 ° C.) or more are preferred. Specifically, for example, alginic acid or an alkali metal salt thereof, Gellan gum, carrageenan and the like can be mentioned, and these can be used alone or in combination of two or more.

  The water-soluble polysaccharide is the stability of the colored paint particles (A) in water, the handleability when producing the colored paint particles (A), and the durability of the coating film formed from the paint containing the colored paint particles (A). From the standpoint of properties, etc., usually 0.1 to 7% by mass, preferably 0.1 to 5% by mass, based on the total mass of the aqueous resin and water-soluble polysaccharide used in the production of the colored paint particles (A). It is preferable to use within the range.

  As a metal compound used as a source of metal ions used when the colored paint (a1) is made into a granular gel, 0.005 mg or more, particularly 0.08 mg or more is desirably dissolved in 100 g of water at 25 ° C. For example, monovalent metals such as potassium and sodium, magnesium, calcium, strontium, barium, chromium, molybdenum, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, copper, zinc, cadmium, aluminum, cerium, etc. Polyhydric metal hydroxides, oxides, carbonates, chlorides, sulfides and the like can be mentioned, and these can be used alone or in combination of two or more.

  In the coating method of the present invention, from the viewpoint of the durability of the composite coating film finally formed, the metal compound is preferably a hydroxide, an oxide, or a carbonate, and more preferably a calcium salt. desirable.

  In the present invention, use of calcium hydroxide as the metal compound is suitable from the viewpoint of durability of the multi-pattern coating film and smoothness of the coating surface.

  An aqueous medium containing monovalent or polyvalent metal ions can be prepared by dissolving at least a part of the metal compound in the aqueous medium. At that time, the metal compound does not need to be completely dissolved in the aqueous medium, and may be partially dissolved. The content of the metal compound in the aqueous medium containing the metal compound is usually 0.05 to 15% by mass, preferably 0.1 to 10% by mass.

  The liquid composition containing the colored paint (a1) and the water-soluble polysaccharide is capable of forming colored paint particles (A) by contacting with an aqueous medium containing metal ions derived from the metal compound. In this contact, for example, a method in which a liquid composition is dropped into an aqueous medium from the tip of a syringe; a method in which a liquid composition is scattered using a centrifugal force and dropped into an aqueous medium; a liquid from a tip of a spray nozzle A method of atomizing the composition and dropping it in an aqueous medium; a method of adding a liquid composition into an aqueous medium and stirring and mixing with a disperser can be used.

  The size (major axis) of the colored paint particles (A) formed as described above is not particularly limited, and can be appropriately changed according to the design properties required for the multicolor paint (II).

  The above-mentioned multicolor pattern paint (II) is a colored paint particle (in order to ensure the physical properties of the paint film such as the durability of the multicolor pattern paint film, and to ensure the durability as a composite paint film obtained by the coating method of the present invention. In addition to A), it contains a coating film forming component (B).

  The coating film-forming component (B) itself has film-forming properties, and may be either non-crosslinked type or crosslinked type.

  In the present invention, from the viewpoints of affinity with the colored paint particles (A) and storage stability as the multicolored paint (II), when the colored paint particles (A) contain an aqueous resin, the coating film forming component (B ) Is preferably an aqueous composition comprising an aqueous resin.

  As the aqueous resin contained in the coating film-forming component (B), those generally used as a resin binder in the aqueous paint field can be used. For example, among those described above as the aqueous resin in the colored paint (I) It can be used by appropriately selecting from.

  In the present invention, it is various that the colored paint (a1) and the coating film forming component (B) contained in the colored paint particles (A) contain functional groups (x) and (y) that can react with each other. Since the durability of the pattern coating film and the composite coating film obtained by the coating method of the present invention can be improved, the colored coating particle (A) contains a reactive functional group (x), and the coating film. It is desirable that the forming component (B) contains a reactive functional group (y) that can react with the reactive functional group (x).

  As a combination of the reactive functional group (x) contained in the colored paint (a1) contained in the colored paint particles (A) and the reactive functional group (y) contained in the coating film forming component (B), The combination is not particularly limited as long as it is a combination that can react with each other under the drying conditions of the coating film, and is appropriately selected from the combinations listed in the reactive functional group (m) and the reactive functional group (n). In particular, a combination of a carbonyl group and a hydrazide group is suitable because it can be cross-linked at one room temperature.

  As the multicolored paint (II), the colored paint particles (A) and the coating film forming component (B) both contain a resin having a reactive functional group (x). The film-forming component (B) can also be in a form containing a crosslinking agent having a reactive functional group (y) that can react with the reactive functional group (x).

  In the method of the present invention, the colored coating particles (A) and the coating are applied from the viewpoints of durability of the composite coating film formed by the coating method of the present invention, storage stability as a multicolored paint, and one-component crosslinking at room temperature. It is desirable that both the film-forming component (B) contain a carbonyl group-containing aqueous resin, and the colored paint particles (A) and / or the coating-film-forming component (B) contain a hydrazine derivative.

  Specific examples of the hydrazine derivative for reacting with the carbonyl group that can be contained in the colored paint particles (A) or the coating film forming component (B) are as described above.

  In the present invention, the coating film forming component (B) may form a colored coating film or may form a clear coating film. Coloring agents can be included.

  The colorant that can be contained in the coating film forming component (B) can be appropriately selected from those exemplified above as the colorant in the colored paint particles (A). Further, from the viewpoint of improving the drying property of the multicolor pattern coating film, improving the appropriate gloss, and improving the touch feeling, it is desirable to incorporate the extender pigment as described above into the coating film forming component (B).

  When the colorant and / or extender pigment is blended in the coating film forming component (B), the total blending amount is usually 5 to 300% by mass with respect to the resin solid content contained in the coating film forming component (B). , Preferably 10 to 200% by mass, more preferably 15 to 150% by mass.

  The blending ratio of the colored coating particle (A) and the coating film forming component (B) is the solid content mass of the colored coating particle (A) / coated film forming component (B) from the viewpoint of durability of the multicolored coating film. The ratio can be within the range of 1/99 to 60/40, preferably 10/90 to 50/50, more preferably 20/80 to 45/55.

  The multicolored paint (II) can contain paint additives as required.

  Examples of the additives for paint include neutralizers, viscosity modifiers, balloon particles, anti-settling agents, antistatic agents, softeners, antibacterial agents, fragrances, curing catalysts, pH adjusters, humidity control agents, powders or fine particles Activated carbon, photocatalytic titanium oxide, aqueous water repellent, dispersant, antifoaming agent, antiseptic, antifungal agent, antifreezing agent, UV absorber, light stabilizer, film-forming aid, zinc whisker, curing acceleration And flame retardants such as agents, aldehyde adsorbents, waxes, antimony trioxide, antimony pentoxide, and aluminum hydroxide.

  When a UV stabilizer and / or a light stabilizer is added to the multicolored paint (II), specific examples of the UV stabilizer and the light stabilizer used are listed in the description of the colored paint (I). It can be the same as a compound, and can be used individually or in combination of 2 or more types.

  As the amount used, the ultraviolet absorber is used in an amount of 0.1 to 5.0% by weight, preferably 0.2 to 2.0% by weight, based on the resin solid content contained in the multicolor paint (II). % Within a range of 0.1% to 5.0% by mass, preferably 0.2% to the resin solid content contained in the multicolor paint (II). It is preferable to be in the range of 3.0% by mass.

The above-mentioned multicolor pattern paint (II) can be applied by using a coating means known per se, for example, using a painting tool such as a roller, air spray, airless spray, lysine gun, universal gun, brush, or iron. It can be carried out. Moreover, when using a roller, a wool roller, a sand-bone roller, etc. can be used, As an application quantity, generally 20-500 g / m < ² > as a solid content of a coating material, Preferably it is 30-350 g / m < ² >. It is good to adjust within the range.

  The formed coating film can be dried by any one of heat drying, forced drying, and room temperature drying depending on the composition of the coating composition used.

  In the method of the present invention, in order to form a composite coating film having excellent durability, the water absorption rate of the colored coating film formed by the colored coating material (I) is important as described above. Although the water absorption rate of the multicolored pattern coating film formed by II) is not limited, the water absorption rate of the multicolored pattern coating film is generally 50% or less, particularly within the range of 0.1 to 40%. Can be.

  In the method of the present invention, it is preferable that the multicolored paint (II) is applied so that the concealment rate of the formed coating film is in the range of 10 to 70%, particularly 15 to 65%.

  When the concealment ratio is within the above range, the color tone of the colored coating film formed from the colored paint (I) and the color tone of the multicolored coating film are fused, and a more impressive appearance can be obtained.

  The test piece for calculating the concealment rate (%) is prepared by fixing the concealment rate test paper described in Method B (Concealment rate test paper) of JIS K 5600 4-1 horizontally on a flat glass plate. Then, the multi-color paint is applied thereon, the coating surface is leveled upward, and dried for 48 hours under conditions of an air temperature of 23 ° C. and a relative humidity of 60%.

In this specification, the concealment rate (%) is in accordance with JIS K 5600 4-1 method B (concealment rate test paper), white (Y _W ) and black (Y _B ) of the test piece (coated opacity test paper). ) the point on the randomly selected each four places, to measure the tristimulus values of the points, to calculate the average of the tristimulus values Y _W and Y _B. Thereafter, a value obtained by calculating Y _B / Y _W at a 100-minute rate is defined as a concealment rate.

  Hereinafter, the present invention will be described in more detail with reference to examples. “Part” and “%” indicate “part by mass” and “% by mass” unless otherwise specified.

Production of emulsion Production example 1
In a 4-liter flask having a capacity of 2 liters, 285 parts of deionized water and 1 part of “NEWCOL707-SF” (trade name, manufactured by Nippon Emulsifier Co., Ltd., an anionic surfactant having a polyoxyethylene chain, non-volatile content of 30%) In addition, after nitrogen substitution, the temperature was kept at 85 ° C. Add 3% of the pre-emulsion obtained by emulsifying the following composition and 41 parts of 123 parts of ammonium persulfate aqueous solution in which 3 parts of ammonium persulfate was dissolved in 120 parts of deionized water. After 20 minutes, the remaining pre-emulsion and the remaining aqueous ammonium persulfate solution were added dropwise to the flask over 4 hours.
Deionized water 368 parts Styrene 150 parts Methyl methacrylate 413 parts n-Butyl acrylate 240 parts 2-ethylhexyl acrylate 150 parts Diacetone acrylamide 20 parts 1,6-hexanediol diacrylate 5 parts 2-hydroxyethyl acrylate 20 parts Acrylic acid 2 parts “NEWCOL707-SF” After 66 parts of the dropwise addition, this was further maintained at 85 ° C. for 2 hours and then cooled to 40-60 ° C. Subsequently, pH was adjusted to 8-9 with aqueous ammonia, and an emulsion (a1) containing a carbonyl group having a solid content of 55%, an average particle diameter of 170 nm, and a pH of 8.3 was obtained.

Production Example 2
In a 4-liter flask having a capacity of 2 liters, 285 parts of deionized water and 1 part of “NEWCOL707-SF” (trade name, manufactured by Nippon Emulsifier Co., Ltd., an anionic surfactant having a polyoxyethylene chain, non-volatile content of 30%) In addition, after nitrogen substitution, the temperature was kept at 85 ° C. Add 3% of the pre-emulsion obtained by emulsifying the following composition and 41 parts of 123 parts of ammonium persulfate aqueous solution in which 3 parts of ammonium persulfate was dissolved in 120 parts of deionized water. After 20 minutes, the remaining pre-emulsion and the remaining aqueous ammonium persulfate solution were added dropwise to the flask over 4 hours.
Deionized water 368 parts Styrene 100 parts Methyl methacrylate 413 parts n-butyl acrylate 240 parts 2-ethylhexyl acrylate 192 parts 2-hydroxyethyl acrylate 50 parts acrylic acid 5 parts "NEWCOL707-SF" 66 parts After holding at 85 ° C. for a time, the temperature was lowered to 40-60 ° C. Subsequently, pH was adjusted to 8-9 with aqueous ammonia, and an emulsion (a2) having a solid content of 53%, an average particle diameter of 185 nm, and a pH of 8.1 was obtained.

Production of white pigment paste Production Example 3
The following components were charged in a 1 liter stainless steel container, and stirred with a disper for 30 minutes until uniform, to obtain a white pigment paste (b1).
Water 225 parts “Slulloff 72N” (Note 1) 15 parts “DISPER BYK-190” (Note 2) 30 parts “SN Deformer 380” (Note 3) 15 parts “TITANIX JR-605” (Note 4) 500 parts (Note) 1) “Sura-off 72N”: trade name, manufactured by Takeda Pharmaceutical Co., Ltd., antiseptic,
(Note 2) “DISPER BYK-190”: trade name, manufactured by BYK Chemie, pigment dispersant,
(Note 3) “SN deformer 380”: trade name, manufactured by San Nopco, antifoaming agent,
(Note 4) “TITANIX JR-605”: trade name, manufactured by Teika, titanium white.

Production and production example 4 of green pigment paste
The following components were charged in a 1 liter stainless steel container, and stirred with a disper for 30 minutes until uniform, thereby obtaining a green pigment paste (b2).
Water 520 parts Monoethylene glycol 40 parts "Slulloff 72N" (Note 1) 8 parts "DISPER BYK-190" (Note 2) 48 parts "SN Deformer 380" (Note 3) 16 parts 240 parts phthalocyanine green

Production and production example 5 of yellow pigment paste
A yellow pigment paste (b3) was obtained by charging the following components in a 1 liter stainless steel container and stirring with a disper until uniform for 30 minutes.
Water 520 parts Monoethylene glycol 40 parts “Slulloff 72N” (Note 1) 8 parts “DISPER BYK-190” (Note 2) 50 parts “SN Deformer 380” (Note 3) 16 parts 300 parts of ocher.

Production and production examples of colored paints 6-9
The components shown in Table 1 below were charged into a 1 liter stainless steel container while sequentially stirring, and then further stirred to produce colored paints (A-1) to (A-4).

(Note 5) “TEXANOL”: trade name, manufactured by Eastman Chemical Company, 2,2,4-trimethylpentanediol monoisobutyrate, film-forming aid,
(Note 6) “TINUVINE 123”: trade name, manufactured by Ciba Specialty Chemicals, piperazine light stabilizer,
(Note 7) “TINUVINE 384-2”: trade name, manufactured by Ciba Specialty Chemicals, benzotriazole ultraviolet absorber,
(Note 8) “Adecanol UH438”: trade name, manufactured by Asahi Denka Co., Ltd., modified polyether urethane, viscosity modifier.

Production Example 10
Production of Red Rust Pigment Paste The following components were charged in a 1 liter stainless steel container and stirred with a disper for 30 minutes to obtain a red rust pigment paste (b4).
Water 520 parts Monoethylene glycol 40 parts “Slulloff 72N” (Note 1) 8 parts “DISPER BYK-190” (Note 2) 48 parts “SN Deformer 380” (Note 3) 16 parts Iron oxide 240 parts.

Production Example 11
Production of Black Pigment Paste A black pigment paste (b5) was obtained by charging the following components in a 1 liter stainless steel container and stirring with a disper for 30 minutes until uniform.
Water 520 parts Monoethylene glycol 40 parts “Slulloff 72N” (Note 1) 8 parts “DISPER BYK-190” (Note 2) 48 parts “SN Deformer 380” (Note 3) 16 parts Carbon black 200 parts.

Production and production example 12 of water-based paint composition for colored paint particles
The following components were sequentially blended in a container, and stirred and mixed so as to be uniform to obtain an aqueous coating composition (B-1) for colored coating particles.
Carbonyl group-containing emulsion (a1) 250 parts White pigment paste (b1) 154 parts 10% adipic acid dihydrazide aqueous solution 4 parts “TEXANOL” (Note 5) 20 parts “SN deformer 380” (Note 3) 2 parts “Adecanol UH-438 (Note 8) 2 parts 2% sodium alginate aqueous solution 280 parts.

Production Examples 13-15
In the said manufacture example 12, except having changed a compounding composition into the compounding composition shown in following Table 2, it carried out similarly to the manufacture example 12, and manufactured water-based coating composition (B-2)-(B-4).

Production of colored paint particles Production Example 16
A water-based coating composition obtained as described above was prepared by charging 1,300 parts of a 0.15% aqueous calcium hydroxide solution into a 4 liter stainless steel container and stirring at a rotational speed of 2500 rpm using a stirring blade having a diameter of 75 mm. (B-1) 650 parts were gradually dropped into the container to produce colored paint particles. Next, the liquid in the container was further stirred for 15 minutes at the same rotation speed, and then filtered using a 200-mesh wire mesh to obtain colored paint particles (C-1) having a solid content of 20%.

Production Examples 17 to 19
In Production Example 16, colored paint particles (C-2) to (C-2) to (C) are produced in the same manner as in Production Example 16 except that the aqueous paint composition shown in Table 3 below is used instead of the aqueous paint composition (B-1). C-4) was obtained.

Production of water-based clear paint for coating film forming component Production Example 20
The following components were charged in a 2 liter stainless steel container, and stirred and mixed with a stirrer for 30 minutes to obtain an aqueous clear coating material (c1) having a solid content of 50%.
55% carbonyl group-containing emulsion (a1) 750 parts “TEXANOL” (Note 5) 50 parts Water 279 parts “Talc SS” (Note 10) 250 parts “SN Deformer 380” (Note 3) 10 parts “Adecanol UH-438” (Note 8) 6 parts (Note 10) “Talc SS”: Trade name, manufactured by Nippon Talc Co., Ltd.

Manufacture of water-based colorful paints Production Examples 21-25
The components shown in the following Table 4 were charged into a 500 ml sterence vessel while sequentially stirring, and then stirred until uniform, thereby obtaining multicolored paints (D-1) to (D-5).

Coating Examples 1-6 and Comparative Examples 1-3
On a slate plate (150 × 70 × 3 mm), “EP sealer transparent” (manufactured by Kansai Paint Co., Ltd., water-based acrylic emulsion sealer) was applied with a roller so that the coating amount was 100 g / m ² and dried. Each colored paint (I) shown in Fig. 5 is applied with a roller so that the coating amount is 100 g / m ² , dried for one day under conditions of an air temperature of 23 ° C and a relative humidity of 60%, The pattern paint was spray-coated at the application amount shown in Table 5. Then, it dried for 7 days under the conditions of air temperature 23 degreeC and relative humidity 60%, each test coating board was obtained, and each test coating board was used for the following performance test. The results are also shown in Table 5. The concealment rate in the table is as follows. The concealment rate test paper described in Method B (Concealment rate test paper) of JIS K 5600 4-1 is fixed horizontally on a flat glass plate, and the various pattern paints on it. Is applied so as to have the coating amount shown in Table 5, the coated surface is leveled upward, and dried for 48 hours under conditions of an air temperature of 23 ° C. and a relative humidity of 60% to create a test piece for measuring the concealment rate, Randomly select four locations on the white and black ground of each test piece (coated coverage test paper), and set the tristimulus value for each location to “CR-300” (trade name, manufactured by Minolta, color difference meter) ) was measured and calculated by calculating the average of the tristimulus values Y _W and Y _B.

(* 1) Appearance of coating film The coating film of each test coated plate was visually observed and evaluated according to the following criteria.
○: The multi-layered coating film has a sense of depth and is excellent in design.
Δ: The design of the multi-layer coating film is good, but the depth is poor.
X: There is no depth feeling of a multi-layered multi-layer coating film, and the design is monotonous.

(* 2) Water resistance Each test coated plate was immersed in deionized water at 23 ° C. for 14 days, pulled up, visually observed, and evaluated according to the following criteria.
○: Good,
Δ: Any one of luster, whitening, and swelling is recognized,
X: Remarkably blistering is observed, or the coating film is softened.

(* 3) Accelerated weather resistance According to JIS K 5600 7-7 (xenon lamp method), the test coated plate after 2000 hours was visually observed and evaluated according to the following criteria.
A: There is no gloss and the design is good.
○: Slight luster is recognized, but practical level,
Δ: Any one of glossiness, swelling, cracking is recognized,
X: Any one of remarkable glossiness, remarkable swelling, and remarkable cracking is recognized.

Claims (6)

After the colored coating (I) having a water absorption of 20% or less is applied to the surface to be coated, the colored coating is formed, and then the multicolored coating (II) is applied on the coated surface. A method for forming a multicolored pattern coating film for forming a multicolored pattern coating film, wherein the multicolored pattern paint (II) is obtained by granulating the colored paint (a1) and a coating material forming component (B). comprise becomes, Ri color difference ΔE is near the range of 15 or more with colored coating film formed from at least one coloring paint particles (a) and the colored coating (I), colored paint particles (a) and the coating Both the film-forming component (B) contain a resin having a reactive functional group (x), and the colored coating particle (A) and / or the coating film-forming component (B) can react with the reactive functional group (x). multicolor coating film forming method characterized that you containing a crosslinking agent having a reactive functional group (y). The method for forming a multicolored paint film according to claim 1, wherein the colored paint (I) contains an ultraviolet absorber and / or a light stabilizer. The colored paint (I) contains a reactive functional group (m), and the multicolored paint (II) contains a reactive functional group (n) capable of reacting with the reactive functional group (m). 2. The method for forming a multicolor pattern coating film according to 2. Both the colored paint (I) and the multicolored paint (II) contain a resin having a reactive functional group (m), and the colored paint (I) and / or the multicolored paint (II) has a reactive functional group (m). The method for forming a multi-colored coating film according to any one of claims 1 to 3, comprising a crosslinking agent having a reactive functional group (n) capable of reacting with. The multicolor paint (II), the formed coating film multicolor coating according to any one of claims 1 to 4 contrast ratio, characterized in that the painting to be within the range of 10% to 70% of Forming method. A composite coating film obtained by the method for forming a multicolored pattern coating film according to any one of claims 1 to 5 .