JP4971661B2 - Water-based colorful pattern paint and painting method - Google Patents

Description

  The present invention relates to a water-based colorful pattern paint suitable for forming a multi-pattern coating film having excellent coating workability, particularly roller coating workability, and good coating surface smoothness, and a coating method using the same.

  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 multicolored paint, Patent Document 1 discloses a copolymer having a weight average molecular weight of 20,000 to 200,000 and an acid value of 2 or less, which is obtained by copolymerizing a monomer mixture containing at least 20% by weight of an acrylic monomer. A multi-pattern coating composition containing at least one enamel-dispersed particle obtained by mixing and dispersing a composition mainly composed of a colorant and an organic solvent into enamel and dispersing it in an aqueous dispersion medium is disclosed. This multicolored paint composition has good stability of enamel-dispersed particles, and the multicolored paint film formed from it has a variety of design feelings and excellent weather resistance and water resistance. From the viewpoint, it is required to further reduce the amount of the organic solvent contained in the multicolor paint.

  For example, Patent Document 2 discloses a water-based resin having a reactive functional group, a color pigment, water, and a gel derived from a reactive compound capable of reacting in the presence of water as a multicolor pattern coating composition having a low organic solvent content. A water-in-water multicolor paint composition is disclosed in which colored gel particles, which are chemicals, are dispersed in a transparent matte paint containing an aqueous resin and an extender having a specific refractive index. If this coating composition is used, it is possible to form a matte multicolored pattern coating film excellent in smoothness and sharpness, but there is a problem that pattern unevenness occurs when roller coating is applied.

  In general, water-based paints tend to be inferior in coating workability because they are easier to sag than solvent-based paints, and are water-based colorful pattern paints that can impart a variety of design properties to the coating film that is formed, and good paint workability Development of water-based colorful pattern paints with good roller coating workability that minimizes scattering to the surroundings is desired.

Japanese Patent Application Laid-Open No. 09-1000042 JP 2005-15645 A

  The object of the present invention is good for forming a multi-pattern coating film having good coating workability, having a variety of design properties with little occurrence of pattern unevenness even when applied with a roller, and having good coating surface smoothness. It is to propose a water-based colorful pattern paint.

As a result of diligent investigations on the above problems, the present inventors have found that an aqueous multicolored pattern paint in which colored paint particles of at least two colors are dispersed in a dispersion medium can be combined with a plurality of specific viscosity modifiers. It was found that the viscosity and thixotropic index of the multicolored paint can be in a specific range, excellent in roller coating workability, and capable of forming a multicolored paint film having good design without causing pattern unevenness, The present invention has been reached. That is, the present invention
1.
An aqueous multicolor pattern paint in which at least two colored paint particles (I) are dispersed in a dispersion medium, wherein the colored paint particles (I) comprise an aqueous resin (a) and a colorant (b). The composition is encapsulated in a polysaccharide metal salt gel (c), and is at least 2 selected from the group consisting of inorganic compounds, fiber derivative compounds, polyether compounds and polyacrylic compounds. A water-based multicolor pattern coating composition characterized by containing a viscosity modifier of a kind,
2.
The combination of viscosity modifiers consists of a combination of a fiber derivative compound and a polyether compound, a combination of a polyacrylic acid compound and a polyether compound, and a combination of an inorganic compound and a polyether compound. The water-based multicolor pattern coating composition according to item 1, selected from:
3.
The colored paint particles (I) are obtained by bringing an aqueous paint composition containing an aqueous resin (a), a colorant (b) and a water-soluble polysaccharide into contact with an aqueous medium containing metal ions 1 The water-based multicolor pattern coating composition according to item 2 or 2,
4).
The water-based multicolored paint composition according to any one of items 1 to 3, further comprising a coating film forming component (II),
5.
It reacts with the colored paint particles (I) containing the aqueous coating composition having the reactive functional group (x) comprising the aqueous resin (a) and the colorant (b), and the reactive functional group (x). 5. The aqueous multicolor pattern coating composition according to item 4, comprising a coating film forming component (II) having a reactive functional group (y) to be obtained,
6).
Item 4 or 5 wherein the aqueous resin (a) contained in the colored paint particles (I) has a reactive functional group (x) that reacts with the reactive functional group (y) contained in the coating film forming component (II). Water-based colorful pattern paint composition according to item ,
7).
The aqueous coating composition contained in the color coating particles (I) is an aqueous multicolor paint composition according to item 6 containing a cross-linking agent (e),
8).
8. The aqueous multicolored paint composition according to any one of items 4 to 7, wherein the coating film forming component (II) further contains a crosslinking agent (f).
9.
Both the aqueous resin (a) contained in the colored paint particles (I) and the aqueous resin (d) contained in the coating film forming component (II) have a reactive functional group (x), and the coating film forming component (II) The water-based multicolored paint composition according to 8, further comprising a crosslinking agent (f) having a reactive functional group (y) capable of reacting with the reactive functional group (x),
10.
The viscosity measured using a B-type viscometer is in the range of 2500 to 15000 mPa · sec when the rotational speed is 6 revolutions / minute, and within the range of 1000 to 50000 mPa · sec when the rotational speed is 60 revolutions / minute. The water-based multicolored pattern paint composition according to any one of items 1 to 9, wherein the water-based multicolor pattern paint composition has a thixotropic index within a range of 2.0 to 5.0,
11.
A coating method characterized by applying the water-based multicolored paint composition according to any one of Items 1 to 10 to the surface of the substrate with or without an undercoat coating film,
About.

  According to the water-based colorful pattern paint of the present invention, the viscosity at a low shear rate is in a specific range, the viscosity at a high shear rate is in a specific range, and the thixotropic index is in a specific range. The coating film obtained has good coating surface smoothness and can have various design properties. In addition, the water-based colorful pattern paint of the present invention is difficult to sag even when applied with a roller, it is easy to spread, and the workability of the roller is easy to move. Without any problems, the coated surface is smooth and finished.

  In the present invention, the water-based multicolor pattern paint is formed by dispersing at least two colored paint particles (I) in a dispersion medium, and includes an inorganic compound, a fibrous derivative compound, a polyether compound, and a polyacrylic compound. It includes at least two viscosity modifiers selected from the group consisting of acid compounds.

  As a result, the water-based colorful pattern paint of the present invention can be adjusted to an appropriate viscosity and thixotropic index. When spray paint or roller paint is applied, the paint becomes difficult to sag and easy to spread with a roller (roller distribution). There is an effect that can be improved.

  Examples of the inorganic compound include silicate, metal silicate, montmorillonite, organic montmorillonite, colloidal alumina, and the like, and among them, metal silicate is preferable. As the metal silicate, for example, it can be easily obtained by purifying clay minerals such as hectorite and bentonite or synthesizing by a known method, and examples of the metal include sodium, magnesium, lithium and the like. it can.

  Examples of the fibrin derivative compound include methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose and the like.

  Examples of polyether compounds include pluronic polyethers, polyether dialkyl esters, polyether dialkyl ethers, polyether urethane modified products, polyether epoxy modified products, and the like.

  Examples of the polyacrylic acid-based compound include a copolymer of monomer components including a carboxyl group-containing vinyl-based monomer, which may be neutralized with a basic substance. The polyacrylic acid compound has an acid value of 30 to 300 mgKOH / g, preferably 80 to 280 mgKOH / g.

  The total amount of the viscosity modifier used is generally 0.01 to 6% by mass, particularly 0.05 to 3% by mass, based on the total resin solids contained in the aqueous multicolored paint. It is desirable that

  In the present invention, it is desirable that the viscosity modifier includes an associative viscosity modifier from the viewpoint of achieving both sagging resistance and smoothness.

  Examples of the association-type viscosity modifier include compounds that can spontaneously associate with each other in an aqueous solution to form an aggregate, and include, for example, a hydrophobic group and / or a hydrophilic group in the molecule. A compound can be mentioned. Examples of the hydrophobic group that promotes the association of molecules include a long-chain alkyl group, and examples of the hydrophilic group include a urethane bond and a polyether group.

  Specific examples of combinations of viscosity modifiers that are particularly suitable in the present invention include combinations of fibrin derivative compounds and polyether compounds, combinations of polyacrylic acid compounds and polyether compounds, and inorganic compounds. It is desirable from the viewpoint of sagging resistance and coating surface smoothness to be selected from the group consisting of combinations with polyether compounds.

  In the case of a combination of a fibrin derivative compound and a polyether compound, the use ratio of both is 1/99 to 99/1, preferably 10/90 to the mass ratio of fibrin derivative compound / polyether compound. It is preferable to be within the range of 90/10.

  In the case of a combination of a polyacrylic acid compound and a polyether compound, the use ratio of both is 1/99 to 99/1, preferably 10/90 to 90, in terms of mass ratio of polyacrylic acid compound / polyether compound. It is preferable to be within the range of / 10.

  In the case of a combination of an inorganic compound and a polyether compound, the ratio of use of both is 1/99 to 99/1, preferably 10/90 to 90/10, in terms of the mass ratio of the inorganic compound / polyether compound. It is preferable to be within.

  In the present invention, it can be appropriately selected whether the viscosity modifier is blended in the colored paint particles (I) or the dispersion medium. In order to further improve the coating workability, it is desirable that the dispersion medium, particularly the coating film forming component, contains a viscosity modifier.

Colored paint particles (I):
In the present invention, the coloring paint particles (I) are not particularly limited in terms of materials, production methods and the like, and conventionally known ones can be used. For example, an aqueous resin containing an aqueous resin (a) and a coloring agent (b) can be used. It is desirable from the viewpoint of roller coating workability that the coating composition is encapsulated in the polysaccharide metal salt gel (c).

Aqueous resin (a) :
The aqueous resin (a) contained in the aqueous coating composition contributes to the durability of the colored coating particles (I), and a resin that can be dissolved or dispersed in water is used. 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 resins, or may be graft-polymerized.

  When the aqueous resin (a) is in the form of dispersed particles, the aqueous resin (a) can be a single layer or a multilayer such as a core / shell type. Further, the aqueous resin (a) can be a resin having an anionic group, for example, a carboxyl group as a hydrophilic group from the viewpoint of the production stability of the colored paint particles, and in this case, the resin is neutralized. Examples of the neutralizing agent that can be used in this case include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, dimethylaminoethanol, 2-methyl-2-amino-1-propanol, and the like. Examples thereof include amines and ammonia, and these can be used alone or in combination of two or more.

  The aqueous resin (a) is preferably an acrylic resin from the viewpoints of durability, weather resistance and the like of the colored paint particles (I).

  Examples of the acrylic resin include those obtained by using an acrylic monomer as an essential monomer component, and appropriately (co) polymerizing the monomer with another polymerizable unsaturated monomer, which can be used for the (co) polymerization. Examples of the monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, Linear or branched alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; alicyclic alkyls such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate ( Meta) Relate; Aralkyl (meth) acrylate such as benzyl (meth) acrylate; Alkoxyalkyl (meth) acrylate such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate; Perfluoroalkyl (meth) acrylate; N N, N-dialkylaminoalkyl (meth) acrylate such as N, diethylaminoethyl (meth) acrylate; (meth) acrylamide; (meth) acrylonitrile; vinyl ester compounds such as vinyl acetate and vinyl propionate; styrene, α- Vinyl aromatic compounds such as 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, trimethylolpropane tri (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-trishydroxymethylethanedi (meth) acrylate, 1,1,1 -Trishydroxymethylethane tri (meth) acrylate, 1,1,1-trishydroxymethylpropane tri (meth) acrylate, triallyl isocyanurate, diallyl terephthalate, divinylbenzene, etc. Polyvinyl compounds having compatible unsaturated groups; hydroxyalkyl such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate Hydroxyl group-containing polymerizable unsaturated monomers such as (meth) acrylate, allyl alcohol, ε-caprolactone modified form of the above hydroxyalkyl (meth) acrylate, polyoxyethylene chain-containing (meth) acrylate having a hydroxyl group at the molecular end; Carboxyl group-containing polymerizable unsaturated monomers such as acrylic acid, maleic acid, crotonic acid and β-carboxyethyl acrylate; (meth) acrolein, formylstyrene, vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl Carbonyl group-containing polymerizable unsaturated monomers such as ethyl ketone, vinyl butyl ketone, acetoacetoxyethyl (meth) acrylate, acetoacetoxyallyl ester, diacetone (meth) acrylamide; glycidyl (meth) acrylate, β-methylglycidyl (meth) ) Epoxy group-containing polymerizable monomers such as acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, and allyl glycidyl ether Saturated monomers; isocyanate group-containing polymerizable unsaturated monomers such as isocyanate ethyl (meth) acrylate and m-isopropenyl-α, α-dimethylbenzyl isocyanate; vinyltrimeth Alkoxysilyl group-containing polymerizable unsaturated monomers such as silane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane; epoxy group-containing polymerizable unsaturated monomers or hydroxyl group-containing polymerizable monomers Oxidative curable group-containing polymerizable unsaturateds such as reaction products of saturated monomers and unsaturated fatty acids, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyloxypropyl (meth) acrylate, dicyclopentenyl (meth) acrylate, etc. A monomer etc. are mentioned, These can be used individually or in combination of 2 or more types, respectively.

  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 surfactants can be used. Examples of applicable surfactants include anionic surfactants and nonionic surfactants. And amphoteric surfactants.

  Examples of the anionic surfactant include alkyl diphenyl ether disulfonates such as diammonium dodecyl diphenyl ether disulfonate, sodium dodecyl diphenyl ether disulfonate, calcium dodecyl diphenyl ether disulfonate, sodium alkyl diphenyl ether disulfonate; sodium dodecylbenzene sulfonate, dodecylbenzene Alkyl benzene sulfonates such as ammonium sulfonate; 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 (eg, polyoxy Sodium ethylene alkyl ether sulfate, polyoxyethylene alkyl ether Polyoxyethylene alkyl ether sulfate such as ammonium sulfate; polyoxyethylene alkyl phenyl ether sulfate sodium, polyoxyethylene alkyl phenyl ether sulfate such as ammonium polyoxyethylene alkyl phenyl 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 dialkylsulfosuccinate, monoalkyl succinate Alkyl succinate sulfonates such as disodium sulfonate and the like. In or in combination of two or more can be used.

  Nonionic surfactants include, for example, polyoxyalkylene unit-containing ether compounds (for example, polyoxyalkylene alkyls such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene tridecyl ether, polyoxyethylene oleyl ether). Ether compounds; 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 mono Polyoxyalkylene alkyl ester compounds such as laurate, polyoxyethylene monostearate, polyoxyethylene monooleate Polyoxyalkylene alkylamine compounds such as polyoxyethylene 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 surfactants 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 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%.

Colorant (b):
As the colorant (b) contained in the colored paint particles (I), pigments and dyes can be used, and color pigments and glitter pigments are particularly suitable. Examples of coloring pigments include white pigments such as titanium dioxide; 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 condensation. Yellow pigments such as azo 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, ansan Red pigments such as throne, anthraquinonyl red, perylene maroon, quinacridone red pigment, diketopyrrolopyrrole, watching red, permanent red; cobalt purple, quinacridone violet, dioxa Purple pigments such as cobalt violet, blue pigments such as cobalt blue, phthalocyanine blue, and selenium blue; green pigments such as phthalocyanine green, and the like. Examples of glittering pigments include aluminum powder, bronze powder, copper powder, and tin powder. Metal pigments such as iron phosphide and zinc powder; pearlescent pigments such as metal oxide-coated mica powder and mica-like iron oxide, and these may be used alone or in combination of two or more. Can do. The titanium dioxide as the white pigment includes functional titanium dioxide such as micro titanium having an average particle diameter of 10 to 80 nm and anatase type titanium dioxide having photocatalytic activity.

  On the other hand, examples of the dye include monoazo dyes, polyazo dyes, metal complex azo dyes, pyrazolone azo dyes, stilbene azo dyes, thiazolazo dyes and other azo dyes; anthraquinone derivatives, anthrone derivatives and other anthraquino dyes; indigo derivatives, thioindigo Indigoid dyes such as derivatives; 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. Not to be able to use.

  In the colored paint particles (I), an extender can be used together with the colorant (b). Specific examples thereof include barita powder, precipitated barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, white carbon, diatomaceous earth, talc, magnesium carbonate, alumina white, gloss white and the like.

  The blending amount of the colorant (b) is usually 0.01 to from the viewpoint of colorability, specific gravity, durability, water resistance and the like due to the colored paint particles (I), based on the mass of the aqueous resin (a). It is suitable to be in the range of 500% by weight, preferably 0.05 to 400% by weight.

  In the present invention, by including a plurality of colored paint particles containing colorants having different color tones, the design of the formed coating film can be improved, and so-called multicolored paint can be prepared. In this case, if a bright pigment such as a metallic pigment or a pearl luster pigment is used as the colorant (b), it is possible to impart a high-grade feeling to the multicolored coating film, which is preferable.

Polysaccharide metal salt gel (c) :
In the present invention, the polysaccharide metal salt gel (c) is a component that constitutes a gelled film for containing the aqueous coating composition inside the particles and can become a shell wall of the colored coating particles (I).

  The colored paint particles (I) form, for example, an aqueous paint composition containing an aqueous resin (a), a colorant (b) and a water-soluble polysaccharide, and form a water-insoluble or sparingly soluble salt with the water-soluble polysaccharide. It can be obtained by contacting with an aqueous medium containing a monovalent or polyvalent metal ion, thereby forming colored paint particles comprising the aqueous paint composition in a polysaccharide metal salt gel. be able to.

  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.

  Water-soluble polysaccharides include the stability of the colored paint particles (I) in water, the handleability when producing the colored paint particles, and the water resistance of the coating film formed from the paint containing the colored paint particles (I). From the viewpoint, it is preferable to use 0.1 to 7% by mass, preferably 0.1 to 5% by mass, based on the total mass of the aqueous resin (a) and the water-soluble polysaccharide.

  The above-mentioned aqueous coating composition further comprises a specific gravity adjusting material such as balloon particles, an antifoaming agent, a curing catalyst, a pigment dispersant, a fragrance, a deodorizing agent, an antibacterial agent, a neutralizing agent, a surfactant, if necessary. Aqueous water repellent, dispersant, antiseptic, antifungal agent, antifreezing agent, UV absorber, light stabilizer, film-forming aid, zinc whisker, formaldehyde adsorbent, antimony trioxide, antimony pentoxide, hydroxylation A flame retardant such as aluminum can be contained.

  In the present invention, the aqueous paint composition for producing the colored paint particles (I) is, for example, an emulsion of the aqueous resin (a), a paste of the colorant (b), and an aqueous solution of the water-soluble polysaccharide as appropriate. It can be prepared by mixing with other ingredients.

  Examples of the metal compound used as a source of metal ions used when the aqueous coating composition is made into a granular gel include monovalent metals such as potassium and sodium, magnesium, calcium, strontium, barium, chromium, molybdenum, and manganese. , Iron, ruthenium, cobalt, rhodium, nickel, palladium, copper, zinc, cadmium, aluminum, cerium and other polyvalent metal hydroxides, oxides, carbonates, chlorides and sulfides.

  The metal in the metal compound is preferably a polyvalent metal, particularly a divalent metal, from the viewpoint of the strength of the colored paint particles to be formed. Examples of the divalent metal include magnesium, calcium, strontium, barium and the like. Periodic table group 2 elements; periodic table group 6 elements such as chromium and molybdenum; periodic table group 7 elements such as manganese; periodic table group 8 elements such as iron and ruthenium; periodic table group 9 elements such as cobalt and rhodium; nickel; Examples include periodic table group 10 elements such as palladium; periodic table group 11 elements such as copper; and periodic table group 12 elements such as zinc and cadmium. Among them, elements of group 2 of the periodic table, particularly calcium, are preferable.

  The metal compound is desirably dissolved in 0.005 mg or more, particularly 0.08 mg or more in 100 g of water at 25 ° C.

  In the present invention, calcium hydroxide is particularly suitable as the metal compound.

  An aqueous medium containing a monovalent or polyvalent metal ion 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.

Preparation of colored paint particles (I) :
The aqueous coating composition can form colored coating particles (I) by contacting with an aqueous medium containing metal ions derived from the metal compound.

  This contact is, for example, a method in which an aqueous coating composition is dropped into an aqueous medium from the tip of a syringe; a method in which the aqueous coating composition is scattered using centrifugal force and dropped into an aqueous medium; from the tip of a spray nozzle A method of atomizing an aqueous coating composition and dropping it in an aqueous medium; a method of adding an aqueous coating composition into an aqueous medium and stirring and mixing with a disperser can be used.

  Colored paint particles formed by encapsulating an aqueous paint composition in a polysaccharide metal salt gel (c) comprising the aqueous resin (a), the colorant (b) and optionally other additive components by the above method. (I) can be obtained.

  The size (major axis) of the colored coating particles (I) formed as described above is not particularly limited, and depends on the finish, coating workability, and the like required for the water-based colorful pattern coating of the present invention. For example, it can be adjusted depending on the composition of the aqueous coating composition, the concentration of metal ions in the aqueous medium, the manner in which the aqueous coating composition is dropped onto the aqueous medium, and the like. In the present invention, the size of the colored paint particles (I) can generally be in the range of 10 to 15,000 μm, preferably 50 to 5,000 μm, and the particle size distribution is 75 μm. The particle groups having a particle size of less than 2,000 μm are preferably in the range of 70 to 100%, particularly 85 to 98% of the total mass of all the particle groups.

  In the present specification, the size of the colored paint particles (I) is the minimum nominal size of the sieve that can be passed when the colored paint particles (I) are sieved (a pore size; one side of the mesh) Approximate with length). As the sieve, six kinds of sieves having nominal sizes (pore size) of 75 μm, 150 μm, 250 μm, 500 μm, 1,000 μm and 2,000 μm are used. The size of the colored paint particles (I) that cannot pass through a sieve having a nominal size (pore size) of 2,000 μm is a line segment that passes through the center of 10 randomly selected colored paint particles (I). The average value of the maximum dimensions when measured with a ruler. In addition, the particle size distribution is determined by classifying all colored paint particles (I) using the above six types of sieves, sufficiently drying the particles remaining on each sieve, and coloring paint particles (I) on each sieve. It can be determined by measuring the mass of the group and calculating the fraction relative to the mass of the dried all colored paint particles (I) group.

  The resulting colored paint particles (I) can be filtered off from an aqueous medium containing metal ions using, for example, a wire mesh having an appropriately sized mesh.

Dispersion medium :
In the aqueous colorful pattern paint of the present invention, the colored paint particles (I) are dispersed in a dispersion medium. In the present invention, the dispersion medium is not particularly limited, and examples thereof include water or a water-organic solvent mixed solution obtained by mixing water with an organic solvent such as a water-soluble organic solvent. it can.

Coating film forming component (II) :
In the present invention, the water-based multicolor pattern paint may contain a coating film forming component (II) as necessary in addition to the colored paint particles (I) and the dispersion medium from the viewpoint of water resistance and weather resistance of the multicolor paint film. it can. The coating film forming component (II) itself has film-forming properties, and may be either non-crosslinked type or crosslinked type.

  In the present invention, the coating film forming component (II) is an aqueous composition comprising an aqueous resin (d) from the viewpoints of affinity with the colored paint particles (I) and storage stability as an aqueous multicolored paint. It is desirable that

  As the water-based resin (d), those generally used as a resin binder in the water-based paint field can be used. For example, the water-based resin (d) is appropriately selected from those described above as the water-based resin (a) in the colored paint particles (I). Can be used in

  When the aqueous colorful pattern paint of the present invention contains a coating film forming component (II), the aqueous coating composition contained in the colored coating particle (I) and the coating film forming component (II) can react with each other. It is preferable to contain the functional groups (x) and (y) from the viewpoint of water resistance, weather resistance, etc. of the multicolored paint film, and the waterborne multicolored paint comprises the water-based resin (a) and the colorant (b). Colored paint particles (I) containing an aqueous coating composition containing a reactive functional group (x) and a coating having a reactive functional group (y) capable of reacting with the reactive functional group (x) It is desirable to contain a film forming component (II).

  As a combination of the reactive functional group (x) contained in the aqueous coating composition contained in the colored paint particles (I) and the reactive functional group (y) contained in the coating film forming component (II), 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. Specifically, for example, a hydroxyl group and an isocyanate group, a hydroxyl group and an alkyl ether group, a hydroxyl group and an imino group, and a carboxyl group Examples include combinations of epoxy groups, amino groups and epoxy groups, amide groups and epoxy groups, carbonyl groups and hydrazine groups, carbonyl groups and hydrazide groups, carbonyl groups and semicarbazide groups, and carbonyl groups and bisacetyldihydrazone groups. Hydroxyl groups and isocyanate groups, hydroxyl groups and alkyl ether groups, hydroxyl groups and imino groups, carbonyl groups and hydrazide groups, etc. Seen together is preferred.

  In the present invention, when the colored paint particles (I) and the coating film forming component (II) contain reactive functional groups that react with each other, the aqueous resin (a) contained in the colored paint particles (I) The reactive functional group (x) which reacts with the reactive functional group (y) contained in component (II) can be contained.

  Examples of the reactive functional group (x) that can be contained in the aqueous resin (a) include a carbonyl group, a hydroxyl group, a carboxyl group, an epoxy group, and an amino group. Particularly, a carbonyl group and a hydroxyl group are preferable. is there. The content of these reactive functional groups (x) in the aqueous resin (a) is usually 0.05 to 2 mmol / g resin, preferably 0.1 to 1 mmol / g resin, more preferably 0.1 to 0. It can be in the range of 0.5 mmol / g resin.

  For example, the reactive functional group (x) is introduced into the aqueous resin (a) by appropriately (co) polymerizing a polymerizable unsaturated monomer containing the reactive functional group (x) together with another polymerizable unsaturated monomer. Or by reacting a resin containing a reactive functional group (x) with a resin serving as a substrate.

  The aqueous coating composition contained in the colored coating particle (I) reacts with the coating film forming component (II), and the colored coating particle (I) and the coating film forming component (II) are cross-linked through the interface. A crosslinking agent (e) capable of reacting with the reactive functional group (y) can be contained so that a film can be formed.

  As the crosslinking agent (e) contained in the colored paint particles (I), a hydrazine derivative, a melamine resin, and the like, from the viewpoints of good storage stability and being able to make the aqueous colorful pattern paint of the present invention into one liquid. Etc. are suitable.

  Examples of the hydrazine derivatives include saturated aliphatic carboxylic acids having 2 to 18 carbon atoms such as hydrazine, hydrazine hydrate, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, and sebacic acid dihydrazide. Dihydrazides of monoolefinic unsaturated dicarboxylic acids 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; nitrilotrizide Acetic acid trihydrazide, citric acid trihydrazide, 1,2,4-benzenetrihydrazide; ethylenediaminetetraacetic acid tetrahydrazide, 1,4,5,8-naphthoic acid Lahydrazide; polyhydrazide obtained by reacting a low polymer having a carboxylic acid lower alkyl ester group with hydrazine or hydrazine hydrate (hydrazine hydride), etc .; dihydrazide carbonate, bissemicarbazide; diisocyanate such as hexamethylene diisocyanate, isophorone diisocyanate and the like Polyfunctional semicarbazide obtained by excessively reacting the derived polyisocyanate compound with N, N-substituted hydrazine such as N, N-dimethylhydrazine or the hydrazide exemplified above; the polyisocyanate compound and polyether polyols or polyethylene glycol An aqueous polyfunctional semi-catalyst obtained by excessively reacting the above-exemplified dihydrazide with an isocyanate group in a reaction product with an active hydrogen compound containing a hydrophilic group such as monoalkyl ethers Bajido; mixture of polyfunctional semicarbazide and aqueous polyfunctional semicarbazide; bis-acetyl and di-hydrazone, and these may be used either alone or in combination of two or more.

  Examples of the melamine resin include a resin having an alkyl ether group and / or an imino group in a molecule obtained by reacting melamine, formaldehyde and water and / or alcohol as necessary. Examples include methylol melamine such as dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, and hexamethylol melamine; alkyl ether compounds of the methylol melamine; condensates of methylol melamine or alkyl ether compounds thereof, and the like. It is done. Examples of the alkyl group in the methyl ether melamine alkyl ether include alkyl groups having 1 to 8 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and 2-ethylhexyl groups.

  When a melamine resin is used as the cross-linking agent (e), if necessary, a sulfonic acid such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, or the like, Salts and the like can be used.

  When the aqueous paint composition contained in the colored paint particles (I) contains the cross-linking agent (e), the amount used is 1 mol of the reactive functional group (y) as the reaction partner in the cross-linking agent. It is desirable that the amount of the reactive functional group is adjusted to be in the range of usually 0.05 to 2 mol, preferably 0.1 to 1 mol.

  On the other hand, the coating film-forming component (II) desirably contains a reactive functional group (y) that can react with the reactive functional group (x) contained in the colored paint particles (I).

  The coating film forming component (II) can comprise an aqueous resin (d) and, if necessary, a crosslinking agent (f). As the aqueous resin (d), for example, it reacts with a reactive functional group (x). It is desirable to contain a reactive functional group (y) that can be used.

  The aqueous resin containing the reactive functional group (y) has a reactive functional group (y) of generally 0.05 to 0.5 mmol / g resin, preferably 0.1 to 0.4 mmol / g resin. It can be contained within the range. Examples of the reactive functional group (y) in the aqueous resin include a carbonyl group, a hydroxyl group, a carboxyl group, an epoxy group, and an amino group, and a carbonyl group and a hydroxyl group are particularly preferable. As the reactive functional group (y) -containing aqueous resin, for example, the reactive functional group (x) -containing aqueous resin in the colored paint particles can be appropriately selected from those described above.

  The coating film-forming component (II) can appropriately contain a crosslinking agent (f) in addition to the aqueous resin (d) which may have a reactive functional group (y). When (d) does not have a reactive functional group (y), it is desirable to use a crosslinking agent (f) in combination.

  The crosslinking agent (f) is a compound having a functional group (y) capable of reacting with the reactive functional group (x) contained in the colored paint particles, and specifically includes, for example, a hydrazine derivative, a melamine resin. And polyisocyanate crosslinking agents.

  The hydrazine derivative and melamine resin that can be used as the crosslinking agent (f) can be appropriately selected from those described above as the crosslinking agent (e) in the colored paint particles.

  Examples of the polyisocyanate crosslinking agent include aliphatic diisocyanates such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate; 4,4′-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, and the like. Alicyclic diisocyanates; aromatic diisocyanates such as xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane diisocyanate; similar compounds such as isocyanurates and burettes of these diisocyanates, each of which can be used alone or Two or more types can be used in combination.

  The polyisocyanate cross-linking agent may be a water-dispersible polyisocyanate obtained by reacting a non-isocyanate emulsifier with a polyisocyanate compound containing at least two isocyanate groups in one molecule. As the nonionic emulsifier capable of reacting with the polyisocyanate compound, the same nonionic emulsifiers as described above can be used, and in particular, an active hydrogen group that reacts with an isocyanate group and an oxyalkylene unit. Those having an oxyethylene unit are preferred.

  The water-dispersible polyisocyanate may be modified by reacting with a silane coupling agent having an active hydrogen group at one end and an alkoxysilyl group at the other end, if necessary. Examples of the silane coupling agent include N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, and γ-aminopropyltriethoxy. Examples include silane, N-phenyl-γ-aminopropyltrimethoxysilane, and γ-mercaptopropyltrimethoxysilane.

  Examples of such commercially available water-dispersible polyisocyanates include “Baihijoule 3100” and “VPLS2319” (trade names, manufactured by Bayer).

  The content of the crosslinking agent (f) in the coating film forming component (II) is usually such that the amount of the reactive functional group (y) in the crosslinking agent is 1 mol of the reactive functional group (x) of the reaction partner. It is desirable to adjust so that it may be in the range of 0.05 to 2 mol, preferably 0.1 to 1 mol.

  In the present invention, from the viewpoint of the water resistance and weather resistance of the resulting multicolored coating film, the aqueous resin (a) contained in the colored paint particles (I) and the aqueous resin (d) contained in the coating film forming component (II). Both have a reactive functional group (x), the coating film forming component (II) further comprises a crosslinking agent (f) having a reactive functional group (y) capable of reacting with the reactive functional group (x). It is desirable to contain.

  In the present invention, the coating film forming component (II) 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 (II) can be appropriately selected from those exemplified above as the colorant (b) that can be contained in the colored paint particles. Further, from the viewpoints of improving the drying property of the multicolored coating film, improving the appropriate gloss, and improving the tactile sensation, it is desirable to incorporate the extender pigment as described above into the coating film forming component (II).

  When the colorant and / or extender pigment is blended in the coating film forming component (II), 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 (II). , Preferably 10 to 200% by mass, more preferably 15 to 150% by mass.

  Moreover, the said coating-film formation component (II) can contain a balloon particle | grain depending on the case, and can improve the texture of the coating film formed by it, a touch feeling, etc. The balloon particles are hollow particles having a cavity in a thin shell, and include resin-based balloon particles and inorganic-based balloon particles. A gas (typically air) is normally enclosed in the cavity of the balloon particles, but may be reduced in pressure or vacuum depending on circumstances.

  Examples of the average particle diameter of the balloon particles include 0.05 to 500 μm, preferably 0.1 to 200 μm.

  In this specification, the average particle diameter of the balloon particles is the median diameter (d50) of the volume-based particle size distribution measured by a laser diffraction scattering method.

  The shell in the resin-based balloon particles can be made of various resins. Examples of the constituent monomer unit of the resin include acrylonitrile, acrylamide, acrylic acid, acrylic ester, methacrylonitrile, methacrylamide, methacrylic acid, methacrylic acid. Examples thereof include esters, vinyl chloride, vinylidene chloride and the like, and these can be (co) polymerized singly or in combination of two or more. Further, a shell crosslinked by adding (co) polymerizing a suitable crosslinkable monomer such as divinylbenzene, polyethylene glycol dimethacrylate, triallyl isocyanurate, trimethylolpropane trimethacrylate, triacryl formal, etc. It can also be formed.

  Examples of the inorganic balloon particles include glass balloon particles, shirasu balloon particles, alumina balloon particles, zirconia balloon particles, and aluminosilicate balloon particles, and these can be used alone or in combination of two or more. Further, the resin-based balloon particles and the inorganic balloon particles may be used in appropriate combination.

  The blending amount of the balloon is usually 0.5 to 15% by mass, preferably 1 to 10% by mass, based on the resin solid content in the coating film forming component (II).

  In the present invention, the point of water resistance and weather resistance of a coating film formed from a water-based multicolored paint, and further, by adjusting the viscoelasticity of the water-based multicolored paint together with the viscosity modifier, from the point of improving the paint workability, It is desirable that the water-based colorful pattern paint contains silica fine particles.

  The silica fine particles may be crystalline or amorphous, and there are no limitations on the type and production method, and conventionally known ones can be used.

  Examples of the average particle diameter of the silica fine particles include 0.1 to 30 μm, preferably 0.1 to 15 μm. The silica fine particles having an average particle diameter of 0.1 to 30 μm include aggregates of primary particles.

In this specification, the average particle diameter of the silica fine particles is the median diameter (d50) of the volume-based particle size distribution measured by the laser diffraction scattering method.
In the present invention, from an aqueous multicolor paint point water resistance and weather resistance of the coating workability and the formed coating film, the specific surface area of the silica fine particles, 30 to 400 m ² / g, preferably 50 to 250 m ² / g It is desirable to be within the range.

In the present specification, the specific surface area means the total surface area (m ² / g) per 1 g of silica fine particles, and is calculated by measuring an adsorption isotherm of nitrogen gas by the BET method.

  The silica fine particles are preferably organically modified in terms of sagging resistance and water resistance of the multicolored coating film.

  Examples of the organically modified silica fine particles include organohalosilanes, dimethylsiloxanes, hexamethyldisilazanes, dimethyldichlorosilanes, trimethoxyoctylsilanes, trimethylsilanes, etc., on silanol groups on the surface of mineral-derived or synthetic silica fine particles. A compound obtained by reacting and bonding silica fine particles and dimethylpolysiloxane or dimethylhydropolyene polysiloxane having a hydroxyl group at the end and heat-treating at 200 to 300 ° C. to form alkylpolysiloxane on the surface of the silica fine particles. Compounds obtained by bonding: compounds obtained by vapor-phase adsorption of silicone oil on the surface of silica fine particles, and the like can be mentioned, and these can be used alone or in combination of two or more.

  In the organically modified silica fine particles, the carbon content of the silica fine particles is 0.1 to 10% by mass, preferably 0.5 to 8% by mass. This is desirable from the viewpoint of stability during coating production.

  In this specification, the carbon content is measured in accordance with JISZ2615 metal material carbon determination method by heating the sample in an oxygen stream to convert carbon to carbon dioxide, which is absorbed by sodium hydroxide and measuring its mass increase. It is calculated by doing.

  As content of the said silica fine particle, it is 0.1-30 mass parts with respect to 100 mass parts of resin solid content in an aqueous | water-based colorful pattern coating material, Preferably it exists in the range of 0.5-15 mass parts. desirable. If the amount is less than 0.1 parts by mass, the effect of improving the water resistance and weather resistance of the multicolored pattern coating film is insufficient, and if it exceeds 30 parts by mass, the coating workability is deteriorated and the appearance of the resulting multicolored pattern coating film is poor. This is not preferable.

  In the present invention, the silica fine particles may be blended in any of the colored paint particles (I) and the dispersion medium. However, in order to further improve the water resistance of the multicolored coating film, the dispersion medium, particularly the coating film forming component ( It is desirable to be blended in II).

  In the present invention, when the aqueous colorful pattern paint contains the colored paint particles (I) and the coating film forming component (II), the blending ratio of the colored paint particles (I) and the coating film forming component (II) is varied. Although it can be changed according to the use of the paint, etc., the solid content mass ratio of the colored paint particles (I) / the coating film forming component (II) is generally 1/99 to 80/20, preferably from the viewpoint of coating workability Can be in the range of 20/80 to 75/25, more preferably 25/75 to 45/55.

Water-based colorful paint :
In the water-based multicolor paint of the present invention, the above-mentioned colored paint particles (I) and the dispersion medium are mixed together with a film-forming component (II) and paint additives, if necessary, by a method known per se. Can be prepared. Moreover, when using a polyisocyanate crosslinking agent as a crosslinking agent in coating-film formation component (II), it is preferable to mix this polyisocyanate crosslinking agent just before apply | coating water-based multicolored paint.

  Examples of the additive for paint include neutralizing agent, surfactant, anti-settling agent, antistatic agent, softening agent, antibacterial agent, perfume, curing catalyst, pH adjuster, humidity control agent as described above for the colored paint particles. Agent, powdered or fine particle activated carbon, photocatalytic titanium oxide, aqueous water repellent, dispersant, antifoaming agent, antiseptic, antifungal agent, antifreezing agent, ultraviolet absorber, light stabilizer, film-forming aid , Zinc whisker, curing accelerator, aldehyde adsorbent, wax, alkyl silicate condensate or low alkylating agent such as modified alkyl silicate obtained by modifying the alkyl silicate condensate with polyalkylene glycol, antimony trioxide, pentoxide Examples include flame retardants such as antimony and aluminum hydroxide.

  Polyvinyl compounds such as polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl benzyl alcohol copolymer; protein derivatives such as sodium caseinate and ammonium caseinate; partial esters of vinyl methyl ether-maleic anhydride copolymer, dryness A viscosity modifier such as a maleic anhydride copolymer such as a half ester of a reaction product of an oil fatty acid allyl alcohol ester-maleic anhydride can also be used.

  From the viewpoint of sagging resistance and coating surface smoothness, it is preferable that the above-mentioned water-based multicolored paint has a paint solid content in the range of 15 to 45% by mass, particularly 20 to 40% by mass.

  The water-based colorful pattern paint of the present invention has a viscosity measured using a B-type viscometer within a range of 2500 to 125000 mPa · sec, particularly 6000 to 45000 mPa · sec, under the condition of a rotation speed of 6 revolutions / minute. Is in the range of 1000 to 50000 mPa · sec, particularly 1200 to 10000 mPa · sec, and the thixotropic index is in the range of 2.0 to 5.0, particularly 2.9 to 4.5. Can be inside.

  In this specification, the viscosity (mPa · sec) is a B-type viscometer with a paint prepared immediately before coating adjusted to 20 ° C. It is set to the value measured using 6 rotors / min and 60 rpm / min.

The thixotropic index (Ti value) is a value calculated by the following formula.
Ti = Va / Vb
Here, Va is the paint viscosity (mPa · sec) measured at a rotational speed of 6 revolutions / minute, and Vb is the paint viscosity (mPa · sec) measured at a rotational speed of 60 revolutions / minute. .

  Here, it is preferable that the viscosity of the coating material at a rotational speed of 6 rotations / minute is in the above range, since it can have sagging resistance after coating and leveling property of the coating film after coating.

  In addition, when the rotation speed is 60 rotations / minute, the viscosity of the paint is in the above range, the roller distribution is good, or unevenness can be suppressed in the finished appearance, and it is easy to move the roller when the roller is coated, and the workability is good. It is preferable.

  Further, it is preferable that the thixotropic index (Ti value) is in the above-mentioned range, since a flat finish can be obtained without leaving a roller eye on the coating film when roller coating is applied.

  The water-based colorful pattern paint of the present invention has a low organic solvent content and can form a protective coating film with excellent performance such as water resistance and coating film appearance. It can be applied to various applications such as sandstone paint, leather paint and ceramic paint.

Painting method :
The water-based colorful pattern paint of the present invention can form a protective coating film having various design properties and excellent performance such as water resistance by coating on the surface of the substrate.

  Examples of the substrate surface to which the aqueous colorful pattern paint of the present invention can be applied include gypsum board, concrete wall, mortar wall, slate board, PC board, ALC board, cemented calcium silicate board, wood, stone, and plastic molding. Surface of base materials such as materials and metal processed materials, acrylic resin system, acrylic urethane resin system, polyurethane resin system, fluororesin system, silicon acrylic resin system, vinyl acetate resin system, epoxy resin system provided on these base materials And a wallpaper surface made of a material such as polyvinyl chloride, polyolefin, paper, and cloth.

The application amount of the aqueous colorful pattern paint of the present invention can be changed according to the composition of the coating composition to be used, the kind of the substrate to be applied, etc., but is usually 100 to 1,000 g / m ² per time, preferably be in the range of 150~700g / ^{m 2.} Moreover, you may apply repeatedly several times in the range which does not impair the coating-film external appearance.

  The water-based colorful pattern paint of the present invention can be applied using a coating means known per se, for example, using a coating device such as a roller, an air spray, an airless spray, a lysine gun, a universal gun or a brush. it can. Moreover, when using a roller, a wool roller, a sand-bone roller, etc. can be used.

  The formed coating film can be dried by any of heat drying, forced drying, or room temperature drying depending on the composition of the coating composition used. In this specification, drying under a drying condition of less than 40 ° C. is performed at room temperature, drying under a drying condition of 40 ° C. or more and less than 80 ° C., forced drying, and drying under a condition of 80 ° C. or more. Drying is heat drying.

  The water-based colorful pattern paint of the present invention may be applied, for example, to a base coat surface in advance for a protective coating, and then the water-based colorful pattern paint of the present invention is applied to the formed undercoat surface. it can.

  The undercoat paint can be appropriately selected according to the type and state of the surface of the base material. For example, an undercoat paint such as a sealer or a base conditioner can be used. It is also possible to apply a normal top coat as a base forming paint of the coating composition of the present invention.

  Examples of the top coat for forming the base include, for example, an aqueous resin composed of a resin type such as an acrylic resin, a polyolefin resin, a silicon resin, a polyurethane resin, an epoxy resin, a phenol resin, a polyester resin, and an alkyd resin. Or the coating material which contains solvent-type resin as a resin binder can be mentioned, It is preferable to use the coating material which contains water-system resin.

  When applying the undercoat paint, two or more kinds of undercoat paints can be repeated as necessary.

  The undercoating can be applied using a coating means known per se, for example, using a coating device such as a roller, an air spray, an airless spray, a lysine gun, a universal gun, or a brush.

The undercoat coating amount of the coating can be varied according to the types of base material to be coated, usually once per 50~2,000g / ^{m 2,} preferably in the range of 70~1,000g / ^{m 2} It can be.

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

  If the water-based colorful pattern paint of the present invention is used, a protective coating film having various design properties and excellent surface smoothness, finish, water resistance, etc. can be formed. On the coating film of the coating material, a known top coating material may be further applied as necessary.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to only these examples. In the following examples, “part” and “%” mean “part by mass” and “% by mass”, respectively.

Production of emulsion Production example 1
285 parts of deionized water and 1 part of “New Coal 707SF” (Note 1) were added to a 4-liter flask having a volume of 2 liters, and maintained at 85 ° C. after purging with nitrogen. Into it, 3% of the pre-emulsion obtained by emulsifying the components of the following composition and 41 parts of 123 parts of the initiator aqueous solution in which 3 parts of ammonium persulfate was dissolved in 120 parts of deionized water were added. 20 minutes after the addition, the remaining pre-emulsion and the remaining aqueous ammonium persulfate solution were dropped into 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 “New Call 707SF” (Note 1) 66 copies.
After completion 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 with ammonia water to obtain an emulsion (a1) having a solid content of 55%. The average particle size of the emulsion (a1) was 170 nm and the pH was 8.3.
(Note 1) “New Coal 707SF”: trade name, manufactured by Nippon Emulsifier Co., Ltd., an anionic surfactant having a polyoxyethylene chain, non-volatile content of 30%.

Production Example 2
An emulsion (a2) was produced in the same manner as in Production Example 1 except that a pre-emulsion formed by emulsifying components having the following composition was used instead of the pre-emulsion in Production Example 1. The solid content of the emulsion (a2) was 55%, the average particle size was 175 nm, and the pH was 8.2.
Deionized water 368 parts Styrene 150 parts Methyl methacrylate 430 parts n-Butyl acrylate 240 parts 2-Ethylhexyl acrylate 150 parts 2-Hydroxyethyl acrylate 20 parts Acrylic acid 10 parts "Newcol 707SF" (Note 1) 66 parts.

Production of water-based clear paint Production Example 3
The following components were charged in a 1 liter stainless steel container, and stirred and mixed with a stirrer for 30 minutes to obtain an aqueous clear paint (C1) having a solid content of 50%.
55% emulsion (a1) 750 parts "TEXANOL" (Note 2) 50 parts Water 279 parts "Talc SS" (Note 3) 250 parts "SN Deformer 380" (Note 4) 10 parts "Adecanol UH-438" (Note 5) 6 parts.
(Note 2) “TEXANOL”: trade name, manufactured by Eastman Chemical Co., Ltd., 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, film-forming aid.
(Note 3) “Talc SS”: trade name, manufactured by Nippon Talc Co., Ltd.
(Note 4) “SN deformer 380”: trade name, manufactured by San Nopco, defoamer.
(Note 5) “Adecanol UH438”: trade name, manufactured by Adeka, modified polyether urethane, 30% active ingredient, viscosity modifier.

Production Example 4
A water-based clear paint (C2) having a solid content of 46% was produced in the same manner as in Production Example 3 except that the component composition was changed to the following in Production Example 3.
55% emulsion (a1) 750 parts "TEXANOL" (Note 2) 50 parts Water 203 parts "Talc SS" (Note 3) 100 parts "SN Deformer 380" (Note 4) 10 parts "Adecanol UH-438" (Note 5) ) 6 parts “Matsumoto Microsphere F-50” (Note 6) 28 parts (Note 6) “Matsumoto Microsphere F-50”: trade name, manufactured by Matsumoto Yushi Co., Ltd., acrylonitrile resin-based balloon, average particle size 15 μm, Active ingredient 15%.

Production Example 5
An aqueous clear paint (C3) having a solid content of 46% was produced in the same manner as in Production Example 4 except that the component composition was changed to the following in Production Example 4.
55% emulsion (a2) 750 parts "TEXANOL" (Note 2) 61 parts Water 192 parts "Talc SS" (Note 3) 100 parts "SN Deformer 380" (Note 4) 10 parts "Adecanol UH-438" (Note 5) ) 6 parts “Matsumoto Microsphere F-50” (Note 6) 28 parts.

Production of white pigment paste Production Example 6
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 white pigment paste.
Water 45 parts “Slulloff 72N” (Note 7) 3 parts “DISPER BYK-190” (Note 8) 6 parts “TITANIX JR-605” (Note 9) 100 parts.
(Note 7) “Sura-off 72N”: trade name, manufactured by Nippon Enviro Chemicals, Inc.
(Note 8) “DISPER BYK-190”: trade name, manufactured by BYK Chemie, a dispersant.
(Note 9) “TITANIX JR-605”: trade name, manufactured by Teika, titanium white.

Production of aqueous coating composition for colored paint particles Production Example 7
The following components were sequentially blended in a container and stirred and mixed so as to be uniform to obtain an aqueous coating composition (A-1) for colored coating particles.
White pigment paste 154 parts 55% emulsion (a1) 250 parts "TEXANOL" (Note 2) 20 parts "SN deformer 380" (Note 4) 2 parts "Adecanol UH-438" (Note 5) 2 parts 2% sodium alginate aqueous solution 280 parts.

Production Examples 8-17
In Production Example 7, water-based coating compositions (A-2) to (A-11) were produced in the same manner as in Production Example 7 except that the formulation was changed to the formulation shown in Table 1 below.

(Note 11) Green pigment paste: Color paste prepared by adjusting “Unilant 88 green” (trade name, manufactured by Yokohama Kasei Co., Ltd.) so that the pigment content is about 20%.
(Note 12) Aluminum paste: 45.5 parts of aluminum pigment paste “MG-51” (Asahi Kasei Co., Ltd., aluminum content 66%, hydrocarbon-based and petroleum-based organic solvent 34%) in a stirring and mixing container, ethylene glycol mono 35 parts of butyl ether and 3 parts of a phosphate group-containing resin solution (*) were added and mixed by stirring to obtain an aluminum pigment paste.

  (*) Phosphate group-containing resin solution: In a reaction vessel equipped with a stirrer, a temperature controller and a refrigerator, put a mixed solvent of 27.5 parts of methoxypropanol and 27.5 parts of isobutanol and heat to 110 ° C. 25 parts of styrene, 27.5 parts of n-butyl methacrylate, 20 parts of “isostearyl acrylate” (manufactured by Osaka Organic Chemical Co., Ltd., branched higher alkyl acrylate), 7.5 parts of 4-hydroxybutyl acrylate, 50% phosphoric acid group 121.5 parts of a mixture comprising 15 parts of a polymerizable monomer (note **), 12.5 parts of 2-methacryloyloxyethyl acid phosphate, 10 parts of isobutanol and 4 parts of t-butylperoxyoctanoate over 4 hours In addition to the above mixed solvent, 0.5 part of t-butylperoxyoctanoate and 20 parts of isopropanol The Ranaru mixture was added dropwise in 1 hour. Thereafter, the mixture was aged and stirred for 1 hour to obtain a phosphate group-containing resin solution having a solid content of 50%.

(Note **) Phosphoric acid group-containing polymerizable monomer: After placing 57.5 parts of monobutyl phosphoric acid and 41.1 parts of isobutanol in a reaction vessel equipped with a stirrer, a temperature controller and a refrigerator, and bringing the temperature to 110 ° C. Then, 42.5 parts of glycidyl methacrylate was added dropwise over 2 hours under air ventilation, and the mixture was further aged and stirred for 1 hour. Thereafter, 5.9 parts of isopropanol was added to obtain a phosphate group-containing polymerizable monomer solution having a solid content of 50%.
(Note 13) “Cymel 327”: trade name, manufactured by Mitsui Cyanamid Co., Ltd., melamine resin.

Production of colored paint particles Production Example 18
Obtained above while stirring 1,300 parts of a 0.15% calcium hydroxide (Note 14) aqueous solution in 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 650 parts of the aqueous coating composition (A-1) was gradually dropped into the container to produce colored coating 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 (I-1). The obtained colored paint particles (I-1) had a solid content of 20%, and the ratio of the colored paint particles having a size of 75 μm or more and less than 500 μm was 95% of all particles.
(Note 14) Calcium hydroxide: 0.15 g dissolved in 100 g of water at 25 ° C.
Production Example 19
In a 4 liter stainless steel container, 24 parts of calcium hydroxide and 1,200 parts of deionized water were charged, and the aqueous coating composition (A-2) was stirred while stirring at a rotational speed of 1500 rpm using a stirring blade having a diameter of 75 mm. 600 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 through a 200-mesh wire mesh to obtain colored paint particles (I-2). The obtained colored paint particles (I-2) had a solid content of 20%, and the ratio of the colored paint particles having a size of 150 μm or more and less than 2000 μm was 95% of all the colored paint particles.

Production Examples 20 to 28
In Production Example 18, colored paint particles (I-3) to (I-3) to (I) were used in the same manner as in Production Example 18 except that the aqueous paint composition shown in Table 2 below was used instead of the aqueous paint composition (A-1). I-11) was obtained.

Production Example 29
Into a 4 liter stainless steel container, 600 parts of 5% calcium chloride aqueous solution was charged, and 660 parts of the aqueous coating composition (A-3) was gradually put into the container while rotating at a rotational speed of 3000 rpm using a stirring blade having a diameter of 75 mm. Was added dropwise 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 through a 200-mesh wire mesh to obtain colored paint particles (I-12). The colored paint particles (I-12) had a solid content of 20%, and the ratio of the colored paint particles having a size of 250 μm or more and less than 2000 μm was 80%.
Production Example 30
In the above Production Example 29, colored paint particles (I-13) are obtained in the same manner as in Production Example 29 except that the aqueous paint composition (A-9) is used instead of the aqueous paint composition (A-3). It was. The colored paint particles (I-13) had a solid content of 16.5%, and the ratio of the colored paint particles having a size of 250 μm or more and less than 2000 μm was 80%.

Production of water-based colorful pattern paint Examples 1 to 16 and Comparative Examples 1 to 4
The components shown in Table 3 below were charged into a 500 ml sterence container while sequentially stirring, and then stirred until uniform, thereby obtaining multicolored paints (P1) to (P20). Table 3 shows the properties of the paints obtained, and Table 4 shows the results of coating performance tests.

(Note 15) “Baihijoule 3100”: trade name, manufactured by Bayer, water-dispersible polyisocyanate curing agent.
(Note 16) “HDK-H20”: trade name, manufactured by Asahi Wacker, silica fine particles, specific surface area 170 m ² / g, carbon content 1.1 mass%, average particle diameter 1.0 μm
(Note 17) 2% hydroxyethyl cellulose aqueous solution: manufactured by Wako Pure Chemical Industries, Ltd. An aqueous solution prepared by dissolving hydroxyethyl cellulose in deionized water to a concentration of 2% (Note 18) “Primal ASE-60”: trade name, Rohm and Haas, polyacrylic acid viscosity modifier, acid value 270 mgKOH / g, active ingredient 28%
(Note 19) “Primal TT-615”: trade name, manufactured by Rohm and Haas, long chain alkyl group-containing polyacrylic acid viscosity modifier, active ingredient 30%
(Note 20) 3% Laponite RD aqueous solution: “Laponite RD” (trade name, manufactured by ROCKWOOD, synthetic sodium magnesium silicate lithium) dissolved in deionized water to a concentration of 3% (Note 21) ) “Adecanol UH530”: trade name, manufactured by Adeka, modified polyether urethane, 30% active ingredient, viscosity modifier.
(Note 22) “ADEKA NOL UH752”: trade name, manufactured by ADEKA, modified polyether urethane, active ingredient 28%, viscosity modifier.

Evaluation test Each water-based multicolor pattern paint obtained above was subjected to the following test.

Preparation of test coated plate On a slate plate (150 × 70 × 3 mm), “EP sealer transparent” (manufactured by Kansai Paint Co., Ltd., water-based acrylic emulsion sealer) is roller-coated to a coating amount of 100 g / m ² and dried. After that, “Vini Deluxe 300” (manufactured by Kansai Paint Co., Ltd., JIS K 5663 1 type compliant acrylic emulsion paint) was applied with a roller so that the coating amount was 100 g / m ² , and the temperature was 20 ° C. and the relative humidity was 60%. After drying for 1 day under the conditions, the coated plate is coated with various fine-colored paints on the surface with sand aggregate regular roller fines (size 7 inch, manufactured by Otsuka Brush Co., Ltd.) so that the coating amount is 350 g / m ^2. did. Thereafter, the normally dry coated plates other than Examples 6, 9 and 14 were dried for 7 days under conditions of an air temperature of 23 ° C. and a relative humidity of 60% to obtain each test coated plate. The baking-type test coated plates obtained in Examples 6, 9 and 14 were dried at 80 ° C. for 10 minutes with an electric dryer and then baked at 140 ° C. for 30 minutes to obtain each test coated plate. Subsequently, each obtained test coating board was used for the following performance test.

(* 1) Sagging characteristics Sagging characteristics when a water-based colorful pattern paint was applied by a roller were evaluated according to the following criteria.
○: There is no sauce and the finish is good.
Δ: Sagging is seen in part and the finish is inferior,
X: Sagging is observed and the finish is remarkably inferior.
(* 2) Roller dispensability One-time application area when a water-based colorful pattern paint was applied with a roller was evaluated in three stages based on the following criteria.
○: Application area of one time is 0.4 m ² or more,
△: and 0.4m below ² in one application area of 0.05 m ² or more,
X: The application area of one time is less than 0.05 m ² .
(* 3) Appearance of coating film The coating film on each test coating plate was visually observed and evaluated according to the following criteria.
A: Variety of design feelings and textures are sufficient, very good.
◯: Various design feeling, texture, good
△: Pattern unevenness is recognized and is somewhat poor,
X: There are coating film defects such as cracks and chijimi.
(* 4) Coating surface smoothness test The coating surface was observed from a distance of 1 meter from the coated plate and evaluated according to the following criteria.
○: flat and smooth,
Δ: Roller marks are conspicuous
X: The roller marks are noticeable.
(* 5) Water resistance Each test coated plate was immersed in clean water at 23 ° C. for 7 days, pulled up, visually observed, and evaluated according to the following criteria.
A: Good,
○: Slight luster is recognized, but practical level,
Δ: Glossiness, whitening, blistering is observed,
X: Remarkably blistering is observed, or the coating film is softened.
(* 6) Accelerated weather resistance For accelerated weather resistance test of 7-7 of JIS K 5600 (General paint test method-Part 7: Long-term durability of paint film-Section 7: Accelerated weather resistance (xenon lamp method)) Similarly, after irradiating the test coating plate for 1000 hours, it was visually observed and evaluated according to the following criteria.
A: Good,
○: Slight luster is recognized, but practical level,
Δ: Glossy, cracking, blistering, peeling is recognized,
X: Remarkable glossiness, cracking, blistering, and peeling are observed.
(* 7) Storage stability 1 kg of each colorful pattern paint was put into an inner-coated can with a capacity of 1 liter and stored in a constant temperature room at 40 ° C. for 60 days. Then, it returned to room temperature, the state of the coating material in a container was observed visually, and the following reference | standard evaluated.
○: Separation is not observed, and coalescence and destruction of colored paint particles are not observed
Δ: Soft caking and separation are observed, but uniform by stirring.
X: Hard caking and separation are recognized and do not return.

Claims (11)

An aqueous multicolor pattern paint in which at least two colored paint particles (I) are dispersed in a dispersion medium, wherein the colored paint particles (I) comprise an aqueous resin (a) and a colorant (b). The composition is encapsulated in a polysaccharide metal salt gel (c), and is at least 2 selected from the group consisting of inorganic compounds, fiber derivative compounds, polyether compounds and polyacrylic compounds. A water-based multicolor pattern coating composition characterized by containing a seed viscosity modifier. The combination of viscosity modifiers consists of a combination of a fiber derivative compound and a polyether compound, a combination of a polyacrylic acid compound and a polyether compound, and a combination of an inorganic compound and a polyether compound. The water-based multicolored pattern paint composition according to claim 1, which is selected from: The colored paint particles (I) are obtained by bringing an aqueous paint composition containing an aqueous resin (a), a colorant (b) and a water-soluble polysaccharide into contact with an aqueous medium containing metal ions. Item 3. The water-based multicolor pattern coating composition according to Item 1 or 2. The aqueous multicolored paint composition according to any one of claims 1 to 3, further comprising a coating film forming component (II). It reacts with the colored paint particles (I) containing the aqueous coating composition having the reactive functional group (x) comprising the aqueous resin (a) and the colorant (b), and the reactive functional group (x). The aqueous multicolor pattern coating composition according to claim 4, comprising a coating film forming component (II) having a reactive functional group (y) to be obtained. The aqueous resin (a) contained in the colored paint particles (I) has a reactive functional group (x) that reacts with the reactive functional group (y) contained in the coating film forming component (II). 5. A water-based colorful pattern paint composition according to 5 . The aqueous multicolored paint composition according to claim 6, wherein the aqueous paint composition contained in the colored paint particles (I) contains a crosslinking agent (e). The water-based multicolored paint composition according to any one of claims 4 to 7, wherein the coating film-forming component (II) further contains a crosslinking agent (f). Both the aqueous resin (a) contained in the colored paint particles (I) and the aqueous resin (d) contained in the coating film forming component (II) have a reactive functional group (x), and the coating film forming component (II) The aqueous multicolored paint composition according to claim 8, further comprising a crosslinking agent (f) having a reactive functional group (y) capable of reacting with the reactive functional group (x). The viscosity measured using a B-type viscometer is in the range of 2500 to 15000 mPa · sec when the rotational speed is 6 revolutions / minute, and within the range of 1000 to 50000 mPa · sec when the rotational speed is 60 revolutions / minute. The water-based multicolored paint composition according to any one of claims 1 to 9, wherein the water-based multicolor pattern coating composition has a thixotropic index within a range of 2.0 to 5.0. A coating method comprising applying the water-based multicolor pattern coating composition according to any one of claims 1 to 10 on the surface of a substrate with or without an undercoat coating film.