JP5016873B2 - Water-based paint composition - Google Patents

Description

  The present invention relates to an aqueous coating composition comprising a granular gel, which is excellent in storage stability and can form a coating film excellent in water resistance, coating film appearance, and the like.

  For example, a multicolor paint is known as a paint in which a granular gel is stably dispersed in a dispersion medium. The multicolored paint is a paint that can form a paint film having various patterns of two or more colors by 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-color paint composition containing at least one kind of enamel-dispersed particles obtained by mixing and dispersing a composition mainly composed of a colorant and an organic solvent into an enamel and dispersing the enamel 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 having excellent smoothness, but the multicolored pattern coating film has a problem that the water resistance is insufficient.
Japanese Patent Application Laid-Open No. 09-1000042 JP 2005-15645 A

  An object of the present invention is to provide an aqueous coating composition comprising a granular gel, which can form a protective coating film having a low content of organic solvent and excellent performance such as water resistance and coating film appearance. That is.

  As a result of intensive studies to achieve the above object, the present inventors have now obtained a granular gel comprising an aqueous liquid composition having a reactive functional group containing an aqueous resin in a polysaccharide metal salt gel. By dispersing it in a film-forming component having a reactive functional group that reacts with the reactive functional group, the aqueous liquid composition is stably maintained during storage of the paint, and a granular gel is formed in the film-forming stage. It was found that an aqueous coating composition capable of forming a coating film excellent in water resistance can be obtained by cross-linking reaction between the coating film forming component and the coating film forming component, thereby completing the present invention.

  Thus, the present invention provides a granular gel (I) formed by encapsulating an aqueous liquid composition containing a reactive functional group (x) comprising an aqueous resin (a) in a polysaccharide metal salt gel (b). An aqueous coating composition comprising a coating film forming component (II) containing a reactive functional group (y) capable of reacting with the reactive functional group (x) is provided.

  In the aqueous coating composition of the present invention, the reactive functional group (x) in the aqueous liquid composition included in the granular gel (I) and the reactive functional group (y) in the coating film forming component (II) are included. The granular gel (I) and the coating film-forming component (II) are firmly bonded to each other through a gel film in the film formation stage, thereby forming a coating film having excellent water resistance. Moreover, since the aqueous liquid composition containing the reactive functional group (x) is included in the granular gel (I), the aqueous coating composition of the present invention is maintained in a stable state at the storage stage.

  Hereinafter, the aqueous coating composition of the present invention will be described in more detail.

  The aqueous coating composition of the present invention comprises a granular gel (I) and a coating film forming component (II), and the aqueous liquid composition and the coating film forming component (II) contained in the granular gel (I) are: Each of them contains functional groups (x) and (y) that can react with each other.

  As a combination of the reactive functional group (x) contained in the aqueous liquid composition included in the granular gel (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 membrane. Specifically, for example, a carbonyl group and a hydrazine residue, a hydroxyl group and an isocyanate group, a hydroxyl group and an alkyl ether group, and a hydroxyl group Examples include combinations of imino groups, carboxyl groups and epoxy groups, amino groups and epoxy groups, amide groups and epoxy groups, and in particular, carbonyl groups and hydrazine residues, hydroxyl groups and isocyanate groups, hydroxyl groups and alkyl ether groups, and hydroxyl groups and imino groups. A combination of groups is preferred.

  Examples of the hydrazine residue include hydrazine group, hydrazide group, semicarbazide group, bisacetyldihydrazone group and the like.

Granular gel (I) :
In the present invention, the granular gel (I) is obtained by encapsulating an aqueous liquid composition containing a reactive functional group (x) comprising an aqueous resin (a) in a polysaccharide metal salt gel (b). It is.

Aqueous resin (a ):
The aqueous resin (a) contributes to the durability of the granular gel (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. In addition, the aqueous resin (a) can be a resin having an anionic group as a hydrophilic group, particularly a carboxyl group that also serves as a reactive functional group (x), from the viewpoint of production stability of the granular gel, In this case, the resin may be neutralized. Examples of the neutralizing agent that can be used in this case include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, dimethylaminoethanol, 2-methyl- Illustrative examples include amines such as 2-amino-1-propanol and ammonia, and these can be used alone or in combination of two or more.

The aqueous resin (a) can contain a reactive functional group (x) that reacts with the reactive functional group (y) contained in the coating film forming component (II). 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,
An amino group etc. can be mentioned, A carbonyl group and a hydroxyl group are especially suitable. 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 resin (a) is preferably an acrylic resin from the viewpoints of durability and weather resistance of the granular gel (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; cycloalkyl (meth) such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate A 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 monomer; Isocyanate group-containing polymerizable unsaturated monomer such as isocyanate ethyl (meth) acrylate, 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 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%.

Polysaccharide metal salt gel (b) :
The polysaccharide metal salt gel (b) in the present invention constitutes a gelled film for enclosing the aqueous liquid composition containing the aqueous resin (a), and can be a shell wall of the granular gel (I). It is an ingredient.

  The granular gel (I) forms, for example, an aqueous liquid composition (c) containing an aqueous resin (a) and a water-soluble polysaccharide (b1), and forms a water-insoluble or hardly soluble salt with the water-soluble polysaccharide (b1). Can be obtained by contacting with an aqueous medium containing monovalent or polyvalent metal ions, whereby an aqueous liquid composition (c) comprising an aqueous resin (a) can be converted to a polysaccharide metal salt gel The granular gel (I) encapsulated in (b) can be formed.

  The water-soluble polysaccharide (b1) 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. Preferred are those having a number average molecular weight in the range of 000 to about 2,000,000, particularly about 5,000 to about 1,000,000 and exhibiting a solubility of about 10 G / L (25 ° C.) or higher. Specific examples include alginic acid or an alkali metal salt thereof, gellan gum, carrageenan and the like, and these can be used alone or in combination of two or more.

  The water-soluble polysaccharide (b1) is the stability of the granular gel (I) in water, the handleability when producing the granular gel (I), and the water resistance of the coating film formed from the coating material containing the granular gel (I). From the viewpoint of properties, etc., it is usually 0.1 to 10% by mass, preferably 0.1 to 7% by mass, more preferably 0.1% by mass, based on the total mass of the aqueous resin (a) and the water-soluble polysaccharide (b1). It is preferable to use within the range of 1-5 mass%.

  The aqueous liquid composition (c) also reacts with the coating film forming component (II), and the granular gel (I) and the coating film forming component (II) are bonded via an interface to form a crosslinked coating film. The crosslinking agent (d) having the reactive functional group (x) can be contained so that the aqueous liquid (a) does not contain the reactive functional group (x). The composition (c) desirably contains a crosslinking agent (d) having a reactive functional group (x).

  As the crosslinking agent (d) that can be contained in the aqueous liquid composition (c), the storage stability of the granular gel (I) is good, and the coating film is formed when the coating film is formed from the aqueous coating composition of the present invention. From the standpoint that the reaction with the component (II) proceeds smoothly and that the aqueous coating composition can be made into one liquid, a hydrazine derivative, a melamine resin, and the like are preferable.

Examples of the hydrazine derivatives include hydrazine; hydrazine hydrate; oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, and the like. 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; nitrilotrido 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 hydrate), 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 crosslinking agent (d), if necessary, as a catalyst, sulfonic acids such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, and the like Salts and the like can be used.

  When the aqueous liquid composition (c) contains the cross-linking agent (d), the amount used thereof is the cross-linking agent (1) with respect to 1 mol of the reactive functional group (y) in the coating partner (II) of the reaction partner. The amount of the reactive functional group (x) in d) is usually adjusted to 0.05 to 2 mol, preferably 0.07 to 1.5 mol, more preferably 0.1 to 1 mol. It is desirable that

  The aqueous liquid composition (c) also contains a colorant and / or extender pigment in order to impart designability, concealment properties, etc. to the coating film formed using the aqueous coating composition of the present invention. Can do.

As the colorant, pigments and dyes can be used, and pigments are particularly preferable. Examples of the pigment 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 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, etc .; cobalt purple, quinacridone violet, dioxazine Purple pigments such as iolet; Blue pigments such as cobalt blue, phthalocyanine blue and selenium blue; Green pigments such as phthalocyanine green; Metallic pigments such as aluminum powder, bronze powder, copper powder, tin powder, iron phosphide and zinc powder; Metal Examples thereof include pearlescent pigments such as oxide-coated mica powder and mica-like iron oxide, and these can be used alone or in combination of two or more. 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, azomethine dyes, etc. Quinoline dyes; nitro dyes; nitrone dyes; benzoquinone and naphthoquinone dyes; naphthalimide dyes; perinone dyes, and the like. Not to be able to use.

  Examples of extender pigments include barita powder, precipitated barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, silica, white carbon, diatomaceous earth, talc, magnesium carbonate, alumina white, and gloss white.

  The blending amount of the colorant and / or extender pigment is usually 0.01 based on the mass of the aqueous resin (a) from the viewpoint of colorability by the granular gel (I), specific gravity, durability, water resistance and the like. It is suitable to be in the range of ˜500 mass%, preferably 0.05 to 400 mass%, more preferably 0.1 to 300 mass%.

  In the water-based paint composition of the present invention, by including a plurality of granular gels (I) containing colorants having different colors, the design of the formed coating film can be improved, and so-called multicolored paint is prepared. can do. In this case, the use of a metallic pigment and / or a pearly luster pigment as the colorant is preferable because it can impart a high-grade feeling to the multicolored coating film.

  In the production of the granular gel (I), a thickener can be further added to the aqueous liquid composition (c) in order to facilitate uniform distribution of the colorant in the granular gel.

As the thickener, those known per se can be used without limitation, and specific examples thereof include, for example, inorganic compounds such as water-soluble alkali silicate, montmorillonite, colloidal alumina; methyl cellulose, hydroxyethyl cellulose Fibrin derivative compounds such as carboxymethylcellulose; polyether compounds such as pluronic polyether, polyether dialkyl ester, polyether dialkyl ether, polyether urethane modified product, polyether epoxy modified product; polyacrylic acid soda, polyacrylic Polyacrylic acid compounds such as acid (meth) acrylic acid ester copolymers; polyvinyl compounds such as polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl alcohol, polyvinylbenzyl alcohol copolymers; Protein derivatives such as sodium acid soda and ammonium caseinate; maleic anhydride copolymers such as partial esters of vinyl methyl ether-maleic anhydride copolymer, half esters of reaction products of drying oil fatty acid allyl alcohol ester-maleic anhydride These can be used, and these can be used alone or in combination of two or more. The amount of the thickener used is usually 0.01 to, based on the mass of the aqueous resin (a).
It can be in the range of 20% by weight, preferably 0.02 to 10% by weight, more preferably 0.05 to 5% by weight.

  The aqueous liquid composition (c) may further comprise, if necessary, a specific gravity adjusting material such as a balloon, an antifoaming agent, a curing catalyst, a pigment dispersant, a fragrance, 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, fragrances, surface conditioners and the like can be contained.

  The aqueous liquid composition (c) is, for example, an emulsion of the aqueous resin (a) and an aqueous solution of the water-soluble polysaccharide (b1), a paste of a crosslinking agent (d), a colorant and / or an extender, as described above. It can be prepared by mixing with other components.

  Examples of the metal compound (e) that is a source of metal ions used when the aqueous liquid composition (c) is made into a granular gel include monovalent metals such as potassium and sodium, magnesium, calcium, strontium, and barium. , Chromium, molybdenum, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, copper, zinc, cadmium, aluminum, cerium and other polyhydric metal hydroxides, oxides, carbonates, chlorides, sulfides, etc. Can be mentioned.

  The metal in the metal compound (e) is preferably a polyvalent metal, particularly a divalent metal, from the viewpoint of the strength of the formed granular gel (I). Examples of the divalent metal include magnesium, calcium, Periodic table group 2 elements such as strontium and barium; 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 9 such as cobalt and rhodium Group element; periodic table group 10 element such as nickel and palladium; periodic table group 11 element such as copper; periodic table group 12 element such as zinc and cadmium; Is preferred.

  The metal compound (e) is desirably dissolved in 0.005 mg or more, particularly 0.01 m 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 (e).

  An aqueous medium containing a monovalent or polyvalent metal ion can be prepared by dissolving at least a part of the metal compound (e) in the aqueous medium. At that time, the metal compound (e) does not need to be completely dissolved in the aqueous medium, and may be partially dissolved. Further, the aqueous medium (B) has a pH of 7.0 to 14.0, particularly 8.5 to 13.5, and is formed from the production stability of the granular gel and the coating material containing the granular gel. It is suitable because it can suppress the feeling of roughness on the surface of the coated film, and the type and content of the metal compound (d) can be adjusted so that the pH is within the above range. The content of the metal compound (e) in the aqueous medium containing the metal compound (e) is usually 0.05 to 15% by mass, preferably 0.07 to 12.5% by mass, more preferably 0.1 to 10%. It is desirable to be within the range of mass%.

Preparation of granular gel (I) :
The granular gel (I) can be formed by bringing the aqueous liquid composition (c) described above into contact with an aqueous medium containing metal ions derived from the metal compound (e). This contact may be performed, for example, by dropping the aqueous liquid composition (c) into the aqueous medium from the tip of a syringe; or by dropping the aqueous liquid composition (c) into the aqueous medium using centrifugal force. A method in which the aqueous liquid composition (c) is atomized from the tip of the spray nozzle and dropped into the aqueous medium; a method in which the aqueous liquid composition (c) is added into the aqueous medium and stirred and mixed by a disperser; Can be performed.

By the above method, an aqueous liquid composition (c) containing a reactive functional group (x) comprising an aqueous resin (a) and optionally a crosslinking agent (d) and other additive components is converted into a polysaccharide metal salt gel. The granular gel (I) encapsulated in (b) can be obtained.

  The size (major axis) of the granular gel (I) formed as described above is not particularly limited and can be appropriately changed depending on the use of the aqueous coating composition of the present invention. It can be adjusted by the composition of the aqueous liquid composition (c), the concentration of metal ions in the aqueous medium, the manner in which the aqueous liquid composition (c) is dropped onto the aqueous medium, and the like. In the present invention, the size of the granular gel (I) can be generally in the range of 10 to 15,000 μm, preferably 50 to 5,000 μm, and the particle size distribution is 75 μm or more. In addition, it is preferable that the particle group of less than 2,000 μm is 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 granular gel (I) is the minimum nominal size of the sieve that can pass through when the granular gel (I) is passed through (the pore size; the length of one side of the mesh) ). 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 granular gel (I) that cannot pass through a sieve having a nominal size (pore size) of 2,000 μm is determined by a line segment that passes through the center of 10 randomly selected granular gels (I). The average value of the maximum dimensions when measured. The particle size distribution is determined by classifying all the granular gel groups using the above six types of sieves, sufficiently drying the particle groups remaining on each sieve, measuring the mass of the granular gel groups on each sieve, and drying. It can obtain | require by calculating the fraction with respect to the mass of the obtained whole granular gel group.

  The shape of the granular gel (I) is not particularly limited, but in general, it is preferably spherical. Here, the term “spherical” is not limited to a true spherical shape that is well-balanced in the vertical and horizontal directions, but is used to include shapes such as a flat spherical shape, a distorted spherical shape, and a teardrop shape.

  The obtained granular gel (I) can be separated from an aqueous medium containing metal ions by using, for example, a wire mesh having an appropriately sized mesh.

Coating film forming component (II) :
The aqueous coating composition of the present invention contains a functional group (y) capable of reacting with the reactive functional group (x) contained in the granular gel (I) in combination with the granular gel (I) described above. Coating film forming component (II) to be included.

  The coating film forming component (II) can comprise an aqueous resin (f) and, if necessary, a crosslinking agent (g). The aqueous resin (f) is generally used as a resin binder in the field of aqueous paint. What can be used similarly can be mentioned, for example, what was mentioned above about aqueous resin (a) is mentioned.

  As the aqueous resin (f), for example, an aqueous resin containing a reactive functional group (y) can be used.

  The aqueous resin (f) containing the reactive functional group (y) generally has a reactive functional group (y) of 0.05 to 0.5 mmol / g resin, preferably 0.1 to 0.4 mmol / It can be contained within the range of g resin. Examples of the reactive functional group (y) in the aqueous resin (f) 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 (f), for example, the reactive functional group (x) -containing aqueous resin (a) in the granular gel (I) is appropriately selected from those described above. be able to.

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

  The crosslinking agent (g) is a compound having a functional group (y) capable of reacting with the reactive functional group (x) contained in the granular gel (I), specifically, for example, a hydrazine derivative, A melamine resin, a polyisocyanate crosslinking agent, etc. can be mentioned.

  The hydrazine derivative and melamine resin that can be used as the crosslinking agent (g) can be appropriately selected from those described above for the crosslinking agent (d) in the granular gel (I).

  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 (g) in the coating film forming component (II) is such that the reaction in the crosslinking agent (g) is 1 mol of the reactive functional group (x) in the granular gel (I) as the reaction partner. It is desirable to adjust the amount of the functional functional group (y) so that it is usually in the range of 0.05 to 2 mol, preferably 0.1 to 1 mol.

In addition, the coating film-forming component (II) can optionally contain a balloon, and can improve the texture and feel of the coating film formed thereby. The balloon is a hollow particle having a cavity in a thin shell, and includes a resin balloon and an inorganic balloon. A gas (typically air) is normally enclosed in the cavity of the balloon, but may be reduced in pressure or vacuum in some cases.

  The shell of the resin balloon can be made of various resins, and examples of the constituent monomer unit of the resin include acrylonitrile, acrylamide, acrylic acid, acrylic ester, methacrylonitrile, methacrylamide, methacrylic acid, methacrylic ester. , Vinyl chloride, vinylidene chloride and the like, and these may 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 inorganic balloons include glass balloons, shirasu balloons, alumina balloons, zirconia balloons, aluminosilicate balloons and the like, and these can be used alone or in combination of two or more. Further, the resin-based balloon and the inorganic balloon may be used in appropriate combination.

  The blending amount of the balloon is usually 0.5 to 15% by mass, preferably 0, based on the total solid content of the aqueous resin (f) and the crosslinking agent (g) contained in the coating film forming component (II). It is desirable that the content be in the range of 7 to 15% by mass, more preferably 1 to 10% by mass.

  The coating film forming component (II) may form a colored coating film or may form a clear coating film. When forming a colored coating film, a colorant may be added as necessary. 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 that can be contained in the granular gel (I). When the aqueous coating composition of the present invention is used as a multicolored paint, the above-mentioned extender pigment is blended with the aqueous paint composition from the viewpoint of improving the drying property of the multicolored paint film, improving the appropriate gloss, and improving the touch. It is desirable. When a colorant and / or an extender pigment is blended in the coating film forming component (II), the total blending amount of the aqueous resin (f) and the crosslinking agent (g) contained in the coating film forming component (II). It can be in the range of usually 5 to 200% by mass, preferably 10 to 150% by mass, and more preferably 15 to 120% by mass with respect to the total solid content.

Water-based paint composition :
The coating composition of the present invention is prepared by mixing the above-described granular gel (I) and coating film-forming component (II) together with a coating additive as required, by a method known per se, and appropriately adding an aqueous medium. It can prepare by adding and adjusting a viscosity and / or pH. 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 use of a coating composition.

  Examples of the paint additive include a neutralizing agent, a thickener, a surfactant, an aqueous water repellent, a dispersant, an antifoaming agent, an antiseptic, an antifungal agent as described above for the granular gel (I). Anti-freezing agent, UV absorber, light stabilizer, film-forming aid, zinc whisker, curing accelerator, formaldehyde adsorbent, wax, alkyl silicate condensate or alkyl silicate condensate modified with polyalkylene glycol etc. And anti-fouling agents such as modified alkyl silicates, flame retardants such as antimony trioxide, antimony pentoxide, and aluminum hydroxide, fragrances, antibacterial agents, and surface conditioners.

The blending ratio of the granular gel (I) and the coating film forming component (II) in the coating composition of the present invention can be changed depending on the use of the coating composition, etc., but the granular gel (I) / coating film forming component The solid content mass ratio of (II) can be generally within the range of 1/99 to 80/20, preferably 20/80 to 75/25, and more preferably 25/75 to 45/55.

  The coating composition of the present invention generally has a viscosity in the range of 200 to 10,000 mPa · s, preferably 1,000 to 4,000 mPa · s, and 6.0 to 13.0 from the viewpoint of storage stability and the like. , Preferably having a pH in the range of 7.0 to 12.0.

  In this specification, the viscosity of the coating composition is adjusted by adjusting the temperature of the sample to 20 ° C. It is a value when measured with 4 rotors and 60 revolutions, and pH is a value when the temperature of the sample is set to 20 ° C. and measured with a pH meter “TOA HM40V”.

  The coating composition 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. For example, it can be applied to various uses such as stone-like paint, sandstone-like paint, leather-like paint, and ceramic-like paint.

Painting method :
The coating composition of the present invention can form a protective coating film excellent in performance such as water resistance and coating film appearance by coating on the substrate surface.

  Examples of the substrate surface to which the coating composition 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 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 etc. And a wallpaper surface made of materials such as polyvinyl chloride, polyolefin, paper, and cloth.

The coating amount of the aqueous coating composition of the present invention can be varied depending on the composition of the coating composition to be used and the type of the substrate to be coated, but is usually 100 to 1,000 g / m ^2, preferably 200. It can be in the range of ˜500 g / m ² .

  Application of the aqueous coating composition of the present invention can be performed using a known coating means, for example, using a coating device such as a roller, air spray, airless spray, lysine gun, universal gun, brush, or the like. it can.

  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 coating composition of the present invention can be applied, for example, to the surface of a base material in advance, and then the aqueous coating composition of the present invention can be applied to the formed undercoating surface for a protective coating, for example. .

  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 application amount of the undercoat paint can be changed according to the type of the substrate to be coated, etc., but is usually in the range of 50 to 2,000 g / m ^2, preferably 70 to 1,000 g / m ^2. Can do.

  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 aqueous coating composition of the present invention is used, a protective coating film having excellent finish, water resistance, and weather resistance can be formed. However, if necessary, the coating film of the aqueous coating composition of the present invention may be used. Further, a top coating material known per se may be further applied.

  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 into a 1 liter stainless steel container, and stirred and mixed with a stirrer for 30 minutes to obtain an aqueous clear paint (C1).

55% emulsion (a1) 750 parts Water 9 parts "TEXANOL" (Note 2) 50 parts "SN Deformer 380" (Note 3) 10 parts "Adecanol UH-438" (Note 4) 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) “SN deformer 380”: trade name, manufactured by San Nopco, defoamer.
(Note 4) “ADEKA NOL UH438”: trade name, manufactured by ADEKA, thickener.

Production Example 4
A water-based clear paint (C2) 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 (a2) 750 parts "TEXANOL" (Note 2) 61 parts "SN deformer 380" (Note 3) 10 parts "Adecanol UH-438" (Note 4) 6 parts Water 60 parts "Talc T-1" ( Note 5) 80 parts "Matsumoto Microsphere F-80E" (Note 6) 28 parts.

(Note 5) “Talc T-1”: trade name, manufactured by Fuji Talc Industrial Co., Ltd., talc.
(Note 6) “Matsumoto Microsphere F-80E”: trade name, manufactured by Matsumoto Yushi Co., Ltd., acrylonitrile resin balloon, 15% active ingredient.

Production of white pigment paste Production Example 5
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 liquid composition for granular gel Production Example 6
The following components were sequentially blended in a container and stirred and mixed so as to be uniform to obtain an aqueous liquid composition (A-1) for granular gel.

White pigment paste 154 parts 55% emulsion (a1) 250 parts "TEXANOL" (Note 2) 20 parts "SN deformer 380" (Note 3) 2 parts "Adecanol UH-438" (Note 4) 2 parts 2% sodium alginate aqueous solution 280 parts.

Production Examples 7 to 16
In the said manufacture example 6, aqueous liquid composition (A-2)-(A-11) was manufactured like the manufacture example 6 except changing a compounding composition into the compounding composition shown in following Table 1.

(Note 10) Red pigment paste: Color paste prepared by adjusting “Unirant 88 Red” (trade name, manufactured by Yokohama Kasei Co., Ltd.) so that the pigment content is about 30%.
(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: Aluminum pigment paste “M”
G-51 "(Asahi Kasei Corporation, aluminum content 66%, hydrocarbon-based and petroleum-based organic solvent 34%) 45.5 parts, ethylene glycol monobutyl ether 35 parts, and phosphate group-containing resin solution (*) 3 Then, the mixture was stirred and mixed to obtain an aluminum pigment paste.
(*) Phosphate group-containing resin solution: Put a mixed solvent of 27.5 parts of methoxypropanol and 27.5 parts of isobutanol in a reaction vessel equipped with a stirrer, temperature controller and cooler and heat to 110 ° C. 25 parts of styrene, n-butyl methacrylate 27.
5 parts, 20 parts of “isostearyl acrylate” (manufactured by Osaka Organic Chemical Co., Ltd., branched higher alkyl acrylate), 7.5 parts of hydroxybutyl acrylate, 15 parts of 50% phosphoric acid group-containing polymerizable monomer (***), 2- 121.5 parts of a mixture consisting of 12.5 parts of methacryloyloxyethyl acid phosphate, 10 parts of isobutanol and 4 parts of t-butylperoxyoctanoate is added to the above mixed solvent over 4 hours, and t-butylperoxyoctanoic acid is further added. A mixture of 0.5 part ate and 20 parts isopropanol was added dropwise over 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: Into a reaction vessel equipped with a stirrer, a temperature controller and a refrigerator, put 57.5 parts of monobutyl phosphate and 41.1 parts of isobutanol.
After 42.5 parts of glycidyl methacrylate was dropped over 2 hours under air ventilation,
The mixture was further aged and stirred for 1 hour. Thereafter, 5.9 parts of isopropanol was added to obtain a phosphoric acid 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 granular gel Production Example 17
Into a 4 liter stainless steel container, 1,300 parts of 0.15% calcium hydroxide (Note 14) aqueous solution (pH = 12.8) was charged and stirred at a rotational speed of 2,500 rpm using a stirring blade having a diameter of 75 mm. However, 650 parts of the aqueous liquid composition (A-1) obtained above was gradually dropped into the container to produce a granular gel. Next, after the liquid in the container was further stirred at the same rotational speed for 15 minutes, it was filtered using a 200-mesh wire mesh to obtain a granular gel (I-1). The obtained granular gel (I-1) had a solid content of 20%, and the proportion of the granular gel having a size of 75 μm or more and less than 500 μm was 95% in the total granular gel.

  (Note 14) Calcium hydroxide: 0.15 g dissolved in 100 g of water at 25 ° C.

Production Example 18
In a 4 liter stainless steel container, 24 parts of calcium hydroxide and 1,200 parts of deionized water are charged, and stirred at a rotational speed of 1500 rpm using a stirring blade having a diameter of 75 mm to prepare an aqueous solution having a pH of 12.8. While stirring at the same stirring speed, 600 parts of the aqueous liquid composition (A-2) was gradually dropped into the container to produce a granular gel. 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 a granular gel (I-2). The obtained granular gel (I-2) had a solid content of 20%, the proportion of the granular gel having a size of 150 μm or more and less than 2000 μm was 95% in the total granular gel.

Production Examples 19 to 27
In Production Example 17, granular gels (I-3) to (I) were produced in the same manner as in Production Example 17 except that the aqueous liquid composition shown in Table 2 below was used instead of the aqueous liquid composition (A-1). -11) was obtained.

Production Example 28
Into a 4 liter stainless steel container, 600 parts of 5% calcium chloride aqueous solution was charged, and 660 parts of the aqueous liquid 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. To form a granular gel. 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 a granular gel (I-12). The granular gel (I-12) had a solid content of 20%, and the proportion of the granular gel having a size of 250 μm or more and less than 2000 μm was 80%.

Production Example 29
In the said manufacture example 28, granular gel (I-13) was obtained like the said manufacture example 28 except using an aqueous liquid composition (A-9) instead of an aqueous liquid composition (A-3). . The granular gel (I-13) had a solid content of 16.5%, and the proportion of the granular gel having a size of 250 μm or more and less than 2000 μm was 80%.

Production of multicolored paints Examples 1-12 and Comparative Examples 1-2
The components shown in Table 3 below were charged in a 500 ml sterence container while sequentially stirring, and then further stirred to obtain multicolored paints (P1) to (P12). Table 3 also shows the properties of the obtained paint and the coating performance test results.

  (Note 15) “Baihijoule 3100”: trade name, manufactured by Bayer, water-dispersible polyisocyanate curing agent.

Coating film performance test Preparation of test coating plate “EP sealer transparent” (manufactured by Kansai Paint Co., Ltd., water-based acrylic emulsion sealer) is applied on a slate plate (150 × 70 × 3 mm) to a coating amount of 100 g / m ² . After being roller-coated and dried, “Vini Deluxe 300” (manufactured by Kansai Paint Co., Ltd., JIS K 5663 type 1 compatible acrylic emulsion paint) is roller-coated so that the coating amount is 100 g / m ^2. What was dried for 1 day under the conditions of 20 ° C. and 60% relative humidity was used as a plate to be coated, and the various pattern paints were applied thereon by spray so that the coating amount was 300 g / m ² . Thereafter, the coated plates of Examples 1 to 4, 6, 8, 10, 11 and Comparative Examples 1 to 2 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 test coated plates obtained in Examples 5, 7, 9 and 12 were dried at 80 ° C. for 10 minutes with an electric dryer and then baked at 140 ° C. for 30 minutes.

  The test coated plate obtained as described above was subjected to the following performance test.

(* 1) Appearance of coating film The coating film of each test coating plate was visually observed and evaluated according to the following criteria.
A: Very good,
○: Good,
Δ: Somewhat bad,
X: There are coating film defects such as cracks and chijimi.

(* 2) Water resistance Each test coating plate was immersed in clean water at 23 ° C. for 4 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.

(* 3) 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.
○: No separation is observed, and no coalescence or destruction of the granular gel is observed.
Δ: Soft caking and separation are observed, but uniform by stirring.
X: Hard caking and separation are recognized and do not return.

(* 4) Low-temperature storage stability 1 kg of each colorful pattern paint is put into an inner-coated can with a capacity of 1 liter, stored at −5 ° C. for 18 hours, then stored at 20 ° C. for 6 hours as one cycle, and this was repeated three times. Then, it returned to room temperature, the state of the coating material in a container was observed visually, and the following reference | standard evaluated.
○: No problem
Δ: Soft caking is observed, but becomes uniform by stirring.
X: Hard caking and separation are recognized and do not return.

Claims (16)

A granular gel (I) comprising an aqueous liquid composition containing a reactive functional group (x) comprising an aqueous resin (a) in a polysaccharide metal salt gel (b) and a reactive functional group (x ) Ri Na comprise a coating film forming component containing a reactive functional group (y) capable of reacting (II) and the combination of the reactive functional group (x) with the reactive functional groups (y) is a carbonyl group hydrazine residue, a hydroxyl group and an isocyanate group, selected from a combination of a hydroxyl group and an alkyl ether group and a hydroxyl group and an imino group aqueous coating composition characterized Rukoto. The aqueous coating composition according to claim 1, wherein the aqueous resin (a) is an aqueous resin containing a reactive functional group (x). The aqueous coating composition according to claim 2 , wherein the reactive functional group (x) is a carbonyl group or a hydroxyl group. The aqueous coating composition according to any one of claims 1 to 3 , wherein the aqueous liquid composition contains a crosslinking agent. The aqueous coating composition according to claim 4 , wherein the crosslinking agent is a hydrazine derivative or a melamine resin. The aqueous coating composition according to any one of claims 1 to 5 , wherein the aqueous liquid composition contains a metallic pigment and / or a pearlescent pigment. The aqueous coating composition according to any one of claims 1 to 6 , wherein the coating film-forming component (II) comprises an aqueous resin containing a reactive functional group (y). The aqueous coating composition according to claim 7 , wherein the reactive functional group (y) is a carbonyl group or a hydroxyl group. The aqueous coating composition according to any one of claims 1 to 8 , wherein the coating film-forming component (II) further comprises a crosslinking agent. The aqueous coating composition according to claim 9 , wherein the crosslinking agent is selected from a hydrazine derivative, a melamine resin, and a polyisocyanate compound. The aqueous coating composition according to any one of claims 1 to 10 , wherein the coating film-forming component (II) further contains an extender pigment. Particulate gel (I) is an aqueous resin (a) and claims 1-11 water-soluble polysaccharide aqueous liquid composition comprising (b1), it is obtained by contacting an aqueous medium containing metal ions The water-based coating composition according to any one of the above. The aqueous coating composition according to any one of claims 1 to 12 , wherein the coating film-forming component (II) further contains a balloon. The blending ratio of the granular gel (I) and the coating film forming component (II) is in the range of 1/99 to 80/20 in terms of the solid mass ratio of the granular gel (I) / the coating film forming component (II). Item 14. The aqueous coating composition according to any one of Items 1 to 13 . A coating method comprising coating the aqueous coating composition according to any one of claims 1 to 14 on a surface of a substrate. 15. A coating method comprising: coating a base coating surface with a base coating, and then coating the water-based coating composition according to any one of claims 1 to 14 on a base coating to be formed.