JP5162115B2 - Method for producing granular gel and coating composition containing the granular gel - Google Patents

Description

  The present invention relates to a method for producing a granular gel and a coating composition containing the granular gel.

  A method for encapsulating liquid particles with a gelled membrane by bringing a water-soluble polymer polysaccharide such as sodium alginate into contact with a metal ion-containing aqueous solution such as an aqueous calcium chloride solution is known, and is in the fields of food, chemistry, biotechnology, etc. Widely used in

  As such an encapsulation method, for example, Patent Document 1 discloses an aqueous liquid composition comprising a hydrophilic photocurable resin, a photopolymerization initiator, a water-soluble polymer polysaccharide, and an inorganic powder, The composition is dropped into an aqueous medium containing metal ions or polyvalent metal ions to form a granular gel, and then the resulting granular gel is irradiated with actinic rays to cure the photocurable resin in the granular gel. There is disclosed a method for producing a granular molded product for immobilizing an enzyme or microbial cells.

  In addition, as an application example of gelation of water-soluble polymeric polysaccharides with metal ions, there is, for example, a multicolored paint.

  A multicolor pattern is a paint that can form a coating film having two or more colors in a single coating. For example, a multicolor pattern is a paint in which a plurality of colored granular gels are stably dispersed in a dispersion medium. It is mainly used for painting buildings.

  As a multicolored paint, for example, Patent Document 2 discloses a colored paint composition containing liquid colored particles in which a film-forming component such as an emulsion resin is encapsulated with a gelled film of a water-soluble polymer compound. According to the composition, it is possible to form a coating film having a varied appearance and excellent appearance, but there are difficulties in coating film properties such as water resistance of the coating film.

  Furthermore, Patent Document 3 discloses an aqueous multicolor coating composition that uses a combination of scaly gel colored particles and colored or colored spherical fine particles as colored aggregates dispersed in an aqueous medium. According to the composition, a multicolored pattern can be easily visually recognized, and a smooth and smooth coating film can be formed. However, the water resistance of the coating film is not sufficient, and for producing scaly gel colored particles. In addition, since a compound such as calcium chloride and aluminum sulfate is used in the production of gel colored particles, the metal part of the production apparatus may corrode and the use of the coating composition However, there is a problem that it is limited to applications that do not touch the metal part.

On the other hand, as a multicolored paint, Patent Document 4 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. Disclosed is a multicolor pattern coating composition containing at least one type of enamel-dispersed particles obtained by mixing and dispersing a composition mainly composed of a polymer, a colorant, and an organic solvent into an enamel and dispersing the enamel in an aqueous dispersion medium. ing. 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.
Japanese Patent Laid-Open No. 10-152511 JP-A-1-16879 JP 07-247450 A Japanese Patent Application Laid-Open No. 09-1000042

  An object of the present invention is to provide a method capable of stably producing a granular gel by a simple method without using a large amount of an organic solvent, and a coating composition containing the granular gel.

  As a result of intensive studies to achieve the above object, the present inventors have brought an aqueous liquid composition containing an aqueous resin, a colorant and a water-soluble polysaccharide into contact with an aqueous medium containing a specific metal compound. Thus, the inventors have found that a granular gel can be easily produced, and that the granular gel can be advantageously used in a coating composition such as a multicolor paint, and the present invention has been completed.

  Thus, in the present invention, the aqueous liquid composition (A) containing the aqueous resin (a), the colorant (b) and the water-soluble polysaccharide (c) is selected from metal hydroxides, metal oxides and metal carbonates. It is intended to provide a method for producing a granular gel, which comprises contacting with an aqueous medium (B) containing a metal compound (d) capable of dissolving at least 0.005 mg in 100 g of 25 ° C. water.

  This invention also provides the coating composition containing the granular gel manufactured by the said method.

  According to the method of the present invention, by using a water-soluble polysaccharide and a specific metal compound whose solubility in water is a specific value or more as a gelling agent, storage stability is good without using a large amount of an organic solvent. Simple granular gel can be produced easily. The granular gel can be widely used in various fields such as chemical products, foods, and biotechnology. For example, a coating composition containing the granular gel has little odor during coating, water resistance, and weather resistance. A coating film excellent in physical properties of the coating film is formed.

  Hereinafter, the manufacturing method of the granular gel of this invention and the coating composition containing this granular gel are demonstrated in detail.

Aqueous liquid composition (A) :
The aqueous liquid composition (A) used in the method of the present invention comprises an aqueous resin (a), a colorant (b) and a water-soluble polysaccharide (c).

Aqueous resin (a ):
The aqueous resin (a) contributes to the durability of the granular gel (C) to be formed, 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, particularly a carboxyl group as a hydrophilic group from the viewpoint of production stability of the granular gel, 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, ammonia and the like. These amines can be exemplified, 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 and weather resistance of the granular gel (C).

  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 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 acrylic resin as the aqueous resin (a) is preferably a carboxyl group-containing acrylic resin from the viewpoint of the production stability of the granular gel, and such carboxyl group-containing resin is, for example, at least a monomer component. It can manufacture by using a carboxyl group-containing polymerizable unsaturated monomer as a part. The amount of the carboxyl group-containing polymerizable unsaturated monomer used is usually based on the mass of the total polymerizable unsaturated monomer subjected to (co) polymerization from the viewpoint of the production stability and storage stability of the granular gel. It can be in the range of 0.05 to 30% by mass, preferably 0.07 to 15% by mass, and more preferably 0.1 to 3% by mass.

  The aqueous resin (a) may be a carbonyl group-containing acrylic resin from the viewpoint of affinity with the pigment in the granular gel, and the carbonyl group-containing acrylic resin further contains a carboxyl group. It is desirable. Such a carbonyl group-containing acrylic resin is produced, for example, by using a carbonyl group-containing polymerizable unsaturated monomer as at least a part of the monomer component and (co) polymerizing with the other polymerizable unsaturated monomer. Can do. The amount of the carbonyl group-containing polymerizable unsaturated monomer used is usually 1 to 30% by mass, preferably 1.5 to 25% by mass, based on the mass of the total polymerizable unsaturated monomer to be subjected to (co) polymerization. %, More preferably in the range of 2-20% by weight.

  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 dimethylalkylbedines, dimethylalkyllaurylbedines, and alkylglycines.

  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 weight of a polymerizable unsaturated monomer, Preferably it can exist in the range of 1-4 mass%.

Colorant (b) :
The colorant (b) used in the method of the present invention is useful for adjusting the specific gravity of the granular gel (C), and is designed and concealed in the coating film formed using the coating composition of the present invention. It is used for imparting sex and the like, and those known per se can be used without limitation.

  As the colorant (b), pigments and dyes can be used, and pigments are particularly preferable. Specific examples of pigments include, for example, 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, and monoazo yellow. , Condensed azo yellow, azomethine yellow, bismuth vanadate, benzimidazolone, isoindolinone, isoindoline, quinophthalone, benzidine yellow, permanent yellow and other yellow pigments; permanent orange and other orange pigments; red iron oxide, naphthol AS azo red , Ansanthrone, Anthraquinonyl Red, Perylene Maroon, Quinacridone Red Pigment, Diketopyrrolopyrrole, Watching Red, Permanent Red, etc. Red Pigment; Cobalt Purple, Quinacridone Violet, Dioxy Purple pigments such as gin violet; 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; Pearlescent pigments such as metal oxide coating mica powder, mica-like iron oxide; barita powder, precipitated barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, silica, white carbon, diatomaceous earth, talc, magnesium carbonate, alumina white And extender pigments such as gloss white, etc., and 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, as dyes, monoazo dyes, polyazo dyes, metal complex salt azo dyes, azo dyes such as pyrazolone azo dyes, stilbene azo dyes, thiazol azo dyes; anthraquino dyes such as anthraquinone derivatives and anthrone derivatives; indigo derivatives, thioindigo derivatives, etc. Indigoid dyes; phthalocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes and acridine dyes; quinone imine dyes such as azine dyes, oxazine dyes and thiazine dyes; methines such as polymethine (or cyanine) dyes and adimethine dyes Dyes; quinoline dyes; nitro dyes; nitrone dyes; benzoquinone and naphthyquinone dyes; naphthalimide dyes; perinone dyes, and the like. It is possible to have.

  The amount of the colorant (b) used is usually 0.00 on the basis of the mass (solid content) of the aqueous resin (a) from the viewpoints of colorability, specific gravity, durability, water resistance and the like due to the granular gel (C). It is suitable to be in the range of 01 to 500% by mass, preferably 0.05 to 400% by mass, more preferably 0.1 to 300% by mass.

Water-soluble polysaccharide (c) :
The water-soluble polysaccharide (c) used in the method of the present invention is brought into contact with the metal ions derived from the metal compound (d) in the aqueous medium (B), so that the water-soluble resin (a) and the colorant (b ) Is used to form a metal salt gel that is insoluble or hardly soluble in water containing the aqueous liquid composition.

  The water-soluble polysaccharide (c) is a polysaccharide capable of turning into a water-insoluble or sparingly soluble gel when contacted with a monovalent or polyvalent metal ion in an aqueous medium, generally about 3,000. Preferred are those having a number average molecular weight in the range of about 2,000,000, in particular about 5,000 to about 1,000,000 and exhibiting a solubility of about 10 G / L (25 ° C.) or more, 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 (c) is the stability of the granular gel (C) in water, the handleability when producing the granular gel (C), and the water resistance of the coating film formed from the coating material containing the granular gel (C). From the viewpoints of surface property and coated surface smoothness, it is usually 0.2 to 10% by mass, preferably 0.8%, based on the total mass of the aqueous resin (a), the colorant (b) and the water-soluble polysaccharide (c). It is preferable to use within the range of 5-6 mass%.

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

  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 a partial ester of vinyl methyl ether-maleic anhydride copolymer, a half ester of a reaction product 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 20% by mass, preferably 0.021 to 10% by mass, more preferably 0.05, based on the mass (solid content) of the aqueous resin (a). It can be in the range of ~ 5% by weight.

  The aqueous liquid composition (A) 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 deodorant, 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 (A) is prepared, for example, by appropriately mixing an emulsion of the aqueous resin (a), a colorant (b), and an aqueous solution of the water-soluble polysaccharide (c) together with the other components described above. can do.

Aqueous medium (B) :
The aqueous medium (B) used in the present invention is at least 0.005 mg, particularly at least 0.01 mg, more particularly at least 0, in 100 g of water at 25 ° C., selected from metal hydroxide, metal oxide and metal carbonate. 0.08 mg of the metal compound (d) that can be dissolved, and when in contact with the aqueous liquid composition (A), the water-soluble polysaccharide (c) in the aqueous liquid composition (A) is converted into an aqueous medium (B ) In which a metal ion derived from the metal compound (d) and water insoluble or hardly soluble salt is formed, and the aqueous liquid composition (A) is formed into a granular gel.

  Examples of the metal species in the metal compound (d) include monovalent metals such as potassium and sodium, magnesium, calcium, strontium, barium, chromium, molybdenum, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, Although polyvalent metals, such as copper, zinc, cadmium, aluminum, and cerium, can be mentioned, from the viewpoint of the strength of the granular gel (C) to be formed, polyvalent metals, particularly divalent metals are preferred. Examples of the valent metal include Group 2 elements of the periodic table such as magnesium, calcium, strontium and barium; Group 6 elements of the periodic table such as chromium and molybdenum; Group 7 elements of the periodic table such as manganese; Periodic table 8 such as iron and ruthenium. Group elements; periodic table group 9 elements such as cobalt and rhodium; periodic table group 10 elements such as nickel and palladium Periodic Table Group 11 elements such as copper, zinc, etc. can be mentioned periodic table group 12 elements such as cadmium, among others, the periodic table 2 group element, especially calcium is preferred.

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

  An aqueous medium (B) containing a monovalent or polyvalent metal ion can be prepared by dissolving at least a part of the metal compound (d) in an aqueous medium. At that time, the metal compound (d) is not necessarily 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 (d) in the aqueous medium containing the metal compound (d) is usually 0.05 to 4% by mass, preferably 0.07 to 3% by mass, more preferably 0.1 to 2.5%. It can be in the range of mass%.

  The aqueous medium (B) is also a metal compound (d) such as calcium chloride, barium chloride, aluminum sulfate, zinc sulfate and the like within a range not affecting the physical properties of the granular gel (C) or a composition containing the same. Other metal compounds can be contained as required.

Preparation of granular gel (C) :
A granular gel (C) can be formed by contacting the aqueous liquid composition (A) with an aqueous medium (B) containing metal ions derived from the metal compound (d). This contact is, for example, a method in which the aqueous liquid composition (A) is dropped into the aqueous medium (B) from the tip of the syringe; the aqueous liquid composition (A) is scattered using centrifugal force, and the aqueous medium (B ) Method of dripping into the aqueous solution; A method of atomizing the aqueous liquid composition (A) from the tip of the spray nozzle and dropping it into the aqueous medium (B); The aqueous liquid composition (A) into the aqueous medium (B) In addition, it can be carried out by a method such as stirring and mixing with a disperser.

In the aqueous liquid composition (A) and the aqueous medium (B), the proportion of the water-soluble polysaccharide (c) in the aqueous liquid composition (A) and the metal compound (d) in the aqueous medium (B) is (c). / (D) is preferably used at such a ratio that it is usually within a range of 1/20 to 10/1, particularly 1/15 to 7/1, more particularly 1/10 to 4/1, The aqueous liquid composition (A) and the aqueous medium (B) have a mass ratio of (B) / (A) of usually ½ or more, preferably ½ to 100/1, more preferably 1/1. It can be used at such a ratio that it is in the range of ˜20 / 1.

  A granular gel obtained by encapsulating an aqueous liquid composition (A) containing an aqueous resin (a), a colorant (b), and other additive components in a metal salt gel of polysaccharide (c) by the above method. (C) can be obtained.

  The size (major axis) of the granular gel (C) formed as described above is not particularly limited, and can be appropriately changed according to its use. For example, the aqueous liquid composition (A) And the concentration of metal ions in the aqueous medium (B), the manner in which the aqueous liquid composition (A) is dropped onto the aqueous medium (B), and the like. In the present invention, the size of the granular gel (C) can generally be in the range of 10 to 40,000 μm, preferably 50 to 15,000 μm, and more preferably 50 to 5,000 μm. As a distribution, it is preferable that a particle group having a size of 75 μm or more and 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 (C) is the minimum nominal size of the sieve that can be passed when the granular gel (C) is sieved (perforation 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 (C) 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 (C). 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 (C) is not particularly limited, but is generally 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 (C) can be separated from the aqueous medium (B) containing metal ions by using, for example, a wire mesh having an appropriate size mesh, whereby the metal ions are separated from the granular gel. Concomitant with (C), it can be prevented from being mixed into a coating composition using the same, and the physical properties such as water resistance of the formed coating film can be improved.

Coating composition :
According to the method of the present invention described above, it is possible to easily produce a granular gel having good storage stability without using a large amount of an organic solvent, and to obtain a coating composition containing the obtained granular gel (C) Forms a coating film with little odor at the time of painting and excellent in coating film properties such as water resistance and weather resistance.

  Therefore, according to this invention, the coating composition containing a granular gel (C) is also provided. In this coating composition, by including a plurality of granular gels having different color tones, a so-called multicolored coating can be prepared, and thereby the design of the formed coating film can be improved. In this case, a metallic pigment and / or a pearlescent pigment can be used as the colorant (b), thereby imparting a high-class feeling to the multicolored coating film.

  The coating composition preferably contains a coating film forming component (D) in addition to the granular gel (C).

  The coating film-forming component (D) itself has film-forming properties, and may be any of a non-crosslinked type and a crosslinked type, and any of an aqueous type, a powder type, an organic solvent type, etc. There may be.

  In the present invention, the coating film-forming component (D) is an aqueous composition comprising an aqueous resin (e) from the viewpoint of affinity with the granular gel (C) and storage stability as a coating composition. It is desirable.

  As said water-based resin (e), what is generally used as a resin binder in the field of water-based paints can be used similarly. For example, it can be used by appropriately selecting from those described above for water-based resin (a). it can.

  The aqueous resin (a) in the granular gel (C) can have a crosslinking reactive group (x), or the granular gel (C) can contain a crosslinking agent having a crosslinking reactive group (x), In that case, the coating film-forming component (D) can optionally contain a functional group (y) that reacts with the crosslinking reactive (x) group contained in the granular gel (C). Examples of combinations of such crosslinkable reactive groups (x) and (y) include carbonyl groups and hydrazine residues, hydroxyl groups and isocyanate groups, hydroxyl groups and alkyl ether groups, hydroxyl groups and imino groups, carboxyl groups and epoxy groups. And combinations of amino group and epoxy group, amide group and epoxy group, and the like. Here, examples of the hydrazine residue include a hydrazine group, a hydrazide group, a semicarbazide group, and a bisacetyldihydrazone group.

  The film-forming component (D) can also comprise a crosslinking agent (f) for the aqueous resin (e). Examples of the crosslinking agent (f) include those known per se, such as hydrazine residue-containing compounds, oxazoline group-containing compounds, carbodiimide group-containing compounds, imino group and / or alkyl ether group-containing compounds, isocyanate group-containing compounds, and the like. And can be used alone or in combination of two or more depending on the crosslinking reactive group contained in the aqueous resin (e).

  The aqueous resin (e) is preferably a carbonyl group-containing aqueous resin. By using this carbonyl group-containing aqueous resin together with a hydrazine derivative as a crosslinking agent that reacts with the carbonyl group, the aqueous resin (e) is stable at the storage stage and forms a coating film. In some cases, it is possible to obtain a coating composition that forms a cured film by a crosslinking reaction between a carbonyl group and a hydrazine residue.

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. These hydrazine derivatives are usually 0.01 to 5% by mass, preferably 0.02 to 3% by mass, and more preferably 0.05 to 2% by mass, based on the solid content mass of the aqueous resin (e). Can be used within range.

  In addition, the aqueous resin (e) can contain a hydroxyl group as a crosslinking reactive group. In that case, for example, a polyisocyanate crosslinking agent, a melamine resin, or the like can be used as a crosslinking agent.

  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).

  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 using a melamine resin as a crosslinking agent, if necessary, as a catalyst, a sulfonic acid such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, a salt of these sulfonic acids with an amine, etc. Can be used.

  The coating film-forming component (D) 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 based on the total solid content of the aqueous resin (e) and the crosslinking agent (f) contained in the coating film forming component (D). It can be in the range of 1-10% by weight.

  The coating film forming component (D) 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 (D) can be appropriately selected from those exemplified above as the colorant that can be contained in the granular gel (C). When the coating composition of the present invention is used as a multicolored paint, it is desirable to add extender pigments to the paint composition from the viewpoints of improving the drying property of the multicolored paint film, improving the appropriate gloss and touch. When the colorant and / or extender pigment is blended in the coating film forming component (D), the total blending amount thereof is that of the aqueous resin (e) and the crosslinking agent (f) contained in the coating film forming component (D). Based on the total solid content, it is usually 5 to 200% by mass, preferably 10 to 150% by mass, and more preferably 15 to 120% by mass.

  Examples of the extender pigment 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.

Coating composition :
In the coating composition of the present invention, the above-described granular gel (C) and coating film-forming component (D) are mixed together with a coating additive as required by a method known per se, and an aqueous medium is appropriately added. It can prepare by adding and adjusting a viscosity and / or pH. Moreover, when using a polyisocyanate crosslinking agent as a crosslinking agent in a coating-film formation component (D), 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 (C). 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 (C) and the coating film forming component (D) in the coating composition of the present invention can be changed according to the use of the coating composition, etc., but the granular gel (C) / coating film forming component The solid content mass ratio of (D) is 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 coating composition of the present invention can be changed according to the composition of the coating composition to be used, the type of substrate to be coated, etc., but is usually 100 to 1,000 g / m ² , preferably 200 to It can be in the range of 500 g / m ² .

  The coating composition 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. .

  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 a base coating surface after the primer coating is applied to the surface of a substrate in advance for a protective coating.

  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 coating composition of the present invention is used, a protective coating film excellent in finish, water resistance, and weather resistance can be formed, but on the coating film of the coating composition of the present invention, if necessary, Further known topcoats may be further applied.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited only to 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 433 parts n-Butyl acrylate 240 parts 2-ethylhexyl acrylate 150 parts 1,6-hexanediol diacrylate 5 parts 2-hydroxyethyl acrylate 20 parts Acrylic acid 2 parts "Newcol 707SF" (Note 1) 66 parts.

  After completion of the dropwise addition, this was further maintained at 85 ° C. for 2 hours, and then cooled to 40-60 ° C. Subsequently, it adjusted to pH 8-9 with aqueous ammonia, and obtained the emulsion (a1) whose solid content is 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 410 parts n-Butyl acrylate 240 parts 2-ethylhexyl acrylate 150 parts Diacetone acrylamide 20 parts 2-hydroxyethyl acrylate 20 parts Acrylic acid 10 parts Newcol 707SF (Note 1) 66 Department.

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 “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 44 parts "Talc T-1" ( Note 5) 80 parts “Matsumoto Microsphere F-80E” (Note 6) 28 parts 16 parts of 10% adipic acid dihydrazide aqueous solution.

(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 (A1) 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 Example 7
In the said manufacture example 6, the aqueous liquid composition (A2) was manufactured like the manufacture example 6 except changing a component composition into the following thing.

Water-based clear paint (C1) 400 parts Red pigment paste (Note 10) 4 parts "Adecanol UH438" (Note 4) 1 part 2% sodium alginate aqueous solution 230 parts.
(Note 10) Red pigment paste: “Unilant 88 red” (trade name, manufactured by Yokohama Kasei Co., Ltd.)
A color paste having a pigment content of about 30%, prepared in the same manner as in Production Example 5.

Production Example 8
An aqueous liquid composition (A3) was produced in the same manner as in Production Example 6 except that the component composition was changed to the following in Production Example 6.

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 Green pigment paste (Note) 11) 12 parts 2% sodium alginate aqueous solution 280 parts.
(Note 11) Green pigment paste: “Unilant 88 green” (trade name, manufactured by Yokohama Kasei Co., Ltd.)
A color paste having a pigment content of about 20%, prepared in the same manner as in Production Example 5.

Production Example 9
In Production Example 8, the same procedure as in Production Example 8 except that the emulsion (a1) is replaced with the emulsion (a2), the green pigment paste is replaced with the black pigment paste (Note 12), and the 2% sodium alginate aqueous solution is replaced with the 2% gellan gum aqueous solution. Thus, an aqueous liquid composition (A4) was produced.

(Note 12) Black pigment paste: “Unilant 88 Black” (trade name, manufactured by Yokohama Kasei Co., Ltd.)
A color paste having a pigment content of about 20%, prepared in the same manner as in Production Example 5.

Production Example 10
An aqueous liquid composition (A5) was produced in the same manner as in Production Example 6 except that the component composition was changed to the following in Production Example 6.

55% emulsion (a1) 250 parts “TEXANOL” (Note 2) 20 parts “SN Deformer 380” (Note 3) 2 parts “Adecanol UH-438” (Note 4) 2 parts Aluminum paste (Note 13) 38.2 parts 200 parts of 2% aqueous sodium alginate solution.

(Note 13) Aluminum paste: The 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.
(*) Phosphoric acid 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 consisting of 0.5 parts of ate and 20 parts of 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 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%.

Production Example 11
An aqueous liquid composition (A6) was produced in the same manner as in Production Example 7 except that the component composition was changed to the following in Production Example 7 and the pigment was removed.

Water-based clear paint (C1) 400 parts “Adecanol UH438” (Note 4) 1 part 230% of a 2% sodium alginate aqueous solution.

Production of granular gel Example 1
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 (A1) 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 rotation speed for 15 minutes, it was separated by filtration using a 200-mesh wire mesh to obtain a white granular gel (C1). The obtained granular gel white (C1) had a solid content of 20%, and the proportion of particles having a size of 75 μm or more and less than 500 μm was 95% in the entire granular gel.

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

Example 2
A 24-liter stainless steel container is charged with 24 parts of calcium hydroxide and 1,200 parts of deionized water and stirred at a rotational speed of 1,500 rpm using a stirring blade having a diameter of 75 mm to produce an aqueous solution having a pH of 12.8. While stirring at the same stirring speed, 600 parts of the aqueous liquid composition (A2) was gradually dropped into the container 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 red color (C2). The obtained granular gel red color (C2) had a solid content of 20%, the proportion of the granular gel having a size of 150 μm or more and less than 2,000 μm was 95% in the total granular gel.

Example 3
In a 4-liter stainless steel container, 2,000 parts of 0.15% aqueous calcium hydroxide solution (pH = 12.8) was charged, and the aqueous solution was stirred while stirring at a rotational speed of 1,500 rpm using a stirring blade having a diameter of 75 mm. 650 parts of the liquid composition (A3) was gradually dropped into the container 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 green color (C3). The obtained granular gel green color (C3) had a solid content of 20%, the proportion of the granular gel having a size of 150 μm or more and less than 2,000 μm was 90% in the total granular gel.

Example 4
Into a 4 liter stainless steel container, 1,300 parts of 0.15% aqueous calcium hydroxide solution (pH = 12.8) was charged, and the above aqueous liquid was stirred while stirring at a rotational speed of 2,000 rpm using a stirring blade having a diameter of 75 mm. 650 parts of the composition (A4) was gradually dropped into the container 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 granular gel gray (C4). The obtained granular gel gray (C4) had a solid content of 20%, and the proportion of the granular gel having a size of 150 μm or more and less than 1000 μm was 95% in the total granular gel.

Example 5
While charging 1,300 parts of 0.15% aqueous calcium hydroxide (pH = 12.8) into a 4 liter stainless steel container and stirring at a rotational speed of 2500 rpm using a stirring blade having a diameter of 75 mm, 650 parts of the obtained aqueous liquid composition (A5) 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 using a 200-mesh wire mesh to obtain a granular gel silver color (C5). The obtained granular gel silver color (C5) had a solid content of 20%, and the proportion of particles having a size of 75 μm or more and less than 500 μm was 95% in the total granular gel.

Comparative Example 1
A granular gel (C6) having a solid content of 20% was obtained in the same manner as in Example 2 except that the aqueous liquid composition (A6) containing no pigment obtained in Production Example 11 was used. The granular gel (C6) had a solid content of 20%, the proportion of the granular gel having a size of 150 μm or more and less than 2,000 μm was 95% in the total granular gel.

Comparative Example 2
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 (A1) was gradually put into the container while rotating at a rotational speed of 3,000 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, to obtain a white dispersion (C7) in which the granular gel white was dispersed in the calcium chloride aqueous solution. The white dispersion (C7) had a solid content of 18%, and the proportion of granular gel having a size of 250 μm or more and less than 2,000 μm was 80% in the total granular gel.

Comparative Example 3
Into a 4-liter stainless steel container, 1,300 parts of 0.22% calcium chloride aqueous solution was charged, and 650 parts of the aqueous liquid composition (A1) was added while rotating at a rotational speed of 2500 rpm using a stirring blade having a diameter of 75 mm. 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 rotational speed, filtered through a 200 mesh wire net, and then washed with water to obtain a granular gel (C8). The obtained granular gel (C8) had a solid content of 20%, and the proportion of particles having a size of 75 μm or more and less than 500 μm was 95% in the entire granular gel.

Manufacture of multicolored paint Example 6
The components shown below were charged into a 500 ml Stellens container while sequentially stirring, and then further stirred to obtain a multicolored paint (X1).

Clear paint (C1) 130 parts Granular white gel (C1) 145 parts Granular gel red color (C2) 15 parts Granular gel green color (C3) 15 parts "Adecanol UH-438" (Note 4) 0.3 part Water 30 parts.

Examples 7-9 and Comparative Examples 4-6
In Example 6 above, multicolor paints (X2) to (X6) were obtained in the same manner as in Example 6 except that the component composition was changed to that in Table 1. Table 1 also shows the properties of the obtained multicolor pattern paint and the coating performance test results.

塗膜性能試験
試験塗板の作製
スレート板（１５０×７０×３ｍｍ）上に、「ＥＰシーラー透明」（関西ペイント社製、水系アクリルエマルション系シーラー）を塗布量が１００ｇ／ｍ^２になるようにローラー塗装し乾燥させた後、「ビニデラックス３００」（関西ペイント社製、ＪＩＳ Ｋ ５６６３ １種適合アクリルエマルション系塗料）を塗布量が１００ｇ／ｍ^２になるようにローラー塗装し、気温２０℃、相対湿度６０％の条件下で１日間乾燥させたものを被塗板とし、この上に実施例５〜７及び比較例３，４で得た各多彩模様塗料を塗布量が３００ｇ／ｍ^２になるようにスプレーで塗装した。その後、気温２３℃、相対湿度６０％の条件下で７日間乾燥して、各試験塗板を得た。得られた試験塗板を下記性能試験に供した。

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 coated plate, and the coating amount of each of the various pattern paints obtained in Examples 5 to 7 and Comparative Examples 3 and 4 was 300 g / m. ^It was painted with spray to become ² . Then, it dried for 7 days on the conditions of air temperature 23 degreeC and relative humidity 60%, and obtained each test coating plate. The obtained test coated plate 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 (14)

An aqueous liquid composition (A) containing an aqueous resin (a), a colorant (b) and a water-soluble polysaccharide (c), 100 g of water at 25 ° C. selected from metal hydroxides, metal oxides and metal carbonates In which the aqueous resin (a) is a carboxyl group-containing polymerizable unsaturated monomer as at least a part of the monomer component. the (co) Ri carboxyl group-containing acrylic resin der produced by using 0.05 to 30% by weight, based on the weight of total polymerizable unsaturated monomer be polymerized, water-soluble polysaccharide (c the method of manufacturing the granular gel) is characterized Rukoto selected from alginic acid or alkali metal salts thereof, gellan gum and carrageenan.   The method according to claim 1, wherein the aqueous resin (a) further contains a carbonyl group.   The method according to claim 1 or 2, wherein the aqueous liquid composition (A) contains the colorant (b) in a range of 0.01 to 500% by mass based on the mass of the aqueous resin (a).   The method according to any one of claims 1 to 3, wherein the colorant (b) is a metallic pigment and / or a pearlescent pigment. The method according to any one of claims 1 to 4 , wherein the metal compound (d) is calcium hydroxide. The method according to any one of claims 1 to 5 , wherein the aqueous liquid composition (A) is contacted with the aqueous medium (B) and then filtered. The granular gel obtained by the method of any one of Claims 1-6 . The coating composition containing the granular gel (C) of Claim 7 . The coating composition according to claim 8 , further comprising a coating film-forming component (D). The coating composition according to claim 9 , wherein the coating film-forming component (D) contains a carbonyl group-containing aqueous resin. Claims containing the granular gel (C) and the coating film forming component (D) in such a ratio that the solid content mass ratio of the granular gel (C) / the coating film forming component (D) falls within the range of 1/99 to 80/20. Item 11. The coating composition according to Item 9 or 10 . The coating composition according to any one of claims 9 to 11 , wherein the coating film-forming component (D) further comprises an extender pigment. Coating method characterized by coating a coating composition according to the substrate surface in any one of claims 8-12. A coating method comprising applying a coating composition according to any one of claims 8 to 12 on the surface of the base coating after coating a base coating on the surface of the substrate.