CN100999625A - Aqueous paint composition - Google Patents
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- CN100999625A CN100999625A CNA2006101719722A CN200610171972A CN100999625A CN 100999625 A CN100999625 A CN 100999625A CN A2006101719722 A CNA2006101719722 A CN A2006101719722A CN 200610171972 A CN200610171972 A CN 200610171972A CN 100999625 A CN100999625 A CN 100999625A
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Abstract
The invention provides a water paint composition including: a granulated gel which is formed in a polyose metal salt gel by waterborne resin and waterborne liquid composition having a reactive functional group; and a paint film forming component which contains a reactive functional group capable of reacting with the above reactive functional group.
Description
Technical field
The present invention relates to a kind of water-based paint compositions, it contains granulated gel, and storage stability is excellent and can form filming of excellences such as water tolerance, appearance of film.
Background technology
The coating that forms as granulated gel stably is distributed in the dispersion medium, known have a for example colorful artistic coating.Colorful artistic coating is to form the coating of filming of the colourful pattern with color more than 2 kinds or 2 kinds by coating once, and is mainly used in the coating of buildings etc.
As colorful artistic coating, Te Kaiping 09-100426 communique discloses a kind of colorful artistic coating composition, it is dispersed in enamel in the water system dispersion medium and forms, contain a kind or a kind with the enameling dispersed particle, described enamel is that the composition that main component is formed forms by blending dispersion with multipolymer, tinting material and organic solvent, wherein multipolymer forms by the monomer mixture copolymerization that will contain 20 weight % or above acrylic monomer at least, and weight-average molecular weight is 20,000～200,000, acid number is below 2 or 2.The good stability of the enamel dispersed particle of this colorful artistic coating composition; film by its colorful fine arts that form and to have colorful artistic feeling; and weathering resistance and water tolerance excellence, but consider from the viewpoint of environment protection, need further to reduce contained organic solvent amount in this colorful artistic coating.
As the few colorful artistic coating of organic solvent content, for example, the spy opens the 2005-15645 communique and discloses a kind of water-in-water type multi-color artistic coating composition, its water-base resin by will having reactive functional groups, tinting pigment, water and as the painted gel particles that comes from the gelation thing of the reactive compounds that can react in the presence of water are dispersed in and contain water-base resin and expect with the body pigment (Ti Quality Yan with specific refractive index) transparent Flat paint in and form.Use this coating composition, the colorful fine arts of delustring that can form the smoothness excellence are filmed, and still the formed colorful fine arts are filmed and had the not enough such problem of water tolerance.
Summary of the invention
The purpose of this invention is to provide a kind of water-based paint compositions that contains granulated gel, its organic solvent content is few, and the protection that can form excellent performances such as water tolerance, appearance of film is filmed.
The inventor has carried out active research for reaching above-mentioned purpose, found that by granulated gel being dispersed in film and form the water-based paint compositions that obtains in the composition, can in the storage of coating, keep this water-based fluid composition stable, simultaneously in the formation stage of filming, granulated gel is formed into branch generation crosslinking reaction and combination securely with filming, can form filming of water tolerance excellence thus, finish the present invention thus.Wherein said granulated gel in polyose metal-salt gel in bag water-based fluid composition and forming, described water-based fluid composition contains water-base resin and has reactive functional groups, described film to form have in the composition and the reactive functional groups of this reactive functional groups reaction.
Therefore, the invention provides a kind of water-based paint compositions, it is characterized in that, it comprises granulated gel (I) and films formation composition (II), described granulated gel (I) is to include water-base resin (a) in polyose metal-salt gel (b) and have the water-based fluid composition of reactive functional groups (x) and form, described film form composition (II) contain can with the reactive functional groups (y) of reactive functional groups (x) reaction.
In the water-based paint compositions of the present invention, in the reactive functional groups (x) that is wrapped in the water-based fluid composition in the granulated gel (I) becoming mem stage to carry out crosslinking reaction with the reactive functional groups (y) that forms in the composition (II) of filming by gel-film, the granulated gel (I) and formation composition (II) combination securely of filming thus, thus filming of water tolerance excellence formed.In addition, water-based paint compositions of the present invention is wrapped in the granulated gel (I) owing to making in the water-based fluid composition that contains reactive functional groups (x), so can keep stable status in the storage stage.
Below, water-based paint compositions of the present invention is described in detail.
Water-based paint compositions of the present invention is characterised in that to comprise granulated gel (I) and film and forms composition (II), and the water-based fluid composition and filming of bag forms composition (II) and contains the functional group (x) of mutually reactive and (y) respectively in the granulated gel (I).
Combination as the reactive functional groups (y) that contains in the reactive functional groups (x) that contains in the interior water-based fluid composition that is wrapped in the above-mentioned granulated gel (I) and the formation composition (II) of filming, so long as under the drying conditions of filming the words of the combination of mutually reactive, then be not particularly limited, specifically can enumerate, for example carbonyl and hydrazine residue, hydroxyl and isocyanate group, hydroxyl and alkylether radicals, hydroxyl and imino-, carboxyl and epoxy group(ing), amino and epoxy group(ing), the combination of amido and epoxy group(ing) etc., wherein carbonyl and hydrazine residue, hydroxyl and isocyanate group, hydroxyl and alkylether radicals, the combination of hydroxyl and imino-is particularly preferred.
As above-mentioned hydrazine residue, can enumerate, for example diazanyl, hydrazide group, Semicarbazido, diacetyl two hydrazone groups (PVC ス ァ セ チ Le ジ ヒ De ラ ソ Application base) etc.
Granulated gel (I):
Among the present invention, granulated gel (I) is to include water-base resin (a) in polyose metal-salt gel (b) and have the water-based fluid composition of reactive functional groups (x) and the material that forms.
Water-base resin (a):
Water-base resin (a) is the contributive material of weather resistance to granulated gel (I), can use water soluble maybe can be scattered in resin in the water.The kind of this resin is not particularly limited, concrete example as, can enumerate acrylic resin, polyolefin resin, silicon resinoid, polyurethanes resin, redix, phenolic resinoid, polyester resin, alkyd based resin, polycarbonate resin etc., these resins can be distinguished use separately, perhaps are used in combination more than 2 kinds or 2 kinds.In addition, these resins can be the resin that is modified as for example urethane is acrylic resin modified, also can be the resins of graft polymerization.
Above-mentioned water-base resin (a) can be multilayer shapes such as individual layer shape or core/integumentary pattern when being the dispersed particle form.In addition, consider from the viewpoints such as manufacturing stability of granulated gel, water-base resin (a) can be to contain the resin of anionic property group as hydrophilic radical, particularly contain the resin of the carboxyl of double as reactive functional groups (x) as hydrophilic radical, in this case, this resin can be neutralized, as spendable neutralizing agent this moment, for example, the methylamine of can giving an example, dimethylamine, Trimethylamine 99, ethamine, diethylamine, triethylamine, dimethylaminoethanol, 2-methyl-2-amino-1-propyl alcohol, amines such as ammonia etc., these neutralizing agents can be distinguished use separately, perhaps are used in combination more than 2 kinds or 2 kinds.
Above-mentioned water-base resin (a) can contain with filming and forms the reactive functional groups (x) of contained reactive functional groups (y) reaction in the composition (II).As the reactive functional groups (x) that can contain in the water-base resin (a), for example, can enumerate carbonyl, hydroxyl, carboxyl, epoxy group(ing), amino etc., carbonyl and hydroxyl are particularly suitable.The content of these reactive functional groups (x) usually can be at 0.05～2mmol/g resin in the water-base resin (a), preferably at 0.1～1 mmol/g resin, further preferably in the scope of 0.1～0.5mmol/g resin.
When hydrotropisms's resin (a) imports reactive functional groups (x), for example can (be total to) polymerization together, perhaps by making the compound that contains reactive functional groups (x) and resin reaction import reactive functional groups (x) as matrix by making the polymerizability unsaturated monomer that contains reactive functional groups (x) and other suitable polymerizability unsaturated monomer.
Consider that from viewpoints such as the weather resistance of granulated gel (I), weathering resistancies water-base resin (a) is preferably acrylic resin.
As such acrylic resin, can enumerate with acrylic monomer as necessary monomer component, and resin by this monomer and other suitable polymerizability unsaturated monomer (being total to) polymerization are obtained, as supplying to be somebody's turn to do (being total to) polymeric monomer, for example, can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) 2-EHA, (methyl) dodecylacrylate, straight or branched (methyl) alkyl acrylates such as (methyl) vinylformic acid stearyl; (methyl) vinylformic acid cycloalkyl esters such as (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate; (methyl) vinylformic acid aralkyl esters such as (methyl) benzyl acrylate; (methyl) alkoxyalkyl acrylates such as (methyl) vinylformic acid 2-methoxyl group ethyl ester, (methyl) vinylformic acid 2-ethoxy ethyl ester; (methyl) perfluoroalkyl acrylate; (methyl) vinylformic acid N, (methyl) vinylformic acid N such as N-diethylamino ethyl ester, N-dialkyl aminoalkyl ester; (methyl) acrylamide; (methyl) vinyl cyanide; Vinyl ester such as vinyl-acetic ester, propionate compound; Vinyl aromatic compounds such as vinylbenzene, alpha-methyl styrene; (methyl) allyl acrylate, two (methyl) vinylformic acid glycol ester, two (methyl) vinylformic acid triglycol ester, two (methyl) vinylformic acid TEG ester, two (methyl) vinylformic acid 1, the 3-butanediol ester, trimethylolpropane tris (methyl) acrylate, two (methyl) vinylformic acid 1, the 4-butanediol ester, two (methyl) vinylformic acid DOPCP, two (methyl) vinylformic acid 1,6-hexylene glycol ester, two (methyl) vinylformic acid pentaerythritol ester, four (methyl) vinylformic acid pentaerythritol ester, two (methyl) vinylformic acid glycerine ester, 1,1,1-trimethylolethane two (methyl) acrylate, 1,1,1-trimethylolethane trimethacrylate (methyl) acrylate, 1,1,1-trimethylolpropane tris (methyl) acrylate, triallyl isocyanurate, the terephthalic acid diallyl, Vinylstyrenes etc. have the polyene-based compound of at least 2 polymerizability unsaturated groups in 1 molecule; The 6-caprolactone modification body of (methyl) vinylformic acid hydroxyalkyl acrylates such as (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid hydroxyl butyl ester, vinyl carbinol, above-mentioned (methyl) vinylformic acid hydroxyalkyl acrylate, contain the polymerizability unsaturated monomer of hydroxyls such as (methyl) acrylate that molecular end is the polyoxyalkylene chain of hydroxyl; (methyl) vinylformic acid, toxilic acid, Ba Dousuan, β-carboxylic polymerizability unsaturated monomers such as carboxy ethyl acrylate; (methyl) propenal, formyl radical vinylbenzene, carbonatoms are the polymerizability unsaturated monomer that 4～7 vinyl alkyl ketone (for example, ethenyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone etc.), (methyl) vinylformic acid acetoacetoxy groups ethyl ester, acetoacetoxy groups allyl ester, two acetone (methyl) acrylamide etc. contain carbonyl; (methyl) glycidyl acrylate, (methyl) vinylformic acid Beta-methyl glycidyl ester, (methyl) vinylformic acid 3,4-epoxycyclohexyl methyl esters, (methyl) vinylformic acid 3,4-epoxycyclohexyl ethyl ester, (methyl) vinylformic acid 3,4-epoxycyclohexyl propyl ester, glycidyl allyl ether etc. contain the polymerizability unsaturated monomer of epoxy group(ing); Pseudoallyl-α between (methyl) vinylformic acid isocyanate group ethyl ester, isocyanic acid, alpha-alpha-dimethyl benzyl ester etc. contains the polymerizability unsaturated monomer of isocyanate group; Vinyltrimethoxy silane, vinyltriethoxysilane, γ-iso-butylene acyl-oxygen base propyl trimethoxy silicane, γ-butylene acyloxy propyl-triethoxysilicane etc. contain the polymerizability unsaturated monomer of alkoxysilyl; Contain the polymerizability unsaturated monomer of epoxy group(ing) or contain the polymerizability unsaturated monomer of hydroxyl and the reaction product of unsaturated fatty acids; (methyl) vinylformic acid two cyclopentenes oxygen base ethyl esters, (methyl) vinylformic acid two cyclopentenes oxygen base propyl ester, (methyl) vinylformic acid dicyclopentenyl ester etc. contain the polymerizability unsaturated monomer of oxidative cure group etc., these monomers can be distinguished use separately, perhaps are used in combination more than 2 kinds or 2 kinds.
Above-mentioned monomeric polymerization process is not particularly limited, and for example, according to general emulsion polymerization, in the presence of emulsifying agent, by making above-mentioned monomer (being total to) polymerization, can make acrylic resin at an easy rate.
Employed emulsifying agent in the manufacturing as the aforesaid propylene acid resin, can use itself known tensio-active agent, as the tensio-active agent that is suitable for, for example, can enumerate anionic surfactant, nonionic surfactant, zwitterionics.
As the anionic surfactant, for example, can enumerate alkyl diphenyl ether disulfonates such as dodecyl phenyl ether disulfonic acid two ammoniums, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, dodecyl phenyl ether disulfonic acid calcium, alkyl diphenyl ether disulphonic acid sodium; Alkylbenzene sulfonates such as Sodium dodecylbenzene sulfonate, Witco 1298 Soft Acid ammonium; Alkyl-sulphate such as sodium lauryl sulphate, ammonium lauryl sulfate; Aliphatic carboxylate such as sodium soap, potassium oleate; Contain the unitary sulfuric acid of polyoxyalkylene (for example, polyethylene oxide alkyl ethers sulfuric acid such as polyethylene oxide alkyl ethers sodium sulfate, polyethylene oxide alkyl ethers ammonium sulfate; Polyoxyethylene alkyl phenyl ether sulfuric acids such as polyoxyethylene alkyl phenyl ether sodium sulfate, polyoxyethylene alkyl phenyl ether ammonium sulfate; Polyoxyethylene encircles phenyl ether sodium sulfate more, polyoxyethylene encircles polyoxyethylenes such as phenyl ether ammonium sulfate more and encircles phenyl ether sulfuric acid etc. more); Naphthalene sulfonic acidformaldehyde condensation product salt such as naphthalene sulfonic acidformaldehyde condensation product sodium etc.; Alkyl succinic acid sulfonated esters such as dialkyl sodium sulfosuccinate, monoalkyl succinate disodium sulfonate etc., these anionic surfactants can distinguish use separately, perhaps are used in combination more than 2 kinds or 2 kinds.
As nonionic surfactant, for example, can enumerate and contain the unitary ether compound of polyoxyalkylene (for example, polyoxyalkylene alkyl compounds such as polyoxyethylene lauryl ether, polyoxyethylene octadecyl ether, polyoxyethylene tridecyl ether, polyoxyethylene oleyl ether; Polyoxyalkylene such as polyoxyethylene octylphenyl ether, polyoxyethylene nonylplenyl ether alkyl phenyl ether compound; Polyoxyethylene encircles polyoxyalkylenes such as phenyl ether more and encircles phenyl ether compound etc. more); Polyoxyalkylene alkyl ester compounds such as polyoxyethylene mono-laurate, polyoxyethylene monostearate ester, polyoxyethylene monoleate; Polyoxyalkylene alkylamines such as polyoxyethylene alkylamine; Anhydro sorbitol compounds such as Arlacel-20, Arlacel-60, sorbitan trioleate, polyoxyethylene Arlacel-20, polyoxyethylene polyoxyethylene-sorbitan mono-oleate etc., these nonionic surfactants can be distinguished use separately, perhaps are used in combination more than 2 kinds or 2 kinds.
As zwitterionics, can enumerate dimethyl alkyl betaine class, dimethyl alkyl lauryl betaine class, alkyl glycine class etc.
As mentioned emulsifier, can also use the reactive emulsifier that in molecule, contains polymerizability unsaturated group and anionic property group or nonionic group.
Total mass with the polymerizability unsaturated monomer is a benchmark, and the usage quantity of mentioned emulsifier usually can be at 0.5～6 quality %, preferably in the scope of 1～4 quality %.
Polyose metal-salt gel (b):
Polyose metal-salt gel (b) among the present invention is the gelating film that includes the water-based fluid composition of above-mentioned water-base resin (a) in being configured for, and can form the composition of the shell wall of granulated gel (I).
Granulated gel (I) can obtain by the water-based fluid composition (c) that contains water-base resin (a) and water-soluble polysaccharides (b1) is contacted with aqueous medium, thus, the granulated gel (I) that includes the water-based fluid composition (c) of water-base resin (a) in can being formed in the polyose metal-salt gel (b), wherein said aqueous medium contain and can form water insoluble with water-soluble polysaccharides (b1) or be insoluble in the monovalence or the polyvalent metal ion of the salt of water.
Above-mentioned water-soluble polysaccharides (b1) is to have in aqueous medium the polyose that becomes the ability of water-insoluble or insoluble gel when contacting with monovalence or polyvalent metal ion, generally have about 3,000～about 2,000,000, particularly about 5,000～about 1,000,000 number-average molecular weight, and show that the polyose of about 10G/L (25 ℃) or above solubleness is preferably, specifically can enumerate for example alginic acid or its an alkali metal salt, gellan gum (ジ ェ ラ Application ガ system), carrageenan (カ ラ ギ one Na Application) etc., these polyoses can be distinguished use separately, perhaps are used in combination more than 2 kinds or 2 kinds.
From the stability of granulated gel (I) water, operability during preparation granulated gel (I) and the viewpoints such as water tolerance of the filming consideration that forms by the coating that contains granulated gel (I), total mass with water-base resin (a) and water-soluble polysaccharides (b1) is a benchmark, preferred water-soluble polysaccharides (b1) is generally 0.1～10 quality %, be preferably 0.1～7 quality %, more preferably the scope of 0.1～5 quality %.
Water-based fluid composition (c) can contain the linking agent (d) with reactive functional groups (x), so that can react with the formation composition (II) of filming, and make granulated gel (I) and film form composition (II) by the interface in conjunction with forming crosslinked filming, particularly do not contain under the situation of reactive functional groups (x) at water-base resin (a), preferred water-based fluid composition (c) contains the have reactive functional groups linking agent (d) of (x).
Good from the storage stability of granulated gel (I), forming when filming by water-based paint compositions of the present invention and the reaction that forms composition (II) of filming is successfully carried out, and as water-based paint compositions can 1 liquefaction etc. viewpoint consider, as the linking agent (d) that can contain in the water-based fluid composition (c), hydrazine derivative, melamine resin etc. is fit to.
As above-mentioned hydrazine derivative, for example, can enumerate hydrazine; Hydrazine hydrate; Carbonatomss such as oxalic acid two hydrazides, propanedioic acid two hydrazides, succinic acid hydrazide ii, pentanedioic acid two hydrazides, adipic dihydrazide, sebacic dihydrazide are two hydrazides of 2～18 representative examples of saturated aliphatic carboxylic; Two hydrazides of monoolefine unsaturated dicarboxylic acids such as Malaysia acid dihydrazide, fumaric acid two hydrazides, methylene-succinic acid two hydrazides; Two hydrazides of phthalic acid, terephthalic acid or m-phthalic acid; Two hydrazides of pyromellitic acid, three hydrazides or four hydrazides; Nitrilotriacetic acid(NTA) three hydrazides, citric acid three hydrazides, 1,2,4-benzene three hydrazides; Ethylenediamine tetraacetic acid (EDTA) four hydrazides, 1,4,5,8-naphthoic acid four hydrazides; The polyhydrazide that makes the reaction of the oligopolymer that contains carboxylic acid low alkyl group ester group and hydrazine or hydrazine hydrate (hydrazine hydrate) and form etc.; Carbonic acid two hydrazides, diaminourea; Make N, the multifunctional Urea,amino-that N such as N-dimethylhydrazine, N-replace vulcabond such as hydrazine or above cited hydrazides and hexamethylene diisocyanate, isophorone diisocyanate and obtained by its deutero-polyisocyanate compounds excessive response; The multifunctional Urea,amino-of water system that makes two above cited hydrazides and this polyisocyanate compounds and polyether glycol class or polyalkylene glycol monoalkyl ethers etc. contain the isocyanate group excessive response in the reactant of active dydrogen compounds of hydrophilic radical and obtain; This multifunctional Urea,amino-and the multifunctional Urea,amino-of water system mixture; Diacetyl dihydrazone etc.These hydrazine derivatives can be distinguished use separately, perhaps are used in combination more than 2 kinds or 2 kinds.
As above-mentioned melamine resin, for example, can enumerate the resin that has alkylether radicals and/or imino-in the molecule that makes melamine and formaldehyde and employed as required water and/or alcohol reaction and obtain, described resin specifically can be enumerated for example methylol melamines such as dimethylolmelamine, tri methylol melamine, tetra methylol melamine, pentahydroxy-methylmelamine, hexamethylol melamine; The alkylether compounds of this methylol melamine; The condenses of methylol melamine or its alkylether compounds etc.As the alkyl in the alkylether compounds of methylol melamine, for example, can enumerate carbonatomss such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, 2-ethylhexyl and be 1～8 alkyl group.
Using under the situation of melamine resin as linking agent (d), as required, the salt etc. that can use sulfonic acid such as tosic acid, Witco 1298 Soft Acid, dinonylnaphthalene sulfonic acid, these sulfonic acid and amine is as catalyzer.
When water-based fluid composition (c) contains linking agent (d), preferably adjust so that its usage quantity with respect to 1 mole of the reactive functional groups (y) that forms as filming of reaction object in the composition (II), the amount of the reactive functional groups (x) in the linking agent (d) is usually at 0.05～2 mole, preferably at 0.07～1.5 mole, further preferably 0.1～1 mole scope.
Use filming of water-based paint compositions formation of the present invention to give artistry, disguise etc. in order to give, water-based fluid composition (c) can further contain tinting material and/or body pigment.
Can use pigment and dyestuff as this tinting material, and pigment is particularly suitable.As pigment, for example, can enumerate white pigments such as titanium dioxide; Black pigments such as carbon black, acetylene black, dim, bone black, graphite, iron oxide black, nigrosine; Yellow ultramarines such as iron oxide yellow, titan yellow, monoazo yellow, condensation azophosphine, azomethine Huang, pucherite, benzimidazolone, isoindolinone, isoindoline, Kui phthalein ketone, diarylide yellow, permanent yellow; Orange pigmentss such as permanent orange; Red pigments such as red iron oxide, naphthols AS class azophloxine, ァ Application サ Application ス ロ Application, anthraquinone is red, perylene is purplish red (ペ リ レ Application マ Le one Application), quinacridine ketone red, diketopyrrolopyrrolecocrystals, Pigment red, permanent red, violet pigments such as cobalt violet, quinacridone violet, two piperazine purples; Cobalt blue, phthalocyanine blue, indanthrene blue blue pigmentss such as (ス レ Application Block Le one); Veridians such as phthalocyanine green; Metallic pigment such as aluminium powder, bronze powder, copper powder, glass putty, iron phosphide, zinc powder; Pearly-lustre tone pigment such as metal oxide-coated mica powder, mica shape ferric oxide (natural pearls Guang Kanazawa Tone Yan material) etc., these pigment can be distinguished use separately, perhaps are used in combination more than 2 kinds or 2 kinds.Titanium dioxide as above-mentioned white pigment can also comprise that median size is the little titanium (マ ィ Network ロ チ Application) of 10～80nm or the functional titanium dioxide such as anatase titanium dioxide with photocatalytic activity.
In addition, as dyestuff, for example, can enumerate azoic dyestuffs such as monoazo-dyes, polyazo dye, metal complex azo dyes, pyrazolone azoic dyestuff, toluylene azodyes, thiazole azo dye; Anthraquinone derivative such as anthraquinone derivative, anthracyclinone derivatives; Indigoid dyestuffs such as indigo derivative, thioindigo derivative; Phthalocyanine pigment; Carboniumion dyes such as diphenylmethane dye, triphenhlmethane dye, xanthene dye, acridine dye; Quinonimine dyes such as azines, piperazine dyestuff, thiazine dyes; Methyne dyestuffs such as polymethine (or cyanine) dyestuff, azomethine dyes; Quinoline dye, nitro-dye, nitrone (ニ ト ロ Application) dyestuff, benzoquinones and naphthoquinone dyestuff; The naphthalimide dyestuff; Purple cyclic ketones (ペ リ ノ Application) dyestuff etc.These dyestuffs can be distinguished use separately, perhaps are used in combination more than 2 kinds or 2 kinds.
In addition, as body pigment, can enumerate for example barium oxide powder, settleability barium sulfate, barium carbonate, lime carbonate, gypsum, clay, silicon-dioxide, white carbon black, diatomite, talcum, magnesiumcarbonate, white lake, gloss white etc.
Consider from viewpoints such as the tint permanence of granulated gel (I), proportion, weather resistance, water tolerance, the use level of above-mentioned tinting material and/or body pigment is a benchmark with the quality of water-base resin (a), usually at 0.01～500 quality %, preferably at 0.05～400 quality %, further preferred scope at 0.1～300 quality % is fit to.
In water-based paint compositions of the present invention, comprise the multiple granulated gel (I) that contains different tone tinting materials by making it, can improve and form the artistry of filming, and can prepare so-called colorful artistic coating.In this case, if use metallic pigment and/or pearly-lustre tone pigment, then can film and give feeling of high class, thereby be fit to the colorful fine arts as tinting material.
In granulated gel (I),, can in water-based fluid composition (c), further contain thickening material in order to make the easy uniform distribution of tinting material in the granulated gel.
As this thickening material, can use itself known substances in indefiniteness ground, as the example, for example, can enumerate mineral-type compounds such as water-soluble silicon acid alkali metal salt, montmorillonite, colloidal aluminum oxide; Derivatived cellulose compounds such as methylcellulose gum, Natvosol, carboxy methyl cellulose; Polyether compounds such as Pluronic (プ Le ロ ニ ッ Network) polyethers, polyethers dialkyl, polyethers dialkyl ether, polyethers urethane modifier, polyethers epoxide modifier; The polyacrylic compounds such as multipolymer of sodium polyacrylate, polyacrylic acid (methyl) acrylate; Polyvinyl compound such as polyvinyl alcohol, Polyvinylpyrolidone (PVP), polyvinyl alcohol, polyvinyl phenylcarbinol multipolymer; Protein derivatives such as sodium-caseinate, ammonium caseinate; The copolymer-maleic anhydrides such as half ester of the reactant of the partial ester of the multipolymer of vinyl methyl ether-maleic anhydride, drying oil fatty acid allyl alcohol ester-maleic anhydride etc., these thickening materials can be distinguished use separately, perhaps are used in combination more than 2 kinds or 2 kinds.The usage quantity of this thickening material is a benchmark with the quality of water-base resin (a), usually can be at 0.01～20 quality %, and preferably at 0.02～10 quality %, further preferably in the scope of 0.05～5 quality %.
As required, water-based fluid composition (c) can further contain fire retardant, spices, surface conditioners etc. such as globe (バ Le one Application) geometric ratio readjust material, defoamer, curing catalysts, pigment dispersing agent, perfume compound, deodorizing composition, antiseptic-germicide, neutralizing agent, tensio-active agent, watery water-proofing agent, dispersion agent, sanitas, mould inhibitor, antifreezing agent, UV light absorber, photostabilizer, film coalescence aid, zinc whisker, formaldehyde adsorbent, ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide, aluminium hydroxide.
Water-based fluid composition (c) for example can be by suitably preparing the aqueous solution of the emulsion of water-base resin (a) and water-soluble polysaccharides (b1) with thickener and above-mentioned other composition mixed together of linking agent (d), tinting material and/or body pigment.
As the metallic compound as the metal ion supply source (e) that can when making the granular gelling of water-based fluid composition (c), use, for example, can enumerate the oxyhydroxide, oxide compound, carbonate, muriate, sulfide etc. of polyvalent metals such as monovalence metals such as potassium, sodium or magnesium, calcium, strontium, barium, chromium, molybdenum, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, copper, zinc, cadmium, aluminium, cerium.
Consider that from the viewpoints such as intensity of formation granulated gel (I) as the preferred polyvalent metal of metal in the metallic compound (e), special preferred divalent metal as divalent metal, for example, can be enumerated periodictable the 2nd family's elements such as magnesium, calcium, strontium, barium; Periodictable such as chromium, molybdenum the 6th family's element; Periodictables such as manganese the 7th family's element; Periodictable such as iron, ruthenium the 8th family's element; Periodictable such as cobalt, rhodium the 9th family's element; Periodictable such as nickel, palladium the 10th family's element; Periodictables such as copper the 11st family's element; Periodictable such as zinc, cadmium the 12nd family's element etc., wherein, preferred cycle table the 2 family's elements, particularly calcium.
Preferable alloy compound (e) in the water of 25 ℃ of 100g, dissolve 0.005mg or more than, preferred especially 0.01mg or more than, more preferred 0.08mg or more than.
Among the present invention, as the special preferably calcium hydroxide of metallic compound (e).
Be dissolved in the aqueous medium by at least a portion that makes metallic compound (e), can prepare the aqueous medium that contains monovalence or polyvalent metal ion.At this moment, metallic compound (e) needn't all be dissolved in the aqueous medium, and it can be partly soluble state.In the aqueous medium that contains metallic compound (e), the content of metallic compound (e) is usually at 0.05～15 quality %, preferably at 0.7～12.5 quality %, further preferably in the scope of 0.1～10 quality %.
The preparation of granulated gel (I):
By above-described water-based fluid composition (c) is contacted with the aqueous medium that contains from the metal ion of metallic compound (e), can form granulated gel (I).This contact for example can be by splashing into the method for water-based fluid composition (c) from the front end hydrotropisms medium of syringe; Utilize centrifugal force that water-based fluid composition (c) is dispersed, and splash into the method in the aqueous medium; Make the water-based fluid composition from the atomizing of atomiser nozzle front end, and splash into the method in the aqueous medium; Add water-based fluid composition (c) in hydrotropisms's medium, and the method that mixes with dispersion machine etc. and carrying out.
Pass through aforesaid method, the granulated gel (I) that includes the water-based fluid composition (c) of reactive functional groups (x) in can obtaining in polyose metal-salt (b), described water-based fluid composition (c) comprise water-base resin (a) and the linking agent (d) that according to circumstances uses waits other additive component.
Size (major diameter) as above-mentioned formed granulated gel (I) is not particularly limited, can be according to the present invention water-based paint compositions purposes etc. and suitably change, for example, can be according to the concentration of metal ion in the composition of water-based fluid composition (c), the aqueous medium, water-based fluid composition (c) be added drop-wise to method in the aqueous medium etc. adjust.Among the present invention, the size of granulated gel (I) usually can be 10～15,000 μ m, preferably 50～5, the scope of 000 μ m, in addition, as its size-grade distribution, be of a size of 75 μ m or above and less than the population of 2,000 μ m in 70～100% of all particles group total mass, be preferred particularly in 85～98% scope.
In this manual, granulated gel (I) is of a size of and is similar to the minimum specified size (perforation size that makes the sieve that granulated gel (I) can pass through when sieving; The length on mesh 1 limit).As sieve, using specified size (perforation size) is 6 kinds of sieves of 75 μ m, 15 μ m, 250 μ m, 500 μ m, 1,000 μ m and 2,000 μ m.Can not be that the granulated gel (I) of the sieve of 2,000 μ m is of a size of with ruler and measures maximum sized mean value by the line at 10 granulated gels (I) center of selecting at random by specified size (perforation size).In addition, size-grade distribution can followingly be tried to achieve: by with above-mentioned 6 kinds of sieves whole granulated gel groups being carried out classification, after each sieve of thorough drying is gone up residual population, measure each oversize shape gel group's weight, and calculate its percentage ratio with respect to whole granulated gel groups' of drying weight.
The shape of granulated gel (I) is not particularly limited, but general preferred spherical.Wherein, term " spherical " is not limited to up and down all well-balanced sphere shape, also can be as the meaning that comprises flat spherical, the shapes such as spherical, tears shape distorted.
The granulated gel that obtains (I) for example can have the filtering separation from the aqueous medium that contains metal ion such as wire netting of appropriate size mesh by use.
Film and form composition (II):
Water-based paint compositions of the present invention comprises and above-mentioned granulated gel (I) combination, and contains and can form composition (II) with the filming of functional group (y) of contained reactive functional groups (x) reaction in this granulated gel (I).
Film and form the linking agent (g) that composition (II) can contain water-base resin (f) and use as required, as water-base resin (f), can use with the water-borne coatings field in the identical material of material that generally uses as resin glue, for example, can be set forth in described in the water-base resin (a) those.
As water-base resin (f), for example, can use the water-base resin that contains reactive functional groups (y).
The above-mentioned water-base resin (f) that contains reactive functional groups (y) usually can be at 0.05～0.5 mmole/gram resin, preferably the scope at 0.1～0.4 mmole/gram resin contains reactive functional groups (y).As the reactive functional groups (y) in this water-base resin (f), for example, can enumerate carbonyl, hydroxyl, carboxyl, epoxy group(ing), amino etc., preferred especially carbonyl, hydroxyl.As the water-base resin that contains this reactive functional groups (y) (f), for example, can from granulated gel (I), contain and suitably select in the resin described in the water-base resin (a) of reactive functional groups (x) to use.
Above-mentioned filming forms composition (II) except containing the water-base resin (f) that can contain reactive functional groups (y), can also contain linking agent (g), particularly water-base resin (f) and not contain under the situation of reactive functional groups (y), and be preferred also with linking agent (g).
Linking agent (g) be have can with the compound of the functional group (y) of contained reactive functional groups (x) reaction in the granulated gel (I), specifically can enumerate for example hydrazine derivative, melamine resin, polyisocyanate crosslinking agent etc.
Can be used as hydrazine derivative and melamine resin that linking agent (g) uses, can from the material described in the linking agent (d) of granulated gel (I), suitably select to use.
As above-mentioned polyisocyanate crosslinking agent, for example, can enumerate aliphatic diisocyanates such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysinediisocyanate; 4, alicyclic diisocyanates such as 4 '-methylene radical two (hexanaphthene isocyanic ester), isophorone diisocyanate; Aromatic diisocyanates such as xylylene vulcabond, tolylene diisocyanate, diphenylmethanediisocyanate, many methylenebis phenyl isocyanates; Similar compounds such as the isocyanuric acid ester body of these vulcabond or biuret (PVC ュ ゥ レ ッ ト) body, these materials can be distinguished use separately, perhaps are used in combination more than 2 kinds or 2 kinds.
In addition, above-mentioned polyisocyanate crosslinking agent also can be the water-dispersible polyisocyanates by non-ionic emulsifier and the polyisocyanate compounds reaction that contains at least 2 isocyanate group in 1 molecule are formed.As can with this non-ionic emulsifier of above-mentioned polymeric polyisocyanate reaction, can use with as the identical material of the described above-mentioned substance of non-ionic emulsifier, especially preferably have with isocyanate group reactive activity hydrogen base and have material as the ethylene oxide unit of oxyalkylene units.
In addition, above-mentioned water-dispersible polyisocyanates, as required, also can be by with at one end have the active hydrogen base and have the silane coupling agent reaction of alkoxysilyl and the material of modification at the other end.As this silane coupling agent, for example, can enumerate N-β-(amino-ethyl)-γ-ammonia-Ji propyl trimethoxy silicane, N-β-(amino-ethyl)-gamma-amino propyl group methyl dimethoxysilane, γ-An Jibingjisanyiyangjiguiwan, N-phenyl-gamma-amino propyl trimethoxy silicane, γ-Qiu Jibingjisanjiayangjiguiwan etc.
As the commercial goods of this water-dispersible polyisocyanates, for example, can enumerate " バ ィ ヒ ジ ュ one Le 3100 ", " VPLS2319 " (trade(brand)name is more than made for Bayer company) etc.
The content of linking agent (g) is preferably with respect to 1 molar reactive functional group (x) in the reaction object granulated gel (I) in the formation composition (II) of filming, the amount of the reactive functional groups (y) in the linking agent (g) is generally adjusted to be in 0.05～2 mole, preferably 0.1～1 mole scope.
In addition, according to circumstances, filming forms composition (II) and can contain globe, can improve thus the texture of filming of forming and sense of touch etc.This globe is the hollow form particle that has the cavity in shell (shell), and it can comprise resene globe and mineral-type globe.Common gases (representational is air) be can enclose in the cavity of this globe, but decompression or vacuum according to circumstances also can be.
Shell in the resene globe can be by various resin formation, formation monomeric unit as this resin, for example, can enumerate vinyl cyanide, acrylamide, vinylformic acid, acrylate, methacrylonitrile, Methacrylamide, methacrylic acid, methacrylic ester, vinylchlorid, vinylidene chloride etc., these monomers can be distinguished separately or combination (being total to) polymerization more than 2 kinds or 2 kinds.In addition, can be by in these monomers, adding a small amount of suitable cross-linkable monomer, for example Vinylstyrene, dimethacrylate macrogol ester, cyanacrylate, trimethylolpropane trimethacrylate, three propenyl methylals (ト リ ァ Network リ Le ホ Le マ one Le) etc., and (being total to) polymerization forms crosslinked shell.
As the inanimate matter globe, for example, can enumerate glass globe, silicon globe (シ ラ ス バ Le one Application), the spherical thing of aluminum oxide, the spherical thing of zirconium white, aluminosilicate globe etc., these can distinguish use separately, perhaps are used in combination more than 2 kinds or 2 kinds.In addition, also can suitably above-mentioned resene globe and inanimate matter globe be used in combination.
The use level of preferred above-mentioned globe forms the water-base resin (f) contained in the composition (II) and the total solids composition of linking agent (g) with respect to filming, usually at 0.5～15 quality %, preferably in the further preferred scope of 0.7～15 quality % at 1～10 quality %.
The formation composition (II) of filming can be to form painted composition of filming or also can be the composition that forms transparent coating, can contain tinting material as required under the painted situation of filming of formation.
As the tinting material that can in the formation composition (II) of filming, contain, can be from suitably selecting in the material that preamble is enumerated as the tinting material that granulated gel (I), can contain and using.Using under the situation of water-based paint compositions of the present invention as colorful artistic coating, from the drying property that improves colorful artistic coating, suitably the viewpoint that improves gloss and sense of touch is considered, preferably cooperates foregoing body pigment in this water-based paint compositions.When in the formation composition (II) of filming, cooperating tinting material and/or body pigment, its total use level is with respect to the total solids composition of contained water-base resin (f) and linking agent (g) in the formation composition (II) of filming, usually can be at 5～200 quality %, preferably at 10～150 quality %, further preferably in the scope of 15～120 quality %.
Water-based paint compositions:
Coating composition of the present invention, can the above-mentioned granulated gel (I) and the coating that forms composition (II) and use as required of filming be mixed together with additive by known method itself, and suitable aqueous medium is adjusted viscosity and/or pH prepares by adding.In addition, filming forms in the composition (II), when using polyisocyanate crosslinking agent as linking agent, preferably mixes this polyisocyanate crosslinking agent before coating composition uses.
As this coating additive, can enumerate as illustrated neutralizing agent in the preamble granulated gel (I), thickening material, tensio-active agent, watery water-proofing agent, dispersion agent, defoamer, sanitas, mould inhibitor, antifreezing agent, UV light absorber, photostabilizer, film coalescence aid, the zinc whisker, curing catalyst, formaldehyde adsorbent, wax, alkyl silicate condenses or make the modification of alkyl silicate condenses and the anti-pollution agent such as modification alkyl silicate that form with polyalkylene glycol, ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide, fire retardants such as aluminium hydroxide, spices, antiseptic-germicide, surface conditioner etc.
The granulated gel in the coating composition of the present invention (I) and the mixture ratio that forms composition (II) of filming can change according to the purposes of coating composition, so that granulated gel (I)/filming forms the solids component mass ratio of composition (II), usually can be 1/99～80/20, preferably 20/80～75/25, further preferably in 25/75～45/55 scope.
Consider that from viewpoints such as storage stabilitys coating composition of the present invention can have 200～10 usually, 000mPas, preferred 1,000～4, the viscosity of 000mPas scope and 6.0～13.0, the pH of preferred 7.0～12.0 scopes.
In this specification sheets, the viscosity of coating composition is that specimen temperature is adjusted to 20 ℃, uses Brookfield viscometer, changes the value of measuring with No.4 rotor, 60, and pH is adjusted to 20 ℃ with specimen temperature, with the value of pH meter " TOAHM40V " mensuration.
Few and the protection that can form excellent performances such as water tolerance, appearance of film of organic solvent content in the coating composition of the present invention is filmed; and go for for example as colorful artistic coating or other artistry coating, as various uses such as stone material tone coating, sandstone tone coating, leather tone coating, pottery tone coating.
Coating process:
Coating composition of the present invention can be by filming in the protection of substrate surface coating formation excellent performances such as water tolerance, appearance of film.
Substrate surface as applicable coating composition of the present invention, for example, wallpaper face that can enumerate coated surfaces such as substrate surfaces such as plasterboard, concrete wall, mortar wall, slabstone, PC plate, ALC plate, cement calcium silicate board, timber, stone material, plastic former, metal work material, the crylic acid resin that on these base materials, is provided with, acrylated polyurethane resin class, polyurethane type resin, fluorine type resin, silicon crylic acid resin, VINYL ACETATE MONOMER (VAM) class, epoxy resin, forms by materials such as polyvinyl chloride, polyolefine, paper, cloth etc.
The glue spread of water-based paint compositions of the present invention can change according to the composition of employed coating composition and the kind of base material to be coated etc., but usually can be 100～1,000g/m
2, preferably at 200～500g/m
2Scope.
Water-based paint compositions coating of the present invention can be undertaken by known coating process itself, for example, can be undertaken by using applicating implements such as roller, air gun, airless sprayer, resin spray gun (リ シ Application ガ Application), omnipotent spray gun, brush.
The drying of filming of forming can be undertaken by any method in heat drying, forced drying or the Air drying according to the composition of the coating composition that uses etc.In addition, in this specification sheets, the drying of carrying out under less than 40 ℃ drying conditions is an Air drying, 40 ℃ or above and less than 80 ℃ drying conditions under the drying of carrying out be forced drying, the drying of carrying out under 80 ℃ or above drying conditions is a heat drying.
When coating composition of the present invention is for example filmed as protection, can after being coated with bottom-coating in advance on the substrate surface, be coated with coating water-based paint compositions of the present invention on the face in formed primary coat.
As above-mentioned bottom-coating, can suitably select according to the kind and the state of substrate surface, for example, can use sealing priming paint, ground to adjust bottom-coatings such as material.In addition, can be coated with the substrate formation coating of common outer coating paint as coating composition of the present invention.
As this substrate formation outer coating paint, for example, can enumerate comprise by acrylic resin, polyolefin resin, silicon resinoid, polyurethanes resin, redix, resin kind such as phenolic resinoid, polyester resin, alkyd based resin and the water system that forms or solvent based resin are as the coating of resin glue, and preferred the use comprises the resinoid coating of water.
In the coating bottom-coating, as required, also can the bottom-coating of overlapping coating more than 2 kinds or 2 kinds.
The coating of above-mentioned bottom-coating can be carried out with known coating process itself, for example, can be undertaken by using applicating implements such as roller, air gun, airless sprayer, resin spray gun, omnipotent spray gun, brush.
The glue spread of above-mentioned bottom-coating can change according to the kind of coated substrate etc., but usually can be 50～2,000g/m
2, preferably 70～1,000g/m
2Scope.
The drying that formed primary coat is filmed can be undertaken by any means in heat drying, forced drying or the Air drying according to the kind of the bottom-coating that uses etc.
If use water-based paint compositions of the present invention, the protection that then can form processibility, water tolerance, has excellent weather resistance is filmed, but as required, also can be on the filming of water-based paint compositions of the present invention the further known outer coating paint of coating itself.
Embodiment
Below, be described more specifically the present invention by embodiment, but the present invention and only limit to these embodiment.In addition, " part " in the following example and " % " represent " mass parts " and " quality % " respectively.
The preparation of emulsion
Preparation example 1
In capacity is 2 liters four neck flasks, add 285 parts of deionized waters and 1 part " ニ ュ one コ one Le 707SF " (annotating 1), behind the nitrogen replacement, remain on 85 ℃.Respectively to wherein adding 3% of the pre-emulsion that forms by the composition emulsification that makes following composition, in 123 parts of initiator solutions that form with making 3 parts of ammonium persulphates be dissolved in 120 parts of deionized waters 41 parts, after adding 20 minutes, remaining pre-emulsion and remaining ammonium persulfate aqueous solution are splashed into to flask with 4 hours.
368 parts of deionized waters
150 parts of vinylbenzene
413 parts of methyl methacrylates
240 parts of n-butyl acrylates
150 parts of 2-EHAs
20 parts of diacetone-acryloamide(DAA)s
Diacrylate 1,5 parts of 6-hexylene glycol esters
20 parts of vinylformic acid 2-hydroxy methacrylates
2 parts in vinylformic acid
66 parts of " ニ ュ one コ one Le 707SF " (annotating 1).
After dropwising, it was further kept 2 hours at 85 ℃ down, be cooled to 40～60 ℃ then.Then, adjust pH, obtain solids component and be 55% emulsion (a1) with ammoniacal liquor.The median size of emulsion (a1) is 170nm, and pH is 8.3.
(annotate 1) " ニ ュ one コ one Le 707SF ": trade(brand)name, Japanese emulsifying agent company makes, and has the anion surfactant of polyethylene oxide chain, and nonvolatile component is 30%.
Preparation example 2
Except that using the pre-emulsion that forms by the composition emulsification that makes following composition to replace the pre-emulsion in the above-mentioned preparation example 1 and preparation example 1 similarly prepares emulsion (a2).The solids component of emulsion (a2) is 55%, and median size is 175nm, and pH is 8.2.
368 parts of deionized waters
150 parts of vinylbenzene
430 parts of methyl methacrylates
240 parts of n-butyl acrylates
150 parts of 2-EHAs
20 parts of vinylformic acid 2-hydroxy methacrylates
10 parts in vinylformic acid
66 parts of " ニ ュ one コ one Le 707SF " (annotating 1).
The preparation of aqueous clear coating
Preparation example 3
By in 1 liter stainless steel vessel, adding following compositions, and mixed 30 minutes, obtain aqueous clear coating (C1) with stirrer.
750 parts of 55% emulsions (a1)
9 parts in water
50 parts of " TEXANOL " (annotating 2)
10 parts of " SN デ Off ォ one マ 1 " (annotating 3)
6 parts of " ァ デ カ ノ one Le UH-438 " (annotating 4).
(annotating 2) " TEXANOL ": trade(brand)name, ィ one ス ト マ Application ケ ミ カ Le company makes, and 2,2,4-trimethylammonium-1,3-pentanediol mono isobutyrate, film coalescence aid.
(annotating 3) " SN デ Off ォ one マ 1 ": trade(brand)name, サ Application ノ プ コ company makes, defoamer.
(annotating 4) " ァ デ カ ノ one Le UH-438 ": trade(brand)name, ァ デ カ company makes, thickening material.
Preparation example 4
Become the following substances and preparation example 3 is similarly made aqueous clear coating (C2) except the one-tenth in the above-mentioned preparation example 3 is grouped into.
750 parts of 55% emulsions (a2)
61 parts of " TEXANOL " (annotating 2)
10 parts of " SN デ Off ォ one マ 1 " (annotating 3)
6 parts of " ァ デ カ ノ one Le UH-438 " (annotating 4)
60 parts in water
80 parts of " Le Network T-1 " (annotating 5)
28 parts of " マ ッ モ ト マ ィ Network ロ ス Off ェ ァ one F-80E " (annotating 6).
(annotating 5) " Le Network T-1 ": trade(brand)name, the of Fuji Le Network industrial makes, talcum.
" マ ッ モ ト マ ィ Network ロ ス Off ェ ァ one F-80E " (annotating 6): trade(brand)name, this grease of pine company makes, acrylonitrile resin near-spherical thing, effective constituent is 15%.
The preparation of white pigments thickener
Preparation example 5
By in 1 liter stainless steel vessel, adding following compositions, and with dispersion machine stir 30 minutes even until it, obtain the white pigments thickener.
45 parts in water
3 parts of " ス ラ ォ Off 72N " (annotating 7)
6 parts of " DISPER BYK-190 " (annotating 8)
100 parts of " TITANIXJR-605 " (annotating 9).
(annotate 7) " ス ラ ォ Off 72N ": trade(brand)name, Japanese エ Application バ ィ ロ ケ ミ カ Le ズ company makes sanitas.
(annotating 8) " DISPER BYK-190 ": trade(brand)name, BYK ケ ミ one company makes, dispersion agent.
(annotating 9) " TITANIX JR-605 ": trade(brand)name, テ ィ カ company makes, titanium white.
The preparation of granulated gel use fluid composition
Preparation example 6
In container, cooperate following compositions successively, and mix and make it even, obtain granulated gel use fluid composition (A-1).
154 parts of white pigments thickeners
250 parts of 55% emulsions (a1)
20 parts of " TEXANOL " (annotating 2)
2 parts of " SN デ Off ォ one マ 1 " (annotating 3)
2 parts of " ァ デ カ ノ one Le UH-438 " (annotating 4)
280 parts of the 2% sodiun alginate aqueous solution.
Preparation example 7～16
Except the cooperation in the above-mentioned preparation example 6 is formed become the cooperation shown in the following table 1 form and preparation example 6 similarly prepare water-based fluid composition (A-2)～(A-11).
Table 1
| Preparation example | ||||||||||||
| 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 | ||
| The water-based fluid composition | A-1 | A-2 | A-3 | A-4 | A-5 | A-6 | A-7 | A-8 | A-9 | A-10 | A-11 | |
| Resinous principle | 55% emulsion (a1) | 250 | 250 | 250 | 250 | 250 | ||||||
| 55% emulsion (a2) | 250 | 250 | 250 | 250 | ||||||||
| Aqueous clear coating (C1) | 392.3 | 392.3 | ||||||||||
| Tinting material | The white pigments thickener | 154 | 154 | 154 | 154 | 154 | 154 | 154 | 154 | |||
| Red thickener (annotating 10) | 4 | 12 | 12 | |||||||||
| Phthalocyanine thickener (annotating 11) | 12 | 4 | 12 | |||||||||
| Aluminium thickener (annotating 12) | 38.2 | |||||||||||
| Solidifying agent | The 10% adipic dihydrazide aqueous solution | 4.2 | 7.7 | 7.7 | ||||||||
| サ ィ メ Le 327 (annotating 13) | 10 | 10 | ||||||||||
| Additive | " TEXANOL " (annotating 2) | 20 | 20 | 20 | 20 | 20 | 20 | 20 | ||||
| " SN デ Off ォ-マ-380 " (annotating 3) | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | |||
| " ァ デ カ ノ-Le UH-438 " (annotating 4) | 2 | 2 | 2 | 1 | 1 | 2 | 2 | 2 | 2 | 2 | 2 | |
| Jelling agent | The 2% sodiun alginate aqueous solution | 280 | 280 | 300 | 230 | 230 | 280 | 300 | 180 | 200 | ||
| 2% exocellular polysaccharide glue solution | 280 | 280 | ||||||||||
(annotating 10) red thickener: adjust " ト 88 is red for ュ ニ ラ Application " (trade(brand)name, Yokohama change into company and make) and make pigment content be about 30% colored thickener.
(annotating 11) phthalocyanine thickener: adjust " ト 88 is green for ュ ニ ラ Application " (trade(brand)name, Yokohama change into company and make) and make pigment content be about 20% colored thickener.
(annotating 12) aluminium thickener: in mixing container, (company of Asahi Chemical Industry makes to add 45.5 parts of aluminium pigment thickeners " MG-51 ", aluminium content is 66%, and hydro carbons and petroleum-type organic solvent are 34%), the resin solution of 35 parts of ethylene glycol monobutyl ether and 3 parts of phosphorous acidic groups (is annotated
*), and mix and the aluminium pigment thickener that obtains.
(annotate
*) resin solution of phosphorous acidic group: in reaction vessel with agitator, thermoswitch and cold-hot machine, the mixed solvent that adds 27.5 parts of pure and mild 27.5 parts of isopropylcarbinols of methoxy propyl, be heated to 110 ℃, in above-mentioned mixed solvent, added by the polymerizable monomer of 25 parts of vinylbenzene, 27.5 parts of n-BMAs, 20 parts " iso stearyl acrylate " (organic chemistry company in Osaka makes, side chain senior alkyl acrylate), 7.5 parts of vinylformic acid hydroxyl butyl esters, 15 part of 50% phosphorous acidic group with 4 hours and (to annotate
*), 12.5 parts of acid phosphoric acid 2-iso-butylene acyl-oxygen base ethyl esters, 10 parts of isopropylcarbinols and 4 parts of 121.5 parts of mixtures that the tert-butyl hydroperoxide octanoate is formed, then splashed into by 0.5 part of tert-butyl hydroperoxide octanoate and 20 parts of mixtures that isopropylcarbinol is formed with 1 hour.Afterwards, stir slaking and obtained the resin solution that solids component is 50% phosphorous acidic group in 1 hour.
(annotate
*) polymerizable monomer of phosphorous acidic group: in reaction vessel with agitator, thermoswitch and cold-hot machine, add 57.5 parts of mono-Dodecyl phosphates and 41.1 parts of isopropylcarbinols, and under airiness, splashed into 42.5 parts of glycidyl methacrylate, and then stir slaking 1 hour with 2 hours.Afterwards, add 5.9 parts of Virahols, obtain solids component and be the polymerizable monomer solution of 50% phosphorous acidic group.
(annotating 13) " サ ィ メ Le 327 ": trade(brand)name, Mitsui サ ィ テ ッ Network company makes, melamine resin.
The preparation of granulated gel
Preparation example 17
In 4 liters stainless steel vessel, add 1,300 part of 0.15% calcium hydroxide (annotating 14) aqueous solution, be that the paddle of 75mm is with 2 on one side with diameter, the speed of rotation of 500rpm stirs, to container in slowly splash into the 650 part above-mentioned water-based fluid compositions (A-1) that obtain on one side, generate granulated gel.Then with identical speed of rotation with the liquid restir in the container 15 minutes, carry out filtering separation with 200 purpose wire nettings then, obtain granulated gel (I-1).Solids component is 20% in the granulated gel that obtains (I-1), and size is at 75 μ m or above and be 95% less than the granulated gel of 500 μ m at the ratio in whole granulated gels.
(annotating 14) calcium hydroxide: in the water of 25 ℃ of 100g, dissolve 0.15g.
Preparation example 18
In 4 liters stainless steel vessel, add 24 parts of calcium hydroxides and 1,200 part of deionized water, with diameter be the paddle of 75mm with the speed of rotation of 1500rpm stirring on one side, in container, slowly splash into 600 parts of above-mentioned water-based fluid compositions (A-2) on one side, generate granulated gel.Then with identical speed of rotation with the liquid restir in the container 15 minutes, carry out filtering separation with 200 purpose wire nettings then, obtain granulated gel (I-2).Solids component is 20% in the granulated gel that obtains (I-2), and size is at 150 μ m or above and be 95% less than the granulated gel of 2000 μ m at the ratio in whole granulated gels.
Preparation example 19～27
The water-based fluid composition (A-1) in using the water-based fluid composition replacement preparation example 17 shown in the following table 2, other and above-mentioned preparation example 17 are operated equally, obtain granulated gel (I-3)～(I-11).
Table 2
| Preparation example | |||||||||||
| 17 | 18 | 19 | 20 | 21 | 22 | 23 | 24 | 25 | 26 | 27 | |
| The granulated gel name | 1-1 | 1-2 | 1-3 | 1-4 | 1-5 | 1-6 | 1-7 | 1-8 | 1-9 | 1-10 | 1-11 |
| Water-based fluid composition kind | A-1 | A-2 | A-3 | A-4 | A-5 | A-6 | A-7 | A-8 | A-9 | A-10 | A-11 |
| Solids component | 20％ | 20％ | 20％ | 20％ | 20％ | 20％ | 20％ | 20％ | 20％ | 20％ | 20％ |
| Particle diameter (μ m) x～y: more than or equal to x and less than the ratio of y in whole granulated gels | 75～500 95％ | 150～2000 95％ | 75～500 95％ | 75～500 95％ | 75～500 95％ | 75～500 95％ | 75～500 95％ | 75～500 95％ | 75～500 95％ | 75～500 95％ | 75～500 95％ |
Preparation example 28
In 4 liters stainless steel vessel, add 600 part of 5% calcium chloride water, on one side with diameter be the paddle of 75mm with the rotation of the speed of rotation of 3000rpm, in container, slowly splash into 660 parts of water-based fluid compositions (A-3) on one side, the generation granulated gel.Then with identical speed of rotation with the liquid restir in the container 15 minutes, carry out filtering separation with 200 purpose wire nettings then, obtain granulated gel (I-12).Solids component is 20% in the granulated gel (I-12), and size is at 250 μ m or above and be 80% less than the ratio of the granulated gel of 2000 μ m.
Preparation example 29
The water-based fluid composition (A-3) in making the above-mentioned preparation example 28 of use fluid composition (A-9) replacement, other and above-mentioned preparation example 28 are operated equally, obtain granulated gel (I-13).Solids component is 16.5% in the granulated gel (I-13), and size is at 250 μ m or above and be 80% less than the ratio of the granulated gel of 2000 μ m.
The preparation of colorful artistic coating
Embodiment 1～12 and comparative example 1～2
In 500 milliliters stainless steel vessel, add the composition shown in the following table 3 successively while stir, further stir then, obtain colorful artistic coating (P1)～(P12) thus.The proterties of gained coating and film performance test-results are shown in Table 3 in the lump.
Table 3
| Colorful artistic coating | Embodiment | Comparative example | ||||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 1 | 2 | |||
| P1 | P2 | P3 | P4 | P5 | P6 | P7 | P8 | P9 | P10 | P11 | P12 | P13 | P14 | |||
| Mix | The formation composition of filming | Aqueous transparent (C1) | 130 | 100 | 140 | 130 | 130 | 140 | 130 | 130 | ||||||
| Aqueous transparent (C2) | 130 | 130 | 130 | 130 | 130 | 130 | ||||||||||
| 10% adipic dihydrazide | 2.5 | 1.9 | 2.7 | 3 | 2.7 | |||||||||||
| バ ィ ヒ ジ コ one Le 3100 (annotating 15) | 3.3 | 3.3 | ||||||||||||||
| サ ィ メ Le 327 (annotating 13) | 4.2 | 8.4 | 4.2 | |||||||||||||
| Colored particles | Granulated gel (I-1) | 145 | 150 | 145 | ||||||||||||
| Granulated gel (I-2) | 80 | 145 | 80 | |||||||||||||
| Granulated gel (I-3) | 15 | 50 | ||||||||||||||
| Granulated gel (I-4) | 50 | 35 | 15 | 35 | ||||||||||||
| Granulated gel (I-5) | 35 | 15 | 20 | |||||||||||||
| Granulated gel (I-6) | 145 | 145 | 145 | 145 | ||||||||||||
| Granulated gel (I-7) | 145 | 145 | 145 | |||||||||||||
| Granulated gel (I-8) | 15 | 15 | ||||||||||||||
| Granulated gel (I-9) | 15 | |||||||||||||||
| Granulated gel (I-10) | 15 | 15 | 15 | |||||||||||||
| Granulated gel (I-11) | 15 | 15 | 30 | 15 | 15 | |||||||||||
| Granulated gel (I-12) | 15 | 15 | 30 | |||||||||||||
| Granulated gel (I-13) | 18.2 | 18.2 | 212 | |||||||||||||
| Additive | ァ デ カ ノ one Le UH-438 (annotating 4) | 0.3 | 0.4 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | |
| Water | 26 | 41 | 36 | 38 | 23 | 45 | 30 | 30 | 30 | 30 | 30 | 30 | ||||
| Granulated gel/formation the composition of filming | 65/35 | 50/50 | 70/30 | 65/35 | 65/35 | 65/35 | 65/35 | 65/35 | 65/35 | 65/35 | 65/35 | 65/35 | 65/35 | 65/35 | ||
| The coating proterties | Solids component (%) | 30 | 29 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 29 | 30 | |
| Viscosity (mPas) | 2300 | 2500 | 2800 | 2200 | 2400 | 1800 | 1700 | 2300 | 2200 | 2700 | 2400 | 2600 | 1900 | 2400 | ||
| pH | 9.5 | 9.7 | 9.3 | 9.5 | 9.5 | 9.2 | 9.2 | 9.5 | 9.5 | 9.4 | 9.3 | 9.3 | 8.3 | 9.2 | ||
| Film performance | Appearance of film (* 1) | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | △ | ◎ | |
| Water tolerance (* 2) | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | × | △ | ||
| Storage stability (* 3) | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | ○ | ||
| Low-temperature stability (* 4) | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | ○ | ||
(annotating 15) " バ ィ ヒ ジ ュ one Le 3100 ": trade(brand)name, バ ィ ェ Le company makes, the water-dispersible polyisocyanates solidifying agent.
The film performance test
The preparation of test coated plate
(150 * 70 * 3mm) go up roller coat coating " EP シ one ラ one is transparent " (Northwest ペ ィ Application ト company makes, and the water system ACRYLIC EMULSION is a sealing agent), and making glue spread is 100g/m at slabstone
2, after the drying, roller coat coating " PVC ニ デ ラ ッ Network ス 300 " (Northwest ペ ィ Application ト company makes, 5663,1 kinds of suitable ACRYLIC EMULSION class coating of JIS K), making glue spread is 100g/m
2, and be 20 ℃ at temperature, relative humidity is under 60% the condition dry 1 day, and as by coated plate, spraying thereon is coated with each colorful artistic coating with the plate of gained, and making glue spread is 300g/m
2Then, for the coated plate of embodiment 1～4,6,8,10,11 and comparative example 1～2, be 23 ℃ at temperature, relative humidity is under 60% the condition dry 7 days, is respectively tested coated plate.The test coated plate that is obtained by embodiment 5,7,9 and 12 carried out 30 minutes baking with the electronics drying machine under 140 ℃ after under 80 ℃ dry 10 minutes.
The above-mentioned test coated plate that obtains is used for following performance test.
(
*1) appearance of film
Visual observations is respectively tested filming of coated plate, estimates with following benchmark.
◎: very good,
Zero: good,
△: bad slightly,
*: have paint film defects such as crack or contraction.
(
*2) water tolerance
With each test coated plate proofing 4 days in 23 ℃ tap water, after the taking-up, visual observation is estimated with following benchmark.
◎: good,
Zero: observe some gloss reduction, but be realistic scale,
△: observe gloss reduction, albefaction and expansion,
*: observe marked inflation, it is softening perhaps to film.
(
*3) storage stability
In being 1 liter interior finishing coat jar, capacity puts into each colorful artistic coating of 1kg, and storage 60 days in 40 ℃ thermostatic chamber.Then, return to room temperature, the state of coating in the visual observation container is estimated with following benchmark.
Zero: do not observe separation, and do not observe the fusion or the destruction of granulated gel,
△: observe soft junction piece or separation, but become evenly by stirring,
*: observe scleroma piece or separation, and can't restore to the original state.
(
*4) low temperature storage stability
In being 1 liter interior finishing coat jar, capacity puts into each colorful artistic coating of 1kg, with after storage under-5 ℃ 18 hours → storage was an one-period in 6 hours under 20 ℃, repeated 3 times like this, return to room temperature, the state of coating in the visual observation container is estimated with following benchmark.
Zero: no problem,
△: observe the soft junction piece, but become evenly by stirring,
*: observe scleroma piece or separation, and can't restore to the original state.
Claims (17)
1, a kind of water-based paint compositions, it comprises granulated gel (I) and films formation composition (II), described granulated gel (I) in polyose metal-salt gel (b) in bag water-based fluid composition form, this water-based fluid composition contains water-base resin (a) and has reactive functional groups (x), described film form composition (II) contain can with the reactive functional groups (y) of reactive functional groups (x) reaction.
2, the described water-based paint compositions of claim 1, wherein, the combination of described reactive functional groups (x) and described reactive functional groups (y) is selected from the combination of carbonyl and hydrazine residue, hydroxyl and isocyanate group, hydroxyl and alkylether radicals and hydroxyl and imino-.
3, claim 1 or 2 described water-based paint compositions, wherein, described water-base resin (a) is the water-base resin that contains reactive functional groups (x).
4, the described water-based paint compositions of claim 3, wherein, described reactive functional groups (x) is carbonyl or hydroxyl.
5, any described water-based paint compositions in the claim 1～4, wherein, described water-based fluid composition contains linking agent.
6, the described water-based paint compositions of claim 5, wherein, described linking agent is hydrazine derivative or melamine resin.
7, any described water-based paint compositions in the claim 1～6, wherein, described water-based fluid composition contains metallic pigment and/or pearly-lustre tone pigment.
8, any described water-based paint compositions in the claim 1～7, wherein, the described formation composition (II) of filming comprises the water-base resin that contains reactive functional groups (y).
9, the described water-based paint compositions of claim 8, wherein, described reactive functional groups (y) is carbonyl or hydroxyl.
10, any described water-based paint compositions in the claim 1～9, wherein, the described formation composition (II) of filming also contains linking agent.
11, the described water-based paint compositions of claim 10, wherein, described linking agent is selected from hydrazine derivative, melamine resin and polyisocyanate compounds.
12, any described water-based paint compositions in the claim 1～11, wherein, the described formation composition (II) of filming also contains body pigment.
13, any described water-based paint compositions in the claim 1～12, wherein, described granulated gel (I) is by making the water-based fluid composition that contains water-base resin (a) and water-soluble polysaccharides (b1) contact the gel that obtains with the aqueous medium that contains metal ion.
14, any described water-based paint compositions in the claim 1～13, wherein, the described formation composition (II) of filming also contains globe.
15, any described water-based paint compositions in the claim 1～14, wherein, form the solids component mass ratio of composition (II) in granulated gel (I)/film, the mixture ratio of the described granulated gel (I) and the formation composition (II) of filming is in 1/99～80/20 scope.
16, a kind of coating process is characterized in that, any described water-based paint compositions in the coating claim 1～15 on substrate surface.
17, a kind of coating process is characterized in that, behind coating bottom-coating on the substrate surface, is coated with on the face any described water-based paint compositions in the coating claim 1～15 in formed primary coat.
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| JP2005-252039 | 2005-08-31 | ||
| JP2005252039 | 2005-08-31 | ||
| JP2005252039 | 2005-08-31 | ||
| JP2006030687 | 2006-02-08 | ||
| JP2006030687 | 2006-02-08 | ||
| JP2006-030687 | 2006-02-08 |
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| CN100999625B CN100999625B (en) | 2010-11-10 |
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