CN101230141B - Method for manufacturing granulated gel and coating composition having the same - Google Patents
Method for manufacturing granulated gel and coating composition having the same Download PDFInfo
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- CN101230141B CN101230141B CN2008100037918A CN200810003791A CN101230141B CN 101230141 B CN101230141 B CN 101230141B CN 2008100037918 A CN2008100037918 A CN 2008100037918A CN 200810003791 A CN200810003791 A CN 200810003791A CN 101230141 B CN101230141 B CN 101230141B
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Abstract
The invention provides a manufacturing method of granulated gel and coating composition formed of the granulated gel obtained from the manufacturing method combined with coating film forming ingredient. The granulated gel manufacturing method comprises bringing aqueous liquid compound including waterborne resin, colorant and water-soluble polysaccharide into contact with water medium containing metal compound, characterized in that organic acid metal salt serves as a component part of the metal compound.
Description
Technical field
The coating composition that the present invention relates to the method for manufacture of granulated gel and contain this granulated gel.
Background technology
Through water-soluble polymer polyoses such as sodiun alginate are contacted with the aqueous solution that calcium chloride water etc. contains metals ion, the method for liquid particle being sealed with gelating film is known, is widely used in the fields such as food, chemistry, biology.
As this method of sealing; For example; Enzyme or the immobilizing microbial cells method of manufacture with granular forming composition is disclosed in the japanese kokai publication hei 10-152511 communique; This method comprises: in the aqueous medium that contains alkalimetal ion or polyvalent metal ion, drip the water-based fluid composition that contains wetting ability light-cured resin, Photoepolymerizationinitiater initiater, water-soluble polymer polyose and inorganic powder body; Make said composition form granulated gel, then resulting granulated gel is shone active ray, the light-cured resin in this granulated gel is solidified.
In addition, the water-soluble polymer by a metal ion forming polysaccharide gel methods have been used in the coatings art, as an example of the use, there are various patterns paint (paint specifications colorful mode).Multicolor pattern paint is once to be coated with just to form the coating of filming with 2 looks above colorful pattern; For example can enumerate; Make multiple painted granulated gel stably be dispersed in the coating that forms in the dispersion medium, it is mainly used in the coating of buildings etc.
As multicolor pattern paint, for example, disclose in the japanese kokai publication sho 64-16879 communique that containing films emulsion resin etc. with the gelating film of water-soluble high-molecular compound is formed into the colored coating composition that branch is sealed the liquid colored particles that forms.According to said composition, can form filming of the excellent outward appearance of changeful appearance design property, but have difficult point aspect the rerum naturas of filming such as water tolerance of filming.
Further, disclose in the japanese kokai publication hei 07-247450 communique and use the flakey gel colored particles and the combination conduct of colored or painted microfine globular particle to be dispersed in the aqueous colorful coating composition of painted framework material in the aqueous medium.If use said composition; Then can easily look and recognize colourful pattern and can form level and smooth, concavo-convex few filming; But in order to make the essential miscellaneous step of flakey gel colored particles, in addition, owing to when making the gel colored particles, use compounds such as calcium chloride, Tai-Ace S 150; Might corrode the metal part of manufacturing installation, further have the inadequate problem of the water tolerance of filming that forms by this coating composition.
For this problem, disclosing through containing this communique defined " chemicalstability " in the TOHKEMY 2004-182788 communique is that the painted water-borne coatings of the synthetic resin emulsion below the 3 weight % is dispersed in the method for making painted gel particles in the aqueous medium that contains polyvalent metal salt.The multicolor pattern paint compsn that contains painted gel particles through this method manufacturing; Can form filming of excellences such as smoothness, water tolerance, weathering resistance; But because the chemicalstability of synthetic resin emulsion is low; Produce residue and stop up problems such as pipe arrangement, in the coating manufacturing step, have the shortcoming that stably to produce.
Summary of the invention
The objective of the invention is to, provide and stably to produce the method for the excellent granulated gel of storage stability and the coating composition that contains this granulated gel with easy method.
The inventor furthers investigate in order to reach above-mentioned purpose; The result finds, this time, contacts with the aqueous medium that contains specific metallic compound through making the water-based fluid composition that contains water-base resin, tinting material and water-soluble polysaccharides; Can easily make the excellent granulated gel of storage stability; In addition, can this granulated gel be advantageously used in the coating compositions such as multicolor pattern paint, thereby accomplish the present invention.
The present invention provides the method for manufacture of a kind of granulated gel (C); This method is for comprising the method that makes the manufacturing granulated gel (C) that the water-based fluid composition (A) that contains water-base resin (a), tinting material (b) and water-soluble polysaccharides (c) contacts with the aqueous medium that contains metallic compound (d) (B); It is characterized in that metallic compound (d) contains the part of metal salts of organic acids (d1) as its composition.
In addition, the present invention provides a kind of coating composition, and this coating composition forms in the granulated gel that obtains through above-mentioned method of manufacture (C), cooperating the formation composition (D) of filming.
Manufacturing method according to the invention; Through using water-soluble polysaccharides and specific metallic compound as jelling agent; Can be easily and stably make the excellent granulated gel of storage stability, in addition, method of manufacture of the present invention has for the little advantage of the load of environment or manufacturing installation.And the concave-convex sense that the coating composition that contains the granulated gel that obtains by method of the present invention can form the face of being coated with is little, clarity (clarity) etc. becomes filming of the physical properties excellent of filming such as moral character (Ga り on the bodyguard) excellence, resistance to water.
Embodiment
Hereinafter is explained the method for manufacture of granulated gel of the present invention and the coating composition that contains this granulated gel more specifically.
Water-based fluid composition (A):
Employed water-based fluid composition (A) contains water-base resin (a), tinting material (b) and water-soluble polysaccharides (c) in the method for the present invention.
Water-base resin (a):
Water-base resin (a) helps the weather resistance through the granulated gel (C) of method manufacturing of the present invention, and as water-base resin (a), use can be dissolved in water or the dispersive resin usually.Resin kind to water-base resin (a) does not limit especially; Specifically; For example can enumerate acrylics, polyolefin resin, silicone based resin, polyurethanes resin, redix, phenolic resinoid, polyester resin, alkyd based resin, polycarbonate resin etc.; They can distinguish independent use, or combination more than 2 kinds is used.In addition, these resins for example can be modified as ammonia ester (ゥ レ タ Application) is acrylic resin modified, perhaps also can graft polymerization.
When water-base resin (a) was the form of dispersed particle, this dispersed particle can be multilayer shapes such as individual layer shape or core-shell.In addition, consider that from the aspects such as manufacturing stability of granulated gel water-base resin (a) is preferably has anionic property group, the particularly carboxyl resin as hydrophilic radical.At this moment; This resin can be neutralized by alkali; As operable neutralizing agent this moment; For example can enumerate amines such as methylamine, dimethyl amine, Trimethylamine, ethylamine, DIETHANOL AMINE, triethylamine, dimethylaminoethanol, 2-methyl-2-amino-1-propyl alcohol, ammonia etc., they can distinguish independent use, or combination more than 2 kinds is used.
Consider from aspects such as the weather resistance of granulated gel (C), weathering resistancies,, water-base resin (a) is preferably acrylics.
As the aforesaid propylene acid resin; Can enumerate with the acrylic monomer be must monomer component, the acrylics through this monomer and other suitable polymerizability unsaturated monomer (being total to) polymerization are obtained; As can for example enumerating straight or branched (methyl) alkyl acrylates such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) NSC 20949, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, the just own ester of (methyl) vinylformic acid, (methyl) 2-EHA, (methyl) dodecylacrylate, (methyl) stearyl acrylate ester in this (being total to) polymeric acrylic monomer and other polymerizability unsaturated monomer; (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate etc. contain (methyl) propenoate of cyclic hydrocarbon group; (methyl) vinylformic acid aralkyl esters such as (methyl) vinylformic acid benzene methyl; Alkoxyalkyl (methyl) propenoate such as 2-methoxy ethyl (methyl) propenoate, 2-ethoxyethyl group (methyl) propenoate; Perfluoroalkyl (methyl) propenoate; N, N such as N-diethylamino ethyl (methyl) propenoate, N-dialkyl aminoalkyl (methyl) propenoate; (methyl) acrylic amide; (methyl) vinyl cyanide; Vinyl acetate such as vinyl-acetic ester, propionate compound; Vinyl aromatic compounds such as vinylbenzene, alpha-methyl styrene, Vinyl toluene; (methyl) allyl acrylate, ethylene glycol bisthioglycolate (methyl) propenoate, triethylene glycol two (methyl) propenoate, TEG two (methyl) propenoate, 1; 3-butyleneglycol two (methyl) propenoate, trimethylolpropane tris (methyl) propenoate, 1; 4-butyleneglycol two (methyl) propenoate, NSC 6366 two (methyl) propenoate, 1; 6-pinakon two (methyl) propenoate, tetramethylolmethane two (methyl) propenoate, tetramethylolmethane four (methyl) propenoate, glycerine two (methyl) propenoate, 1; 1; 1-trihydroxy methyl ethane two (methyl) propenoate, 1,1,1-trihydroxy methyl ethane three (methyl) propenoate, 1; 1, have many vinyl compounds of at least 2 polymerizability unsaturated groups in 1 molecules such as 1-trihydroxy methyl propane three (methyl) propenoate, cyanacrylate, diallyl terephthalate, Vinylstyrene; Hydroxyalkyl (methyl) propenoate such as 2-hydroxyethyl (methyl) propenoate, 2-hydroxypropyl (methyl) propenoate, 3-hydroxypropyl (methyl) propenoate, hydroxybutyl (methyl) propenoate, 6-caprolactone modification body, the molecular end of vinyl carbinol, above-mentioned hydroxyalkyl (methyl) propenoate is the polymerizability unsaturated monomer that (methyl) propenoate etc. that contains polyoxyethylene chain of hydroxyl contains hydroxyl; (methyl) vinylformic acid, fumaric acid, methylene-succinic acid, toxilic acid, Ba Dousuan, β-carboxy ethyl propenoate etc. contain the polymerizability unsaturated monomer of carboxyl; (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.), acetoacetoxy groups ethyl (methyl) propenoate, acetoacetoxy groups allyl ester, diacetone (methyl) acrylic amide etc. contain carbonyl; Glycidyl (methyl) propenoate, Beta-methyl glycidyl (methyl) propenoate, 3; 4-epoxycyclohexyl methyl (methyl) propenoate, 3; 4-epoxycyclohexyl ethyl (methyl) propenoate, 3,4-epoxycyclohexyl propyl group (methyl) propenoate, allyl glycidyl ether etc. contain the polymerizability unsaturated monomer of epoxy group(ing); Isocyanic ester ethyl (methyl) propenoate, pseudoallyl-α, α-Er Jiajibianji isocyanic ester etc. contains the polymerizability unsaturated monomer of NCO; Vinyltrimethoxy silane, vinyltriethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxyl silane etc. contain the polymerizability unsaturated monomer of alkoxysilyl; Reaction product, two cyclopentenes oxygen base ethyl (methyl) propenoate, two cyclopentenes oxygen base propyl group (methyl) propenoate, dicyclopentenyl (methyl) propenoate that contains the polymerizability unsaturated monomer of epoxy group(ing) or contain polymerizability unsaturated monomer and the unsaturated fatty acids of hydroxyl etc. contains polymerizability unsaturated monomer of oxidative cure property group etc.; They can distinguish independent use, or combination more than 2 kinds is used.
Consider from the aspects such as manufacturing stability of granulated gel (C); Acrylics as water-base resin (a) is preferably the acrylics that contains carboxyl; This contains the resin of carboxyl; For example, can make as at least a portion of monomer component through the polymerizability unsaturated monomer that use contains carboxyl.The said consumption that contains the polymerizability unsaturated monomer of carboxyl; Consider from the manufacturing stability and the storage stability aspect of granulated gel (C); Total mass in (being total to) polymeric polymerizability unsaturated monomer is a benchmark; Be generally 0.05～30 quality %, be preferably 0.1～5 quality % especially, further be preferably 0.3～4 quality % especially.
In addition, from granulated gel (C) the aspects such as affinity of tinting material (b) consider that above-mentioned water-base resin (a) can be for containing the acrylics of carbonyl, this acrylics that contains carbonyl preferably further contains carboxyl.This contains the acrylics of carbonyl, for example can contain the polymerizability unsaturated monomer of carbonyl at least a portion as monomer component through use as stated, makes with other polymerizability unsaturated monomer (being total to) polymerization.Total mass in (being total to) polymeric polymerizability unsaturated monomer is a benchmark, and the above-mentioned consumption that contains the polymerizability unsaturated monomer of carbonyl is generally 0.2～30 quality %, is preferably 0.2～20 quality %, further is preferably 0.3～15 quality %.
Above-mentioned monomeric polymerization method is not limited especially, for example,, in the presence of emulsifying agent,, can easily make acrylics thus above-mentioned monomer (being total to) polymerization according to general emulsion polymerization.
Employed emulsifying agent in the manufacturing as the aforesaid propylene acid resin; Can the known tensio-active agent of use itself; As operable tensio-active agent, can enumerate for example aniorfic surfactant, non-ionics, zwitterionics.
As above-mentioned aniorfic surfactant; For example can enumerate; Alkyl diphenyl base ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonates such as dodecyl diphenyl ether disulfonic acid two ammoniums, dodecyl diphenyl ether sodium disulfonate, dodecyl diphenyl ether disulfonic acid calcium, alkyl diphenyl base ether sodium disulfonate; Sulfonated alkylbenzenes such as X 2073, Witco 1298 Soft Acid ammonium, alkyl sulfuric ester salt such as sodium lauryl sulphate, ammonium lauryl sulfate, aliphatics carboxyl salt such as fatty acid sodium salt, potassium oleate; (for example contain the unitary sulfuric acid of polyoxyalkylene; Voranol EP 2001 sulfuric acids such as Voranol EP 2001 sodium sulfate, Voranol EP 2001 ammonium sulfate, polyoxyethylene alkyl phenyl ether sulfuric acids such as polyoxyethylene alkyl phenyl ether sodium sulfate, polyoxyethylene alkyl phenyl ether ammonium sulfate, T 46155 encircle phenyl ether sodium sulfate more, T 46155 encircles T 46155 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., they can distinguish independent use, or combination more than 2 kinds is used.
As above-mentioned non-ionics; For example can enumerate; Contain the unitary ether compound of polyoxyalkylene (4 as; Polyoxyalkylene alkyl compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, T 46155 tridecyl ether, polyoxyethylene oleyl ether; Polyoxyalkylene alkyl phenyl ether compounds such as polyoxyethylene octyl phenyl ether, T 46155 nonylplenyl ether, T 46155 encircle polyoxyalkylenes such as phenyl ether more and encircle phenyl ether compound etc. more), polyoxyalkylene alkyl ester compounds such as Vinlub 73, POLYOXYL 40 STEARATE, Aceonon 300 MO; Polyoxyalkylene alkyl ammonium compounds such as polyoxyethylene alkyl amine; Sorbitan compounds such as sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan mono-laurate, polyoxyethylene sorbitan monoleate etc., they can distinguish independent use, or combination more than 2 kinds is used.
As above-mentioned zwitterionics, for example can enumerate dimethyl-alkyl betaine class, dimethyl-alkyl empgen BB class, alkyl glycocoll class etc.
In addition, as mentioned emulsifier, also can use reactive emulsifier that in molecule, contains polymerizability unsaturated group and anionic property group or nonionic group etc.
Total mass with the polymerizability unsaturated monomer is a benchmark, and the consumption of mentioned emulsifier can be 0.5～6 quality % usually, is preferably 1～4 quality %.
Consider from the aspects such as weather resistance of the granulated gel (C) of manufacturing; The consumption of water-base resin (a) is a benchmark with the quality (solids component) of water-based fluid composition (A); Be generally 10～90 quality %, be preferably 15～80 quality %, further be preferably 25～70 quality %.
Tinting material (b):
Employed tinting material (b) in the method for the present invention; Play a part the proportion of adjustment granulated gel (C); Be in order to use the known tinting material of use at random itself in addition to using filming of coating composition formation of the present invention to give appearance design property, clarity, concealment property etc.
As tinting material (b), can use pigment and/or dyestuff, special preferred pigments.Specific examples of the pigment include, for example: a white pigment such as titanium dioxide; carbon black, acetylene black, lamp black, bone charcoal, graphite, iron black, aniline black, black pigment; yellow iron oxide, titanium yellow, monoazo yellow, condensed azo yellow, azomethine yellow, bismuth vanadate, benzimidazolone, iso-indolinone, isoindoline, quinophthalone, benzidine yellow, permanent yellow yellow pigment; Permanent Orange in Orange pigment ; red iron oxide, naphthol AS type azo red, anthracene embedded anthracene dione (Farmer nn thermal nn su ro nn), anthraquinone red, perylene purple (pe re re nn ma Hikaru an nn), quinacridone red pigments, diketo pyrrolo pyrrole pigment Red (Xiang-Io ッ チ nn bag Ritz ッ cloth), a permanent red red pigment; cobalt violet, quinacridone violet, two
triazine purple purple pigment; cobalt blue, phthalocyanine blue, Vat Blue (su re nn Jewellery Hikaru ~) and other blue pigment; phthalocyanine green and other green pigment; aluminum powder, bronze powder, copper powder, tin powder, iron phosphide, zinc and other metal pigments; metal oxide coated mica, micaceous iron oxide pigment pearlescent colors (true tone pearlescent pigments Kanazawa); barium oxide powder, precipitated barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, silica, white carbon, diatomaceous earth, talc, magnesium carbonate, alumina white, gloss white and extender pigment (pigment), etc. They may be used alone, or two or more kinds in combination.
In the titanium oxide as above-mentioned white pigment, also comprising median size is the little titanium (マ イ Network ロ チ タ Application) of 10～80nm or the functional titanium oxide such as anatase titanium dioxide with photocatalyst activity.
In addition, as dyestuff, for example can enumerate: azoic dyestuffs such as monoazo-dyes, polyazo dye, metal complex azo dyes, pyrazolone azoic dyestuff, Stilbene azoic dyestuff, thiazole azo dye; Anthraquinone dye such as anthraquinone derivative, anthracyclinone derivatives; Indigoid dyestuffs such as indigo derivative, thioindigo verivate; Phthalocyanine pigment; Carboniumion dyes such as ketone imines, triphenhlmethane dye, xanthene dye, acridine dye; Quinonimine dyes such as azines,
piperazine dyestuff, thiazine dyes; Methyne dyestuffs such as polymethine (or flower cyanines) dyestuff, azomethine (ァ ジ メ チ Application) dyestuff; Quinoline dye; Nitro-dye; Nitrone (ニ ト ロ Application) dyestuff; Benzoquinones and naphthoquinone dyestuff; The naphthalimide dyestuff; Perylene ketone (ペ リ ノ Application) dyestuffs etc., they can distinguish independent use, or combination more than 2 kinds is used.
Consider from aspects such as the tinting strength of granulated gel (C), proportion, weather resistance, water tolerance; Quality (solids component) with water-base resin (a) is a benchmark; The consumption of tinting material (b) is generally 0.01～500 quality %; Be preferably 0.05～400 quality % especially, further be preferably 0.1～300 quality % especially.
In addition, be benchmark with the quality (solids component) of water-based fluid composition (A), the consumption of tinting material (b) is generally 0.1～80 quality %, is preferably 0.5～70 quality %, further is preferably 1～60 quality %.
Water-soluble polysaccharides (c):
In the method for the present invention employed water-soluble polysaccharides (c) be for derive from aqueous medium (B) in the metals ion of the metallic compound (d) that contained contact, include in water, the using of water-based fluid composition of water-base resin (a) and tinting material (b) in the formation for the metal-salt gel of insoluble or insoluble.
As water-soluble polysaccharides (c); Generally can use the polyose that has 10000～about weight-average molecular weight of 2000000, preferred 10000～100000 and show the above solubleness of above, the preferred 10g/L (25 ℃) of about 5g/L (25 ℃) suitably; Specifically; For example can enumerate alginic acid or its an alkali metal salt, gellan gum (ジ ェ ラ Application ガ system), X 5189 (カ ラ ギ one Na Application) etc., they can distinguish independent use, or combination more than 2 kinds is used.
Quality (solids component) with water-based fluid composition (A) is a benchmark; The consumption of water-soluble polysaccharides (c) generally can be 0.5～10 quality %, is preferably 0.7～9 quality %, further is preferably 1.0～8.0 quality %; Thus; Can make the storage stability of granulated gel (C), the excellences such as clarity of filming of using the coating contain granulated gel to form, in addition, the concave-convex sense that can reduce to film (harsh feeling).
In addition; Consider from aspects such as the tint permanence of granulated gel (C), proportion, weather resistance, water tolerance; Quality (solids component) with water-base resin (a) is a benchmark; The consumption of water-soluble polysaccharides (c) is generally 0.6～30 quality %, is preferably 0.8～29 quality % especially, further is preferably 1.1～23 quality % especially.
Thickening material:
Aspects such as in addition, the uniform distribution of the tinting material (b) from make granulated gel (C) is easy consider that above-mentioned water-based fluid composition (A) preferably further contains thickening material.
As this thickening material, the known thickening material of use itself as its object lesson, for example can be enumerated arbitrarily, mineral-type compounds such as water-soluble silicon acid alkali metal salt, polynite, colloidal aluminum oxide; Derivatived cellulose compounds such as methylcellulose gum, hydroxy ethyl cellulose, carboxy methyl cellulose; Polyether compounds such as pluronic (Pluronic) polyethers, polyethers dialkyl, polyethers dialkyl ether, poly(ether-urethene) modifier, the epoxide modified thing of polyethers; ZX-I, vinylformic acid-polyacrylic compounds such as (methyl) Yodo Sol GH 28; Polyvinyl compounds such as Z 150PH, Vinylpyrrolidone polymer, 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 vinyl methyl ether-copolymer-maleic anhydride, drying oil fatty acid allyl alcohol ester-maleic anhydride etc., they can distinguish independent use, or combination more than 2 kinds is used.Quality with water-base resin (a) is a benchmark, and the consumption of this thickening material is generally 0.01～20 quality %, is preferably 0.03～10 quality %, further is preferably 0.05～5 quality %.
In the above-mentioned water-based fluid composition (A), further can suitably contain the reconditioning material of globe (balloon) geometric ratio, skimmer, curing catalysts, pigment dispersing agent, perfume compound as required; Deodorizing composition, antiseptic-germicide, neutralizing agent, tensio-active agent, watery water-proofing agent; Dispersion agent, sanitas, mould inhibitor, antifreezing agent, UV light absorber; Photostabilised dose, film coalescence aid, zinc whisker, formaldehyde adsorbent, fire retardants such as ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide, white lake etc.
Aqueous medium (B):
Employed aqueous medium (B) contains metallic compound (d) in the method for the present invention; With above-mentioned water-based fluid composition (A) when contacting; The metals ion that derives from metallic compound (d) in water-soluble polysaccharides (c) in the water-based fluid composition (A) and the aqueous medium (B) is formed on and is the salt of insoluble or insoluble in the water, makes water-based fluid composition (A) form granulated gel.
Metallic compound (d):
Method of the present invention is characterised in that above-mentioned metallic compound (d) contains the part of metal salts of organic acids (d1) as its composition.
Through using the part of metal salts of organic acids (d1) as metallic compound (d); Can easily form and not have the excellent granulated gel (C) of the interior effusive storage stability of bag thing; In addition; Can make the physical properties excellent of filming such as water tolerance of filming that form by the coating that contains granulated gel, and waste liquid that can reduce in the manufacturing of granulated gel, to generate or granulated gel suspension-s are to the load of manufacturing installation or environment.
As the metal species in the above-mentioned metal salts of organic acids (d1), consider from the aspects such as intensity of formed granulated gel (C), be preferably polyvalent metal, particularly divalent metal; As divalent metal, can enumerate for example periodictable the 2nd family's elements such as magnesium, calcium, strontium, barium, periodictables such as chromium, molybdenum the 6th family's element; Periodictables such as manganese the 7th family's element, periodictables such as iron, ruthenium 8 family's elements, periodictables such as cobalt, rhodium the 9th family's element; Periodictable such as nickel, palladium the 10th family's element, periodictables such as copper, silver the 11st family's element, periodictables such as zinc, cadmium the 12nd family's element; Periodictables such as aluminium the 13rd family's element, periodictables such as cerium the 16th family's element etc.Wherein, be preferably periodictable the 2nd family's element, preferred especially calcium.
As the organic acid in the above-mentioned metal salts of organic acids (d1); Limit the ground use if can then can not add, can enumerate for example formic acid, acetate, propionic acid, butyric acid, lactic acid, oxalic acid, fumaric acid, succsinic acid, phosphoric acid, Hydrocerol A, glucono-etc. with the salifiable compound of as above enumerating of metal shape.Wherein, molecular weight is 50～1000, particularly 50～400, further 170～400 organic acid particularly, considers preferred from the aspects such as storage stability of the produceability of granulated gel, resulting granulated gel.
Among the present invention, as metal salts of organic acids (d1), above-mentioned in, consider preferred especially lime acetate, calcium propionate, lactic acid ca from aspects such as the manufacturing stability of granulated gel (C), storage stabilitys.
In addition; As the metallic compound among the present invention (d); Except metal salts of organic acids (d1), can also and use and be selected from the metallic compound (d2) in metal hydroxides, MOX and the metal carbonate, thus; Except the storage stability of granulated gel (C), make the stability, make the clarity excellence when concave-convex sense of filming that is formed by the coating that contains granulated gel (C) is diminished.
As the object lesson of the metal in the metallic compound (d2) that uses with this purpose,, can also enumerate the basic metal class that belongs to periodictable 1 family's element except for the illustrated metal of metal salts of organic acids (d1).
As metallic compound (d2), consider from the aspects such as manufacturing stability of granulated gel (C), preferably use oxyhydroxide.
In the metallic compound (d); And during with metal salts of organic acids (d1) and metallic compound (d2); Clarity is excellent when diminishing owing to the storage stability of granulated gel (C) with by the concave-convex sense of filming that the coating that contains granulated gel (C) forms; Waste liquid that is further generated in the manufacturing of granulated gel (C) or granulated gel suspension-s are to reasons such as the load of manufacturing installation or environment diminish, and its usage ratio is generally 99/1～10/90 with the molar ratio computing of metal salts of organic acids (d1)/metallic compound (d2); Be preferably 90/10～15/85 especially, further be preferably 80/20～15/85 especially.
Be dissolved in through at least a portion in the aqueous mediums such as water, can prepare the aqueous medium (B) that contains metals ion metallic compound (d).At this moment, metallic compound (d) needn't all be dissolved in the aqueous medium, can be a part of dissolved state.To the not strict qualification of concentration of the metallic compound (d) in the aqueous medium (B), but be generally 0.05～20 quality %, be preferably 0.05～15 quality %, further be preferably 0.1～10 quality %.
From the storage stability of granulated gel (C) or make aspect such as stability and consider that the pH of aqueous medium (B) is 4.0～13.7, is preferably 6.0～13.5 especially, further is preferably 7.0～13.5 especially.
The manufacturing of granulated gel (C):
According to the present invention, contact with the aqueous medium (B) that contains the metals ion that derives from metallic compound (d) through making water-based fluid composition (A), can form granulated gel (C).This contact for example can be carried out through following method: the method that from syringe front end hydrotropisms medium (B), drips water-based fluid composition (A); Utilize cf-to make water-based fluid composition (A) disperse, drip the method in aqueous medium (B); Make water-based fluid composition (A) atomizing, drip the method aqueous medium (B) from the front end of atomiser nozzle; The method that water-based fluid composition (A) is added in the aqueous medium (B), mixes with dispersion machine etc.
Among the present invention; Water-based fluid composition (A) and aqueous medium (B) use with following ratio; Promptly make with respect to the group 1mol that derives from the carboxyl that the water-soluble polysaccharides (c) that contains in the water-based fluid composition (A) had; The amount of the metallic compound (d) that is contained in the aqueous medium (B) is generally 0.2～3mol, particularly 0.3～2.5mol, the further ratio of 0.4～2mol particularly, and the storage stability of formed like this granulated gel (C) improves, and the concave-convex sense of filming that is formed by the coating that contains granulated gel (C) in addition diminishes; And it is excellences such as the clarity of filming, water tolerance, thereby preferred.
As the above-mentioned group that derives from carboxyl, can enumerate carboxyl, carboxylic acid metal's alkali and the ionic base of carboxylic acid (COO-).
In addition; About the usage ratio of aqueous medium (B) with respect to water-based fluid composition (A), the mass ratio in aqueous medium (B)/water-based fluid composition (A) is adjusted at least 1/2 usually; Especially preferably be adjusted to 1/2～100/1, further especially preferably be adjusted to 1/1～20/1.
Through aforesaid method, can obtain containing water-base resin (a) and tinting material (b) and further wrapping in the granulated gel (C) that forms in the metal-salt gelating film of polyose (c) in as required the water-based fluid composition (A) of other additive component.
To the as above qualification especially of size (major diameter) of the granulated gel (C) of formation; Can be according to appropriate changes such as its purposes; For example, composition that can be through water-based fluid composition (A), stirring velocity, water-based fluid composition (A) is dripped method in aqueous medium (B) etc. regulate.
Resulting granulated gel (C); For example; Can use the wire netting etc. of mesh from aqueous medium (B), to filter with appropriate size, thus, because metals ion or residue and aqueous medium (B) accompany; Can prevent to sneak in the coating composition that utilizes granulated gel (C), can improve formed rerum naturas such as water tolerance of filming.In addition, as required,, can further remove impurity etc. through the granulated gel (C) after the washing filtrations such as water.
Coating composition:
The storage stability of the granulated gel (C) that the method through the invention described above obtains is excellent; Through being engaged in the coating compositions such as multicolor pattern paint, can make that the concave-convex sense that can form the face of being coated with is little, the coating composition of filming of the physical properties excellent of filming such as one-tenth moral character excellence, water tolerance such as clarity of filming.
Therefore, according to the present invention, the coating composition that contains granulated gel (C) is provided also.
Through in coating composition of the present invention, containing the different multiple granulated gel (C) of tone, can make so-called multicolor pattern paint, thus, can further improve and form the appearance design property of filming.
Aforementioned coating composition, except granulated gel (C), preferably also containing films forms composition (D).
Filming forms composition (D) and comprises the resin that itself has film-forming properties, and this resin can be any one of non-crosslinked type or cross-linking type, can be in water-based type, powder type, the organic solvent type etc. any one in addition.
From considering with the affinity of granulated gel (C) or the storage stability aspect of coating composition, film that forming composition (D) is preferably the waterborne compositions that contains water-base resin (e).
As water-base resin (e), can likewise use the general water-base resin that in the water-borne coatings field, uses as resin glue, for example, can from the above material of explain for water-base resin (a), suitably select use.
In addition; For the granulated gel (C) and the formation composition (D) of filming; Contain the functional group (x) that can react to each other respectively and (y) can further improve the water tolerance of filming that forms by coating composition of the present invention; Thereby preferred, preferred granulated gel (C) contains reactive functional groups (x), and film form composition (D) contain can with the reactive functional groups (y) of reactive functional groups (x) reaction.
Combination as the reactive functional groups (y) that is contained in the reactive functional groups (x) that is contained in the granulated gel (C) and the formation composition (D) of filming; If the combination that under the dried coating film condition, can react to each other; Then do not limit especially; Specifically, for example can enumerate combinations such as hydroxyl and NCO, hydroxyl and alkylether radicals, hydroxyl and imino-, carboxyl and epoxy group(ing), amino and epoxy group(ing), carboxamido-group and epoxy group(ing), carbonyl and diazanyl, carbonyl and hydrazide group, carbonyl and Semicarbazido, carbonyl and diacetyl group two hydrazone groups; Particularly the combination of carbonyl and hydrazide group can form the coating composition of normal temperature one liquid cross-linking type, thereby preferred.
In addition; Coating composition of the present invention can be following form; Be granulated gel (C) and film and form composition (D) and all contain resin with reactive functional groups (x), further granulated gel (C) and/or film form composition (D) contain have can with the linking agent of the reactive functional groups (y) of reactive functional groups (x) reaction.
Among the present invention; From the storage stability of formed water tolerance of filming, coating composition, can carry out aspects such as normal temperature one liquid is crosslinked and consider; The preferred granulated gel (C) and the formation composition (D) of filming all contain the water-base resin with carbonyl, and the granulated gel (C) and/or the formation composition (D) of filming contain hydrazine derivative as linking agent.
As granulated gel (C) and/or film and form the object lesson of being used for of can containing in the composition (D) and the hydrazine derivative of carbonyl reaction, can enumerate for example hydrazine, hydrazine hydrate; Carbonatomss such as oxalic acid two hydrazides, propanedioic acid two hydrazides, amber acid dihydrazide, pentanedioic acid two hydrazides, adipic dihydrazide, sebacic dihydrazide are two hydrazides of 2～18 representative examples of saturated aliphatic carboxylic, two hydrazides of monoolefine property 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; NTA three hydrazides, Hydrocerol A three hydrazides, 1,2,4-benzene three hydrazides; YD 30 four hydrazides, 1; 4,5,8-naphthoic acid four hydrazides; Have low-grade polymer and the hydrazine of carboxylic acid low alkyl group ester group or polyhydrazide that hydrazine hydrate (Hydrazine Hydrate 80) reaction forms etc.; Carbonic acid two hydrazides, two Urea,amino-, vulcabond such as hexamethylene diisocyanate, isophorone diisocyanate and by its deutero-polyisocyanate compounds and N, N such as N-dimethylhydrazine; The multifunctional Urea,amino-that N-replacement hydrazine or the above hydrazides excessive response of enumerating obtain; This polyisocyanate compounds and polyether glycol class or polyalkylene glycol monoalkyl ethers etc. contain the multifunctional Urea,amino-of water system that NCO and the above two hydrazides excessive responses of enumerating in the reactant of active dydrogen compounds of hydrophilic radical obtain, this multifunctional Urea,amino-with the multifunctional Urea,amino-of water system mixture, diacetyl group dihydrazone etc.; They can distinguish independent use, or combination more than 2 kinds is used.
In addition, when the granulated gel (C) and/or the formation composition (D) of filming contained the water-base resin with hydroxyl, the formation composition (D) of filming can contain polyisocyanate crosslinking agent as linking agent.
As above-mentioned polyisocyanate crosslinking agent; For example can enumerate; Aliphatic diisocyanates such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, LDI; 4; Alicyclic diisocyanates such as 4 '-methylene-bis (cyclohexyl isocyanate), isophorone diisocyanate, aromatic diisocyanate such as xylylene vulcabond, tolylene diisocyanate, diphenylmethanediisocyanate, polyphenylene methane diisocyanate, similar compounds such as the isocyanuric acid ester body of these vulcabond or biuret body; They can distinguish independent use, or combination more than 2 kinds is used.
In addition, above-mentioned polyisocyanate crosslinking agent can react the water-dispersible polyisocyanates that obtains for polyisocyanate compounds and the non-ionic emulsifier that contains at least 2 NCOs in 1 molecule.As can with this non-ionic emulsifier of above-mentioned polyisocyanate compounds reaction; Can use and the above identical emulsifying agent of emulsifying agent, especially preferably have with NCO reactive activity hydrogen group and have the emulsifying agent of ethylene oxide unit as oxyalkylene units as nonionic emulsifier explanation.
In addition, above-mentioned water-dispersible polyisocyanates as required, can have silane coupling agent reaction the carrying out modification that active hydrogen group and the other end have alkoxysilyl with an end.As this silane coupling agent; For example can enumerate N-β-(amino-ethyl)-gamma-amino 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 commercially available article of this water-dispersible polyisocyanates, for example can enumerate " バ ィ ヒ ジ ュ one Le 3100 ", " VPLS2319 " (trade(brand)name, more than by the Bayer corporate system).
Filming forms composition (D) when containing polyisocyanate crosslinking agent, preferably is being about to mix this polyisocyanate crosslinking agent before using coating composition.
In addition, when the granulated gel (C) and/or the formation composition (D) of filming contained the water-base resin with hydroxyl, the granulated gel (C) and/or the formation composition (D) of filming can contain melamine resin as linking agent.
As above-mentioned melamine resin; For example can enumerate; The resin that has alkylether radicals and/or imino-in the molecule that trimeric cyanamide and formaldehyde and water as required and/or alcohol reaction obtain; Specifically, for example can enumerate melamine methylols such as dihydroxymethyl trimeric cyanamide, trimethylol melamine, tetra methylol trimeric cyanamide, pentamethylol melamine, hexamethylolmelamine; The alkylether compounds of this melamine methylol, the condenses of melamine methylol or its alkylether compounds etc.As the alkyl in the alkyl etherate of melamine methylol, can enumerate carbonatomss such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, 2-ethylhexyl for example and be 1～8 alkyl.
When using melamine resin, as required, as catalyzer, can use sulfonic acid such as tosic acid, Witco 1298 Soft Acid, dinonylnaphthalene sulfonic acid, the salt of these sulfonic acid and amine etc. as linking agent.
In addition, among the present invention, the formation composition (D) of filming preferably contains metal salts of organic acids (d1) and/or metallic compound (d2).Thus, the interior bag thing that can in manufacturing stage of coating composition of the present invention or storage, suppress granulated gel (C) oozes out, and can form little the filming of concave-convex sense.
With the metal salts of organic acids (d1) of this purpose use and/or the consumption of metallic compound (d2); Consider from the storage stability of granulated gel (C), the final aspects such as water tolerance of filming that form; Forming the resin solid composition that is contained in the composition (D) to film is benchmark; Be generally below the 10 quality %, be preferably 0.01～7.5 quality % especially, further be preferably 0.01～5.0 quality % especially.
Form metal salts of organic acids (d1) and the object lesson of metallic compound (d2) in the composition (D) as being engaged in to film; Can enumerate above-mentioned substance; But consider from the aspects such as produceability of granulated gel, use preferably that metal salts of organic acids, molecular weight wherein are 50～1000, preferred especially 50～400, further preferred especially 170～400 metal salts of organic acids.
Film form composition (D) can be for forming painted composition of filming or form the composition that transparent (Network リ ャ one) films, when forming painted composition of filming, can contain tinting material as required.
Form the tinting material in the composition (D) as may reside in to film, can may reside in the tinting material that the tinting material the granulated gel (C) enumerates from above conduct and suitably select to use.
When coating composition of the present invention was used as multicolor pattern paint, from improving the drying property that colourful pattern is filmed, aspects such as suitable gloss, raising sense of touch were considered, preferably in this coating composition, cooperate pigment extender.
As above-mentioned pigment extender; The pigment extender of in the explanation of tinting material (b), being enumerated can be enumerated, for example barium oxide powder, settleability permanent white, barium carbonate, lime carbonate, gypsum, clay, silicon-dioxide, WHITE CARBON BLACK, zeyssatite, talcum, magnesiumcarbonate, white lake, gloss white etc. can be enumerated.
When in the formation composition (D) of filming, cooperating pigment extender, it is benchmark that its use level forms the resin solid composition that is contained in the composition (D) to film, and is generally 5～300 quality %, is preferably 10～200 quality %, further is preferably 15～150 quality %.
The cooperation ratio of the granulated gel in the coating composition of the present invention (C) and the formation composition (D) of filming can be according to the changes such as purposes of coating composition; But so that granulated gel (C)/filming forms the solids component mass ratio of composition (D); Be generally 1/99～80/20; Be preferably 10/90～75/25, further be preferably 20/80～50/50.
In addition; In the coating composition of the present invention, be benchmark with the solids component quality of coating composition of the present invention, the granulated gel (C) and the total content that forms composition (D) of filming are generally 50～99 quality %; Be preferably 60～99 quality %, further be preferably 70～99 quality %.
In coating composition of the present invention, as required, can contain neutralizing agent, thickening material, tensio-active agent, anti-sedimentation agent; Static inhibitor, antiseptic-germicide, spices, pH regulator agent, humextant; Watery water-proofing agent, dispersion agent, skimmer, sanitas, mould inhibitor; Antifreezing agent, UV light absorber, Photostabilised dose, film coalescence aid, zinc whisker; Curing catalyst, formaldehyde adsorbent, wax, alkyl silicate condenses or the low pollution agent such as modification alkyl silicate that this alkyl silicate condenses modification formed with polyalkylene glycol etc., coating such as fire retardant such as ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide, white lake are used additive.
Coating process:
Be contained on the substrate surface through coating composition of the present invention is coated with, can form filming of excellent performances such as appearance of film, water tolerance.
As the substrate surface that can be suitable for coating composition of the present invention; For example can enumerate; The surface of base materials such as plasterboard, concrete wall, mortar wall, slabstone, PC plate, ALC plate, cement calcium silicate board, timber, stone material, plastic shaping thing, metal work material; Be arranged on the coated surface of crylic acid resin on these base materials, vinylformic acid ammonia ester resene, polyurethane type resin, fluorine type resin, silicon crylic acid resin, vinyl acetate resin class, epoxy resin etc., wallpaper face that forms by materials such as SE, polyolefine, paper, cloth etc.
The glue spread of coating composition of the present invention can change according to the composition of employed coating composition or the differences such as kind of needs substrates coated, is generally 50～1000g/m per 1 time
2, be preferably 100～700g/m
2The scope repeated multiple times coating of appearance of film can not damaged in addition.
The application of coating composition of the present invention can be carried out by the known painting device of use itself, for example, and can be according to suitable roller, air gun, airless sprayer, resin spray gun, omnipotent rifle, brush, scraper (コ テ), roller coating machines etc. selected such as purposes.
The drying that formation is filmed according to composition of employed coating composition etc., can be carried out with any one method of heat drying, forced drying or Air drying.
Can be coated with application coating composition of the present invention on the face in formed primary coat on the substrate surface in advance behind the application bottom-coating.
As above-mentioned bottom-coating, can suitably select according to the kind of substrate surface or state etc., for example, can use bottom-coatings such as sealing priming paint, substrate adjustment material.In addition, also can be coated with common outer coating paint and use coating as the end formation of coating composition of the present invention.
Form the outer coating paint of usefulness as above-mentioned substrate; For example can enumerate: contain by acrylics, polyolefin resin, silicone based resin, polyurethanes resin, redix, the water system that resin kinds such as phenolic resinoid, polyester resin, alkyd based resin constitute or the resin of solvent system be as the coating of resin glue, the preferred coating that contains aqueous resin that uses.
During the coating bottom-coating, as required, can be with range upon range of the carrying out of the coating of the primary coat more than 2 kinds.
The coating of above-mentioned bottom-coating can be carried out by the known apparatus for coating of use itself, for example, and can be according to suitable roller, air gun, airless sprayer, resin spray gun, omnipotent rifle, brush, scraper, roller coating machines etc. selected such as purposes.
The glue spread of above-mentioned bottom-coating can change according to the differences such as kind of substrates coated, can be 50～2000g/m usually per 1 time
2, be preferably 70～1000g/m
2In addition, the scope repeated multiple times coating of appearance of film can not damaged.
The drying that formed primary coat is filmed can be carried out with any one method of heat drying, forced drying or Air drying according to kind of employed bottom-coating etc.
Embodiment
Hereinafter is explained the present invention through embodiment more specifically, but the present invention is not limited in these embodiment." part " in the following example and " % " refer to " mass parts " and " quality % " respectively
The manufacturing of emulsion
Make example 1
In 4 flasks of capacity 2L, add 285 parts of deionized waters and 1 part of " ニ ュ one コ one Le 707SF " (annotating 1), carry out nitrogen replacement after, remain on 85 ℃.To wherein adding respectively the composition of following composition is processed emulsion and 3% part of the pre-emulsion that obtains; With 41 parts that 3 parts of ammonium persulphates are dissolved in 123 parts of the initiator solutions that obtain in 120 parts of the deionized waters, add after 20 minutes with in flask, dripping remaining prefabricated liquid making and ammonium persulfate aqueous solution in 4 hours.
368 parts of deionized waters
150 parts of vinylbenzene
413 parts of TEB 3Ks
240 parts of n-butyl acrylates
150 parts of 2-EHAs
20 parts of diacetone-acryloamide(DAA)s
5 parts of 1,6 hexanediol diacrylates
20 parts of 2-Hydroxy ethyl acrylates
2 parts in vinylformic acid
66 parts of " ニ ュ one コ one Le 707SF " (annotating 1).
After the dropping, it further is cooled to 40～60 ℃ in maintenance under 85 ℃ after 2 hours.Then, regulate pH, obtain solids component and be 55% emulsion (a1) with ammoniacal liquor.The median size of emulsion (a1) is that 170nm, pH are 8.3.
(annotate 1) " ニ ュ one コ one Le 707SF ": trade(brand)name, Japanese emulsifying agent society system has the aniorfic surfactant of polyoxyethylene chain, nonvolatile component 30%.
The manufacturing of white pigments thickener
Make example 2
In the stainless steel vessel of 1L, add following compositions, mixed 30 minutes, obtain white pigments thickener (b1) thus with stirrer.
225 parts in water
15 parts of " ス ラ オ Off 72N " (annotating 2)
30 parts of " DISPER BYK-190 " (annotating 3)
15 parts of " SN デ Off オ one マ 1 " (annotating 4)
500 parts of " TITANIX JR-605 " (annotating 5).
(annotating 2) " ス ラ オ Off 72N ": trade(brand)name, military field pharmaceutical industries (strain) system, sanitas.
(annotating 3) " DISPER BYK-190 ": trade(brand)name, BYK ケ ミ one society's system, pigment dispersing agent.
(annotating 4) " SN デ Off オ one マ 1 ": trade(brand)name, サ Application ノ プ コ society system, skimmer.
(annotating 5) " TITANIX JR-605 ": trade(brand)name, テ イ カ society system, titanium white.
The manufacturing of red rust (red Qiang) pigment thickener
Make example 3
In the stainless steel vessel of 1L, add following compositions, mixed 60 minutes, obtain red rust pigment thickener (b2) thus with stirrer.
400 parts in water
15 parts of " ス ラ オ Off 72N " (annotating 2)
48 parts of " DISPER BYK-190 " (annotating 3)
15 parts of " SN デ Off オ one マ 1 " (annotating 4)
240 parts of red stone.
The manufacturing of granulated gel use fluid composition
Make example 4
In container, cooperate following compositions successively, mix, obtain granulated gel use fluid composition (A-1) to evenly.
250 parts of 55% emulsions (a1)
154 parts of white pigments thickeners (b1)
4 parts of the 10% adipic dihydrazide aqueous solution
20 parts of " TEXANOL " (annotating 6)
2 parts of " SN デ Off オ one マ 1 " (annotating 4)
2 parts of " ァ デ カ ノ one Le UH-438 " (annotating 7)
280 parts of the 2% sodiun alginate aqueous solution.
(annotating 6) " TEXANOL ": trade(brand)name, ィ one ス ト マ Application ケ ミ カ Le society system, 2,2,4-neopentyl glycol mono isobutyrate, film coalescence aid.
(annotating 7) " ァ デ カ ノ one Le UH-438 ": trade(brand)name, ァ デ カ society system, poly(ether-urethene) modifier, viscous regulator.
Make example 5～7
In above-mentioned manufacturing example 4, form the cooperation composition of changing into shown in the following table 1 with cooperating, in addition,, make granulated gel use fluid composition (A-2)～(A-4) with manufacturing example 4 operation likewise.
Table 1
| The preparation example | |||||
| 4 | 5 | 6 | 7 | ||
| Granulated gel use fluid composition | A-1 | A-2 | A-3 | A-4 | |
| Resinous principle | 55% emulsion (a1) | 250 | 250 | 250 | 250 |
| Tinting material | White pigments thickener (b1) | 154? | 154? | ||
| Red rust pigment thickener (b2) | 276 | 276 | |||
| Solidifying agent | The 10% adipic dihydrazide aqueous solution | 4 | 4 | 4 | 4 |
| Additive | " TEXANOL " (annotating 6) | 20 | 20 | 20 | 20 |
| " SN デ Off オ one マ 1 " (annotating 4) | 2 | 2 | 2 | 2 | |
| " ァ デ カ ノ one Le UH-438 " (annotating 7) | 2 | 2 | 2 | 2 | |
| Jelling agent | The 2% sodiun alginate aqueous solution | 280 | 280 | 200 | 200 |
The manufacturing of granulated gel use medium
Make example 8
In the 4L stainless steel vessel, add 2000 parts of 7.0 parts of lime acetate monohydrates and deionized waters, be stirred to evenly, make the aqueous medium (B-1) that contains lime acetate thus.
Make example 9～17
In above-mentioned manufacturing example 8, make to cooperate to consist of shown in the following table 2, in addition, likewise operate with making example 8, make aqueous medium (B-2)～(B-10).
Table 2
| Make example | |||||||||||
| 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | ||
| The aqueous medium name | B-1 | B-2 | B-3 | B-4 | B-5 | B-6 | B-7 | B-8 | B-9 | B-10 | |
| Cooperate | The lime acetate monohydrate | 7 | 11 | 3 | 6 | 7 | |||||
| Calcium propionate | 7 | 4 | |||||||||
| Calcium lactate pentahydrate | ¨ | ||||||||||
| Calcium hydroxide | 3 | 3 | 1 | ||||||||
| Sodium hydroxide | 1 | ||||||||||
| Calcium chloride | 7 | ||||||||||
| Calcium sulfate dihydrate | 7 | ||||||||||
| Deionized water | 2000 | 2000 | 2000 | 2000 | 2000 | 2000 | 2000 | 2000 | 2000 | 2000 | |
| pH | 7.4 | 7.5 | 8.1 | 7.2 | 12.2 | 12.5 | 12.1 | 11.5 | 6.8 | 6.8 | |
Film and form the manufacturing of composition use Clear paint
Make example 18
In the stainless steel vessel of 2L, add following compositions, mixed 30 minutes, obtain aqueous clear coating (C-1) thus with stirrer.
750 parts of 55% emulsions (a1)
50 parts of " TEXANOL " (annotating 6)
279 parts in water
250 parts of " タ Le Network SS " (annotating 8)
10 parts of " SN デ Off オ one マ 1 " (annotating 4)
6 parts of " ァ デ カ ノ one Le UH-438 " (annotating 7).
(annotate 8) " タ Le Network SS ": trade(brand)name, Japanese タ Le Network society system, talcum.
Contain filming of calcium salt and form the manufacturing example of composition with Clear paint
Make example 19,20
Except in above-mentioned manufacturing example 18, make cooperate form as shown in table 3 below outside, and make example 18 operation likewise, obtain aqueous clear coating (C-2), (C-3).
Table 3
| Make example | ||||
| 18 | 19 | 20 | ||
| Aqueous clear coating | C-1 | C-2 | C-3 | |
| Cooperate | 55% emulsion (a1) | 750 | 750 | 750 |
| " TEXANOL " (annotating 6) | 50 | 50 | 50 | |
| Water | 279 | 279 | 279 | |
| Calcium propionate | 2 | |||
| Calcium lactate pentahydrate | 4 | |||
| " タ Le Network SS " (annotating 8) | 250 | 250 | 250 | |
| " SN デ Off オ one マ 1 " (annotating 4) | 10 | 10 | 10 | |
| " ァ デ カ ノ one Le UH-438 " (annotating 7) | 6 | 6 | 6 | |
The manufacturing of granulated gel
Embodiment 1
In the 4L stainless steel vessel, add 1300 parts of the aqueous mediums (B-1) that obtain by above-mentioned manufacturing example 8; When the agitating wing that use has a 75mm diameter stirs with rotating speed 2500rpm; In container, drip 650 parts of the water-based fluid compositions (A-1) that obtain by above-mentioned manufacturing example 4 lentamente, generate granulated gel.Then, after 15 minutes, use 200 purpose wire nettings to filter, obtain granulated gel (D-1) with liquid in the further stirred vessel of identical rotating speed.The solids component of resulting granulated gel is 20%.
Embodiment 2～20 and comparative example 1～4
The cooperation of the water-based fluid composition of aqueous medium in making the foregoing description 1 and dropping is as shown in table 4 below, likewise operate, make granulated gel (D-2)～(D-24), the storage stability of granulated gel is estimated with the foregoing description 1.In comparative example 1 and the comparative example 2,, find that the metal part of manufacturing installation has some corrosion though the storage stability of the granulated gel that generates is excellent.In addition, illustrated with respect to derive from 1 mole of the group of the carboxyl of sodiun alginate in the table 4, the mole number of the metallic compound that is contained in the aqueous medium when using multiple compound (and be to add up to mole number) as metallic compound.Wherein, the molecular weight of sodiun alginate is 90000.
Table 4
| Embodiment | Comparative example | ||||||||||||||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | 1 | 2 | 3 | 4 | ||
| The granulated gel name | D-1 | D-2 | D-3 | D-4 | D-5 | D-6 | D-7 | D-8 | D-9 | D-10 | D-11 | D-12 | D-13 | D-14 | D-15 | D-16 | D-17 | D-18 | D-19 | D-20 | D-21 | D-22 | D-23 | D-24 | |
| Water-based fluid composition kind | A-1 ?650 | A-2 ?760 | A-3 ?650 | A-4 ?775 | A-1 ?650 | A-2 ?760 | A-1 ?650 | A-2 ?760 | A-1 ?650 | A-2 ?760 | A-1 ?650 | A-2 ?760 | A-1 ?650 | A-2 ?760 | A-1 ?650 | A-2 ?760 | A-1 ?650 | A-2 ?760 | A-1 ?325 | A-2 ?380 | A-1 ?650 | A-2 ?760 | A-1 ?650 | A-2 ?760 | |
| The aqueous medium name | B-1 | 1300 | 1300 | 1300 | 1300 | 1625 | 1625 | ||||||||||||||||||
| B-2 | 1300 | 1300 | |||||||||||||||||||||||
| B-3 | 1300 | 1300 | |||||||||||||||||||||||
| B-4 | 1300 | 1300 | |||||||||||||||||||||||
| B-5 | 1300 | 1300 | |||||||||||||||||||||||
| B-6 | 1300 | 1300 | |||||||||||||||||||||||
| B-7 | 1300 | 1300 | |||||||||||||||||||||||
| B-6 | 1300 | 1300 | |||||||||||||||||||||||
| B-9 | 820 | 820 | |||||||||||||||||||||||
| B-10 | 1300 | 1300 | |||||||||||||||||||||||
| The total mole of metallic compound/the derive from group mole of the COOH of sodiun alginate | 0.9 | 0.9 | 1.1 | 1.1 | 1.4 | 1.4 | 0.9 | 0.9 | 0.9 | 0.9 | 1.3 | 1.3 | 1.3 | 1.3 | 1.1 | 1.1 | 0.9 | 0.9 | 4.5 | 4.5 | 0.9 | 0.9 | 0.9 | 0.9 | |
| The storage stability of granulated gel (* 1) | ○ | ○ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | ○ | ○ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | ◎ | ◎ | ○ | ○ | △ | △ | |
The storage stability of (* 1) granulated gel
With 500 parts of adding capacity of the granulated gel shown in the table 4 is in the interior finishing coat still of 1L, and storage is 7 days under the condition of 40 ℃ of temperature, relative humidity 60%.Then, return to room temperature, in 500 parts of 55% emulsions (a1), add 500 parts of granulated gels, be stirred to evenly, the visual observation state is estimated with following benchmark.
◎: can know the identification granulated gel, look does not ooze out,
Zero: though can discern granulated gel, look has slightly and oozes out,
△: find colored oozing out and the breaking of granulated gel,
*: can not discern granulated gel fully.
The manufacturing of multicolor pattern paint
Embodiment 21～36 and comparative example 5～6
In the stainless steel vessel of 500mL, when stirring, add the composition shown in the following table 5 successively, be stirred to then evenly, make multicolor pattern paint (E-1)～(E-18) thus.The film performance evaluation of resulting coating also is shown in table 5 in the lump.
Table 5
| Embodiment | Comparative example | |||||||||||||||||||
| 21 | 22 | 23 | 24 | 25 | 26 | 27 | 2B | 29 | 30 | 31 | 32 | 33 | 34 | 35 | 36 | 5 | 6 | |||
| Multicolor pattern paint | E-1 | E-2 | E-3 | E-4 | E-5 | E-6 | E-7 | E-8 | E-9 | E-10 | E-11 | E-12 | E-13 | E-14 | E-15 | E-16 | E-17 | E-18 | ||
| Coating cooperates | The formation composition of filming | Aqueous clear coating (C-1) | 130 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | ||||
| Aqueous clear coating (C-2 | 130 | 130 | ||||||||||||||||||
| Aqueous clear coating (C-3) | 130 | 130 | ||||||||||||||||||
| 10% adipic dihydrazide | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | ||||
| Ha ィ ヒ Star コ-Le 3100 (annotating 9) | 3.3 | |||||||||||||||||||
| サ ィ メ Le 327 (annotating 10) | 4.2 | |||||||||||||||||||
| Granulated gel | D-1 | 145 | 145 | 145 | 145 | 145 | ||||||||||||||
| D-2 | 30 | 30 | 30 | 30 | 30 | |||||||||||||||
| D-3 | 145 | |||||||||||||||||||
| D-4 | 30 | |||||||||||||||||||
| D-5 | 145 | |||||||||||||||||||
| D-6 | 30 | |||||||||||||||||||
| D-7 | 145 | |||||||||||||||||||
| D-8 | 30 | |||||||||||||||||||
| D-9 | 145 | 145 | 145 | |||||||||||||||||
| D-10 | 30 | 30 | 30 | |||||||||||||||||
| D-11 | 145 | |||||||||||||||||||
| D-12 | 30 | |||||||||||||||||||
| D-13 | 145 | |||||||||||||||||||
| D-14 | 30 | |||||||||||||||||||
| D-15 | 145 | |||||||||||||||||||
| D-16 | 30 | |||||||||||||||||||
| D-17 | 145 | |||||||||||||||||||
| D-18 | 30 | |||||||||||||||||||
| D-19 | 145 | |||||||||||||||||||
| D-20 | 30 | |||||||||||||||||||
| D-21 | 145 | |||||||||||||||||||
| D-22 | 30 | |||||||||||||||||||
| D-23 | 145 | |||||||||||||||||||
| D-24 | 30 | |||||||||||||||||||
| Additive | ァ デ カ ノ-Le UH-438 (annotating 7) | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | |
| Performance evaluation | Become moral character (* 2) | ○? | ○? | ○? | ○? | ◎? | ◎? | ◎? | ◎? | ◎? | ○△? | ○? | ○? | ○? | ◎? | ○? | ◎? | ○? | △? | |
| Water tolerance (* 3) | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | △ | △ | ||
(annotating 9) " バ ィ ヒ ジ ュ one Le 3100 "): trade(brand)name, バ ィ ェ Le society system, water-dispersible polyisocyanates solidifying agent.
(annotating 10) " サ ィ メ Le 327 ": trade(brand)name, Japanese サ ィ テ ッ Network ィ Application ダ ス ト リ one ズ society system, melamine resin.
The manufacturing of test coated plate
With 100g/m
2Glue spread slabstone (150 * 70 * 3mm) go up roller coat " EP シ one ラ one is transparent " (trade(brand)name, Northwest ペ ィ Application ト society system, water system ACRYLIC EMULSION class sealing priming paint) and drying after, with 100g/m
2Glue spread roller coat " PVC ニ デ ラ ッ Network ス 300 " (trade(brand)name, Northwest ぺ ィ Application ト society system, a kind of suitable ACRYLIC EMULSION class coating of JIS K5663), under the condition of 20 ℃ of temperature, relative humidity 60% dry 1 day, with it as by coated plate, with 300g/m
2Glue spread sprays various multicolor pattern paints above that.
Then, for the coated plate beyond the embodiment 32, drying is 7 days under the condition of 23 ℃ of temperature, relative humidity 60%, obtains each test board.For the use of embodiment 32 coated plate of melamine resin,,, each test coated plate is supplied to test in property at 80 ℃ down after dry 10 minutes with electric drying apparatus 140 ℃ of bakings 30 minutes down.
(* 2) become moral character
Filming of coated panel respectively tested in visual observation, estimates with following benchmark.
◎: clarity is arranged, the no concave-convex sense,
Zero: though clarity is arranged, concave-convex sense is arranged slightly,
Zero △: though clarity is arranged, concave-convex sense is arranged,
△: find coloured oozing out, when touching, the harsh feeling of be stuck (draw っ and hang the か Ru) is arranged with hand,
*: color is obviously oozed out, and when touching with hand, jammed harsh feeling is arranged.
(* 3) water tolerance
Each test coated plate was flooded 7 days in 23 ℃ tap water, and after mentioning, visual observation is estimated with following benchmark.
Zero: excellence
△: find that loss of gloss is arranged, albefaction, expansible any one
*: finding has significant expansion or films softening.
Claims (11)
1. the method for manufacture of granulated gel (C); It is for comprising the method that makes the manufacturing granulated gel (C) that the water-based fluid composition (A) that contains water-base resin (a), tinting material (b) and water-soluble polysaccharides (c) contacts with the aqueous medium that contains metallic compound (d) (B); It is characterized in that; Said metallic compound (d) contains the part of metal salts of organic acids (d1) as its composition, and metallic compound (d) further contains at least a kind of metallic compound (d2) that is selected from metal hydroxides, MOX and the metal carbonate.
2. the described method of claim 1, wherein, said water-base resin (a) is an acrylics.
3. the described method of claim 1, wherein, said water-soluble polysaccharides (c) is selected from alginic acid or its an alkali metal salt, gellan gum and X 5189.
4. any described method in the claim 1～3 wherein, is a benchmark with the solids component quality of water-based fluid composition (A), and the content of said water-soluble polysaccharides (c) is 0.5～10 quality %.
5. any described method in the claim 1～4, wherein, metal salts of organic acids (d1) is selected from lime acetate, calcium propionate and lactic acid ca.
6. the described method of claim 1, wherein, the metal salts of organic acids (d1) in the said metallic compound (d) and the usage ratio of metallic compound (d2) are 99/1～10/90 with the molar ratio computing of metal salts of organic acids (d1)/metallic compound (d2).
7. any described method of manufacture in the claim 1～6; Wherein, With with respect to the group 1mol that derives from the carboxyl that the water-soluble polysaccharides (c) that contained in the water-based fluid composition (A) had, the amount of the metallic compound (d) that is contained in the aqueous medium (B) is that the ratio of 0.2～3mol makes use fluid composition (A) and aqueous medium (B).
8. coating composition, it contains the granulated gel (C) that obtains through any described method in the claim 1～7 and films and forms composition (D).
9. the described coating composition of claim 8, wherein, said filming forms composition (D) and contains metal salts of organic acids (d1) and/or metallic compound (d2).
10. claim 8 or 9 described coating compositions, wherein, so that granulated gel (C)/filming forms the solids component mass ratio of composition (D), the ratio with 1/99～80/20 contains granulated gel (C) and the formation composition (D) of filming.
11. coating process is characterized in that, any described coating composition in the coating claim 8～10 on substrate surface.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007012880 | 2007-01-23 | ||
| JP2007-012880 | 2007-01-23 | ||
| JP2007012880 | 2007-01-23 |
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| Publication Number | Publication Date |
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| CN101230141A CN101230141A (en) | 2008-07-30 |
| CN101230141B true CN101230141B (en) | 2012-05-30 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2008100037918A Active CN101230141B (en) | 2007-01-23 | 2008-01-23 | Method for manufacturing granulated gel and coating composition having the same |
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| Country | Link |
|---|---|
| JP (1) | JP5268370B2 (en) |
| CN (1) | CN101230141B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5258385B2 (en) * | 2007-06-20 | 2013-08-07 | 関西ペイント株式会社 | Granular gel production method and granular gel production apparatus |
| JP5547367B2 (en) * | 2007-09-12 | 2014-07-09 | 関西ペイント株式会社 | Water-based colorful pattern paint |
| JP5873432B2 (en) * | 2011-04-27 | 2016-03-01 | 関西ペイント株式会社 | Water-based colorful pattern paint composition |
| JP2013060554A (en) * | 2011-09-14 | 2013-04-04 | Seiko Epson Corp | Gel production apparatus and gel production method |
| JP5672291B2 (en) * | 2012-11-26 | 2015-02-18 | 藤倉化成株式会社 | Multi-color paint and multi-color paint film |
| JP6026938B2 (en) * | 2013-03-29 | 2016-11-16 | 関西ペイント株式会社 | Thermal barrier matte water-based coating composition and thermal barrier matte coating film forming method |
| JP6238293B2 (en) * | 2014-02-21 | 2017-11-29 | 関西ペイント株式会社 | Colored resin particles and aqueous multicolor pattern coating composition containing the same |
| WO2016064188A1 (en) * | 2014-10-24 | 2016-04-28 | 주식회사 아모텍 | Porous protective layer for gas sensor, method for producing same, and gas sensor comprising same |
| CN105111873A (en) * | 2015-10-09 | 2015-12-02 | 张家口家诚首佳新型建材有限公司 | Method for improving storage time of faux marble paint |
| KR102293017B1 (en) | 2016-05-13 | 2021-08-23 | 산 노프코 가부시키가이샤 | Granulation stabilizer for multicolor coating material |
| KR101747915B1 (en) * | 2017-03-09 | 2017-06-15 | 승탑건설(주) | Composite coating method for improving durability of concrete structure using permeability nano-silane coating agent |
| JP6972726B2 (en) * | 2017-07-20 | 2021-11-24 | 藤倉化成株式会社 | Multicolored paint composition |
| CN113337181B (en) * | 2021-07-23 | 2022-07-01 | 广东宝伯力新材料科技有限公司 | EVA and BS double-component middle paint and preparation method thereof |
| CN113512340A (en) * | 2021-08-03 | 2021-10-19 | 广东宝伯力新材料科技有限公司 | Water-based colored ultraviolet-proof finish paint and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2513726B2 (en) * | 1987-02-03 | 1996-07-03 | バスフ コーポレーション | Aqueous colored acrylic hydrosol coating composition |
| CN1420170A (en) * | 2001-11-15 | 2003-05-28 | 关西油漆株式会社 | Method for producing formed grain for immobilization of enzyme or microbiologic cell |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2706728B2 (en) * | 1988-10-31 | 1998-01-28 | 株式会社アサヒペン | Method for producing colored polymer powder |
| US20080139697A1 (en) * | 2004-12-27 | 2008-06-12 | Takashi Ueda | Aggregated-Particle Composition |
| JP5147096B2 (en) * | 2005-08-08 | 2013-02-20 | エスケー化研株式会社 | Multi-color paint composition |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2513726B2 (en) * | 1987-02-03 | 1996-07-03 | バスフ コーポレーション | Aqueous colored acrylic hydrosol coating composition |
| CN1420170A (en) * | 2001-11-15 | 2003-05-28 | 关西油漆株式会社 | Method for producing formed grain for immobilization of enzyme or microbiologic cell |
Non-Patent Citations (2)
| Title |
|---|
| JP第2513726号B2 1996.07.03 |
| 陈明木等.海藻酸钙凝胶特性影响因素的探讨.《广州食品工业科技》.2002,第18卷(第3期),1－4. * |
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| CN101230141A (en) | 2008-07-30 |
| JP5268370B2 (en) | 2013-08-21 |
| JP2008202037A (en) | 2008-09-04 |
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