CN1986665B - Aqueous coating composition - Google Patents
Aqueous coating composition Download PDFInfo
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- CN1986665B CN1986665B CN2006101617396A CN200610161739A CN1986665B CN 1986665 B CN1986665 B CN 1986665B CN 2006101617396 A CN2006101617396 A CN 2006101617396A CN 200610161739 A CN200610161739 A CN 200610161739A CN 1986665 B CN1986665 B CN 1986665B
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Abstract
The invention provides a water paint combination which is good for finshing, and is suitable for forming paint film with good polishing quality, adhesive quality, and water resistance. A water paint combination is characterized in that it is consisted of base paint (A) and diluting agent (B), inwhich base paint (A) includes water acroleic acid resin (A1), which polymerizes by polymerized unsaturated unit which contains phosphate group by 0.1-10 mass%. Diluting agent (B) includes tackifier (B1) and water, preferred the solid component mass ratio of water acroleic acid resin (A1) and water urethane resin (A2) is in the range of 1/99 to 90/10.
Description
Technical field
It is good to the present invention relates under the condition of Air drying or forced drying, cover with paint, lacquer, colour wash, etc. operability, can form polishability, good the filming of tack, can be used as the water-based paint compositions that base coating coating uses.
Background technology
As the formation method of last coating films such as body of a motor car, for example, implement to cover with paint, lacquer, colour wash, etc. earlier base coating coating, cover with paint, lacquer, colour wash, etc. the covering with paint of the last processing of varnish colour again.In recent years,, adopting aqueous coating as base coating coating from point of view of environment protection, and, there is the car repair covering with paint field that forms the situation of filming through Air drying and forced drying, also carrying out the research of water systemization.
For example; In patent documentation 1; The applicant has proposed to be characterized as with water soluble resin and/or water-dispersed resin and pigment as staple, adopts boiling point to be below 150 ℃, has the water-based paint compositions of the amine of 1 above hydroxyl as neutralizing agent in 1 molecule.
This water-based paint compositions all can form filming of having excellent water-resistance under the condition of Air drying and forced drying; But; With this water-based paint compositions is base coating; The bilayer that on this base coating is filmed, applies organic spirit thinned type varnish and form is filmed; Be under the outdoor situation throughout the year, can occurring taking place the isolating situation of interlayer between base coating is filmed and varnish is filmed especially, and can produce the problem of in water dipping postadhesion property (the being also referred to as water-fast tack) variation of filming.
To this problem, the applicant has proposed to contain the waterborne polyurethane resin with hydroxyl and the water-based paint compositions of specific water soluble vinyl resin with specific ratios in patent documentation 2.Said composition can form water-fast tack, weathering resistance is good; And what polishability was good films, but this base coating thickness is thicker, under the thin situation of surface layer varnish thickness; Different according to the material of covering with paint, lacquer, colour wash, etc., tack, the particularly imperfect problem of water-fast tack can appear.And on-the-spot in the covering with paint of car repair covering with paint etc., coverings with paint environment such as humidity and temperature on-the-spot differently have very big difference according to each, thereby also have polishability that operability and formation the films different and different problem with the covering with paint scene of covering with paint, lacquer, colour wash, etc.
[patent documentation 1] japanese kokai publication hei 11-124545 communique
[patent documentation 2] TOHKEMY 2005-89613 communique
Summary of the invention
It is good to the purpose of this invention is to provide a kind of covering with paint operability, is applicable to the coating method that forms polishability, tack, the water-based paint compositions of filming that has excellent water-resistance and adopt it.
Present inventors have carried out particular study in order to address the above problem; The result finds; The water-based paint compositions of being made up of base coating that contains specific water-borne acrylic resin and the thinner that contains tackifier and water can form good the filming of rerum natura such as covering with paint, lacquer, colour wash, etc. operability, tack, water tolerance, thereby has accomplished the present invention.
That is, the present invention relates to:
1, a kind of water-based paint compositions; It is characterized in that it is to contain base coating (A) and thinner (B) and the water-based paint compositions that forms; Wherein base coating (A) comprises by containing the composition copolymerization of polymerizability unsaturated monomer and the water-borne acrylic resin (A1) that obtains that 0.1-10 quality % has the polymerizability unsaturated monomer of phosphate, and thinner (B) contains tackifier (B1) and water.
2, the 1st described water-based paint compositions, the polymerizability unsaturated monomer that wherein has phosphorous acidic group are the compound of formula (1) expression,
(in the formula, R
1Expression Wasserstoffatoms or methyl, R
2The expression carbonatoms is the alkylidene group of 2-4);
3, the 1st or the 2nd described water-based paint compositions, wherein base coating (A) further comprises waterborne polyurethane resin (A2).
4, the 3rd described water-based paint compositions, wherein the mixture ratio of water-borne acrylic resin (A1) and waterborne polyurethane resin (A2) is counted 1/99～90/10 scope with the solids component mass ratio of water-borne acrylic resin (A1)/waterborne polyurethane resin (A2).
5, each described water-based paint compositions in the 1st～4, wherein base coating (A) further comprises vinylformic acid Emulgating polymers (A3).
6, each described water-based paint compositions in the 1st～5, wherein base coating (A) further comprises tackifier (A4).
7, each described water-based paint compositions in the 1st～6, wherein the content of the tackifier (B1) in the thinner (B) is the scope of 0.01-10 quality %.
8, each described water-based paint compositions in the 1st～7, wherein thinner (B) contains hydrophilic organic solvent.
9, the 8th described water-based paint compositions, wherein hydrophilic organic solvent contains glycol ether ether organic solvent and/or dipropylene glycol ethers organic solvent.
10, the 8th described water-based paint compositions, wherein hydrophilic organic solvent contains at least a organic solvent that is selected from alcohol organic solvent, gylcol ether organic solvent, Ucar 35 ethers organic solvent and ester class organic solvent.
11, each described water-based paint compositions in the 1st～10, wherein the consumption of thinner (B) is the scope of 30-200 quality % with respect to the quality of base coating (A).
12, each described water-based paint compositions in the 6th～11, wherein tackifier (A4) and tackifier (B1) are selected from the combination of mineral-type tackifier and polyacrylic tackifier, urethane association type tackifier and polyacrylic tackifier, urethane association type tackifier and mineral-type tackifier.
Base coating and thinner difference package stability used among the present invention are good; The water-based paint compositions of the present invention that before using, both mixing is obtained; The covering with paint operability is good; Drying property is all good under the condition of Air drying or forced drying, can form good filming such as polishability, tack, water tolerance, water-fast tack.And, have above-mentioned composition through making water-based paint compositions, can suppress polishability, the rerum natura of filming descends along with the variation of covering with paint, lacquer, colour wash, etc. environment.
Embodiment
Base coating (A)
As the phosphorous acidic group polymerizability unsaturated monomer of the copolymer composition of contained water-borne acrylic resin (A 1) in the used base coating of the present invention (A), can enumerate the compound that contains phosphate and polymerizability unsaturated group in the molecule.As the polymerizability unsaturated group, can enumerate (methyl) acryloxy, allyl group, vinyl etc. in the present invention, be particularly suitable for using (methyl) acryloxy.
As an example of the polymerizability unsaturated monomer of above-mentioned phosphorous acidic group, can enumerate the for example compound of following formula (1) expression,
(in the formula, R
1Expression Wasserstoffatoms or methyl, R
2The expression carbonatoms is the alkylidene group of 2-4).As its concrete example; Can enumerate for example (2-acryloxy ethyl) acid phosphoric acid ester, (2-methacryloxyethyl) acid phosphoric acid ester, (2-acryloxy propyl group) acid phosphoric acid ester, (2-methacryloxypropyl) acid phosphoric acid ester etc., they can make up use more than a kind or 2 kinds.
In addition, in the present invention, the polymerizability unsaturated monomer of above-mentioned phosphorous acidic group can also be the polymerizability unsaturated monomer that has the phosphorous acidic group of polyalkylene oxide units in the molecule.
As this polymerizability unsaturated monomer with phosphate and polyalkylene oxide units, can enumerate the for example monomer of following formula (2) expression,
(in the formula, R
1Expression Wasserstoffatoms or methyl, R
2The expression carbonatoms is the alkylidene group of 2-4, and n representes the integer of 1-30).
The monomer of above-mentioned formula (2) expression can pass through, and for example, in solvent, uses catalyzer oxirane to be added on (methyl) vinylformic acid, forms and gathers the alkane diol monoester, and this material and phosphorus oxychloride reaction are made phosphoric acid esterification, then, makes the products therefrom hydrolysis and prepares.In addition, can also use ortho-phosphoric acid, metaphosphoric acid, Vanadium Pentoxide in FLAKES, phosphorus trichloride, phosphorus pentachloride to replace POCl3 through the ordinary method preparation.
In above-mentioned addition reaction, used oxirane is that carbonatoms is the better of 2-4.Particularly, can enumerate oxyethane, propylene oxide and butylene oxide ring and their block thing etc., they can be to make up separately or more than 2 kinds.
As above-mentioned monomer (2); For example, can enumerate acid phosphorus acyloxy polyethyleneglycol (methyl) propenoate, acid phosphorus acyloxy W 166 list (methyl) propenoate, acid phosphorus acyloxy six glycol monomethyls (methyl) propenoate, acid phosphorus acyloxy six Ucar 35 list (methyl) propenoate, acid phosphorus acyloxy ten Diethylene Glycol list (methyl) propenoate, acid phosphorus acyloxy ten dipropylene glycol list (methyl) propenoate etc.
In addition; As the polymerizability unsaturated monomer of above-mentioned phosphorous acidic group, also can be included in the polymerizability unsaturated monomer of addition methyl propenoic acid glycidyl base ester gained on monoalkyl (butyl, decyl, dodecyl, the octadecyl etc.) phosphoric acid, the polymerizability unsaturated monomer of addition methyl propenoic acid glycidyl base ester gained on benzyl phosphoric acid.
In the present invention; Through going up this monomer of copolymerization at above-mentioned water-borne acrylic resin (A1); Can improve by tack, water tolerance, the water-fast tack of filming of forming of water-based paint compositions of the present invention coated; Its copolymerization amount is the 0.1-10 quality % in used whole monomers in water-borne acrylic resin (A1) preparation, is preferably 0.1-7 quality %, more preferably 0.3-3 quality %.
In above-mentioned water soluble acrylic resin (A1); As with other polymerizability unsaturated monomer of the polymerizability unsaturated monomer copolymerization of above-mentioned phosphorous acidic group; Give an example contain can with the compound of the polymerizability unsaturated group of above-mentioned monomer copolymerization, its object lesson for example can be enumerated the polymerizability unsaturated monomer that contains alkyl of (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, the just own ester of (methyl) vinylformic acid, (methyl) vinylformic acid octyl group ester, (methyl) 2-ethylhexyl acrylate, (methyl) vinylformic acid nonyl ester, (methyl) tridecyl acrylate, (methyl) dodecylacrylate, (methyl) vinylformic acid stearyl, " vinylformic acid isooctadecane base ester " straight or brancheds such as (productions of Osaka organic chemistry society); (methyl) vinylformic acid cyclohexyl ester, (methyl) vinylformic acid methylcyclohexyl ester, (methyl) vinylformic acid tert-butylcyclohexyl ester, (methyl) vinylformic acid cyclo-dodecyl ester etc. contain the polymerizability unsaturated monomer of naphthenic base; (methyl) isobornyl acrylate etc. contains the polymerizability unsaturated monomer of isobornyl; (methyl) vinylformic acid adamantane esters etc. contains the polymerizability unsaturated monomer of adamantyl (ア ダ マ Application チ Le); Aromatic vinyl monomers such as vinylbenzene, alpha-methyl styrene, Vinyl toluene; (methyl) vinylformic acid hydroxyalkyl acrylates such as (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid 2-hydroxy-propyl ester, (methyl) vinylformic acid 3-hydroxy-propyl ester, (methyl) vinylformic acid 4-hydroxybutyl ester; (methyl) propenoate of the hydroxyls such as 6-caprolactone modification body of vinyl carbinol, above-mentioned (methyl) vinylformic acid hydroxyalkyl acrylate; Having molecular end is the hydroxyl polymerizability unsaturated monomers such as (methyl) propenoate of the polyethylene oxide chain of hydroxyl; (methyl) vinylformic acid, toxilic acid, Ba Dousuan, propenoic acid beta-carboxylic polymerizability unsaturated monomers such as carboxy ethyl ester; Vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, γ-(methyl) acryloxy propyl trimethoxy silicane, γ-(methyl) acryloxy propyl-triethoxysilicane etc. contain the polymerizability unsaturated monomer of alkoxysilane group; (methyl) perfluoroalkyl acrylate such as (methyl) vinylformic acid perfluoro butyl ethyl ester, (methyl) vinylformic acid perfluoro capryl ethyl ester; Fluoroolefins etc. have the polymerizability unsaturated monomer of fluoro-alkyl; (methyl) vinylformic acid glycidyl esters, (methyl) vinylformic acid Beta-methyl glycidyl esters, (methyl) vinylformic acid 3; 4-epoxycyclohexyl methyl ester, (methyl) vinylformic acid 3; 4-epoxycyclohexyl ethyl ester, (methyl) vinylformic acid 3,4-epoxycyclohexyl propyl diester, allyl glycidyl ether etc. contain the polymerizability unsaturated monomer of epoxy group(ing); Polymerizability unsaturated monomer with photopolymerizable functional groups such as dimaleoyl iminos; (methyl) vinylformic acid 1,2,2,6,6-pentamethyl-piperidines ester, (methyl) vinylformic acid 2,2,2,6,6-tetramethyl piperidine ester etc.; Vinyl compounds such as N-vinyl pyrrolidone, ethene, divinyl, chloroprene, ethyl propionate, vinyl acetic monomer; The nitrogenous polymerizability unsaturated monomers such as affixture of (methyl) vinyl cyanide, (methyl) acrylic amide, dimethylamino-propyl (methyl) acrylic amide, dimethylaminoethyl (methyl) acrylic amide, (methyl) vinylformic acid glycidyl esters and amine; Having molecular end is (methyl) propenoate of the polyalkylene oxide chain of alkoxyl group; 2-acrylic amide-2-methyl propane sulfonic acid, allyl sulphonic acid, styrene sulfonic acid sodium salt, methylacrylic acid sulphonyl ethyl ester and sodium salt or ammonium salt etc. contain sulfonic polymerizability unsaturated monomer; Propenal, methyl ethyl diketone acrylic amide, methyl ethyl diketone USAF RH-1, methylacrylic acid acetoacetoxy groups ethyl ester, formyloxy vinylbenzene, the vinyl alkyl ketone (for example ethenyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) etc. with 4-7 carbon atom have the polymerizability unsaturated monomer of acyl group etc., their can be separately or more than 2 kinds compsn use.
Above-mentioned water-borne acrylic resin of the present invention (A1); From the tack of filming that is formed by water-based paint compositions of the present invention, the angle of water-fast tack, the second-order transition temperature of the multipolymer that is made by the polymerizability unsaturated monomer that constitutes water-borne acrylic resin (A1) hopes to drop in-50～60 ℃, preferred-20～35 ℃ the scope.
In this manual, second-order transition temperature (T) is the value of calculating through following formula:
1/Tg＝W
1/T
1+W
2/T
2+...W
n/T
n
In the formula, W
1, W
2... W
nBe each monomeric quality % [=(each monomeric combined amount/monomeric total mass) * 100], T
1, T
2... T
nSecond-order transition temperature (T) for each monomer homopolymer.In addition; The second-order transition temperature of each monomer homopolymer is the value among " polymer handbook " (Polymer Hand Book) (the 4th edition); For the monomeric second-order transition temperature of not putting down in writing in the document; Synthetic weight-average molecular weight is this monomer homopolymer of about 50,000, and its second-order transition temperature uses the value through the hot assay determination of differential scanning type.
In above-mentioned water-borne acrylic resin (A1), other polymerizability unsaturated monomer preferably comprises and for example has the polymerizability unsaturated monomer that carbonatoms is the alkyl more than 6.
Has the polymerizability unsaturated monomer that carbonatoms is the alkyl more than 6 as this; For example; Can enumerate (methyl) vinylformic acid n-hexyl ester, (methyl) vinylformic acid octyl group ester, (methyl) 2-ethylhexyl acrylate, (methyl) vinylformic acid nonyl ester, (methyl) tridecyl acrylate, (methyl) dodecylacrylate, (methyl) vinylformic acid stearyl, " vinylformic acid isooctadecane base ester " (production of Osaka organic chemistry society) etc., can separately or make up more than 2 kinds and use.
Through this monomer, can improve the tack of filming, the water tolerance that form by water-based paint compositions of the present invention, when being coated with the varnish colour that contains the linking agent composition outside, can improve the perviousness of linking agent.
This has the polymerizability unsaturated monomer that carbonatoms is the straight or branched alkyl more than 6, and 1～50 quality % of all polymerizability unsaturated monomers that use in the time of can be with the preparation that accounts for water-borne acrylic resin (A1), the scope of preferred 15～35 quality % are used.
In addition, above-mentioned other polymerizability unsaturated monomer, the angle from the water-fast tack of filming that formed by water-based paint compositions of the present invention preferably comprises the polymerizability unsaturated monomer with hydroxyl.
As polymerizability unsaturated monomer with hydroxyl; For example, can enumerate (methyl) vinylformic acid hydroxyalkyl acrylates such as (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid 2-hydroxy-propyl ester, (methyl) vinylformic acid 3-hydroxy-propyl ester, (methyl) vinylformic acid 4-hydroxybutyl ester; The 6-caprolactone modification body of vinyl carbinol, above-mentioned (methyl) vinylformic acid hydroxyalkyl acrylate etc. has (methyl) propenoate of hydroxyl; Have molecular end and be (methyl) propenoate etc. of the polyethylene oxide chain of hydroxyl, their can be separately or more than 2 kinds combination use.Through this monomer, can improve the solvability of water-borne acrylic resin (A1) for water, and, can improve the tack of filming that forms by water-based paint compositions of the present invention.
This polymerizability unsaturated monomer with hydroxyl, 1～40 quality % of all polymerizability unsaturated monomers that use in the time of can be with the preparation that accounts for water-borne acrylic resin (A1), the scope of preferred 5～30 quality % are used.
In addition, above-mentioned other polymerizability unsaturated monomer, expectation comprises the polymerizability unsaturated monomer with carboxyl.
As polymerizability unsaturated monomer with carboxyl, for example, can enumerate (methyl) vinylformic acid, toxilic acid, Ba Dousuan, propenoic acid beta-carboxy ethyl ester etc., they can separately or make up more than 2 kinds and use.
Through above-mentioned polymerizability unsaturated monomer, can improve the package stability of water-based paint compositions of the present invention with carboxyl.
This polymerizability unsaturated monomer with carboxyl, 0.1～15 quality % of all polymerizability unsaturated monomers that use in the time of can be with the preparation that accounts for water-borne acrylic resin (A1), the scope of preferred 0.1～10 quality % are used.
Above-mentioned water-borne acrylic resin of the present invention (A1) can prepare through for example in the presence of hydrophilic organic solvent, adopting polymerization starter to carry out polymerization above-mentioned polymerizability unsaturated monomer.
As hydrophilic organic solvent, for example, can enumerate alcohol organic solvent such as methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol; Ether organic solvent such as dioxane, THF; Gylcol ether organic solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, glycol monomethyl isopropyl ether, ethylene glycol mono-n-butyl ether, glycol monomethyl ethyl isobutyl ether, glycol monomethyl uncle butyl ether; Glycol ether ether organic solvents such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diglycol monotertiary positive propyl ether, diglycol monotertiary isopropyl ether, diglycol monotertiary n-butyl ether, diglycol monotertiary ethyl isobutyl ether, diglycol monotertiary uncle butyl ether; Ucar 35 ethers organic solvents such as propylene glycol monomethyl ether, dihydroxypropane single-ether, Ucar 35 list positive propyl ether, Ucar 35 list isopropyl ether; Dipropylene glycol ethers organic solvents such as dipropylene glycol monomethyl ether, dipropylene glycol list ether, dipropylene glycol list positive propyl ether, dipropylene glycol list isopropyl ether; Ester class organic solvents such as vinyl acetic monomer, N-BUTYL ACETATE, isobutyl acetate, 3-methoxyl group butylacetic acid ester etc., they can separately or make up more than 2 kinds and use.
As the polymerization starter that uses in the polymerization; For example, can enumerate organo-peroxides such as benzoyl peroxide, decoyl superoxide, lauroyl peroxide, stearyl superoxide, cumene hydroperoxide, tert-butyl peroxide, tert-butyl hydroperoxide laurate, tert-butyl hydroperoxide sec.-propyl carbonic ether, tert-butyl hydroperoxide acetic ester, diisopropyl benzene superoxide; Diisopropyl azodicarboxylate, azo two (2; The 4-methyl pentane nitrile), azo two (2-methyl propionitrile), azo two (2-methylbutyronitrile), 4,4 '-azo (4-cyano butyric acid), dimethyl-azo two (2 Methylpropionic acid ester), azo [2-methyl-N-(2-hydroxyethyl)-propionic acid amide], azo two azo cpds such as { 2-methyl-N-[2-(1-hydroxybutyl)]-propionic acid amide }; Persulphates such as Potassium Persulphate, ammonium persulphate, Sodium Persulfate etc.They can separately or make up more than 2 kinds and use respectively.
In addition, above-mentioned water-borne acrylic resin (A1) for improving the water-soluble of this resin (A1), improves the purpose of the polishability of water-based paint compositions of the present invention, when having carboxyl on the resin (A1), preferably uses in the neutralizing agent and carboxyl.As this neutralizing agent; As long as can in and carboxyl; Then it is had no particular limits; Can enumerate for example amine compound such as ammonia, ethamine, diethylamine, triethylamine, propylamine, dipropylamine, monoethanolamine, diethylolamine, butylamine, quadrol, Mono Methyl Ethanol Amine, dimethylethanolamine, dimethyl propanol amine, be particularly suitable for using dimethylethanolamine.
As the weight-average molecular weight of above-mentioned water-base resin (A1), can be 1000-100000, the scope of preferred 8000-70000.
In this manual, weight-average molecular weight is to be the value of benchmark conversion gained with cinnamic weight-average molecular weight with the weight-average molecular weight of measuring through gel permeation chromatography (eastern ソ one (strain) society make, " HLC8120GPC ").Chromatographic column adopting " tsk gel G-4000H * L ", " tsk gel G-3000H * L ", " tsk gel G-2500H * L ", " tsk gel G-2000H * L " (make by eastern ソ one (strain) society; Trade(brand)name) four posts; Moving phase: THF; Measure temperature: 40 ℃, flow velocity: 1cc/ minute, detector: under the RI condition, carry out.
In the present invention, above-mentioned base coating (A), from the covering with paint operability of water-based paint compositions of the present invention, the face that the is coated with smoothness that formation is filmed, the angle of water-fast tack, expectation comprises waterborne polyurethane resin (A2).
As waterborne polyurethane resin of the present invention (A2), known waterborne polyurethane resin before can unrestrictedly using preferably uses median size to be 0.01-1.0 μ m, the particularly emulsion of the particle form of 0.01-0.5 mu m range.
In this manual, median size is that sample is diluted with deionized water, with " Na ノ マ イ ザ one N-4 " (trade(brand)name, コ one Le タ one society makes, particle size distribution device) values of mensuration under 20 ℃.
Above-mentioned waterborne polyurethane resin of the present invention (A2) from the water-proof angle of filming of package stability and formation, hopes that acid value is 5-100mgKOH/g, is preferably 10-70mgKOH/g.
Above-mentioned waterborne polyurethane resin of the present invention (A2) for example, can enumerate making polymeric polyisocyanate, polyvalent alcohol and the reaction of carboxylic glycol obtain urethane prepolymer, more as required in the presence of the chain extension agent, is scattered in the water and the resin that obtains.
As polymeric polyisocyanate, can enumerate aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylammonium hexamethylene diisocyanate, dipolymer acid vulcabond, LDI; The titration type of these diisocyanate cpds (PVC ユ one レ Star ト タ イ プ) affixture, isocyanurate ring affixture; Isophorone vulcabond, 4,4 '-methylene radical two (cyclohexyl isocyanate), methylcyclohexane-2,4-(perhaps 2; 6-) vulcabond, 1; 3-(perhaps 1,4-) two (isocyanic ester methyl) hexanaphthene, 1,4-cyclohexyl diisocyanate, 1; 3-pentamethylene vulcabond, 1, alicyclic diisocyanate compounds such as 2-cyclohexyl diisocyanate; The titration type affixture of these vulcabond, isocyanurate ring affixture; Xylylene vulcabond, an xylylene vulcabond, tetramethyl-benzene dimethyl-vulcabond, Tolylamine vulcabond, 4; 4 '-diphenylmethanediisocyanate, 1; 5-naphthalene diisocyanate, 1,4-naphthalene diisocyanate, 4,4 '-Tolylamine vulcabond, 4; 4 '-diphenyl ether isocyanic ester, (m-or p-) phenylene diisocyanate, 4; 4 '-biphenyl diisocyanate, 3,3 '-dimethyl--4,4 '-biphenyl diisocyanate, two (4-NCO phenyl) sulfone, isopropylidene two aromatic diisocyanate compounds such as (4-phenyl isocyanate); The titration type affixture of these diisocyanate cpds, isocyanurate ring affixture; Triphenyl methane-4,4 ', 4 "-and triisocyanate, 1,3; 5-triisocyanate base benzene, 2,4,6-triisocyanate base toluene, 4,4 '-dimethyl diphenylmethane-2; 2 ', 5 has the polyisocyanate compound of 3 above NCOs in 1 molecule such as 5 '-tetraisocyanate; The titration type affixture of these polyisocyanate compounds, isocyanurate ring affixture; So that the excessive ratio of NCO makes polyisocyanate compound and terepthaloyl moietie, Ucar 35,1,4-butyleneglycol, dimethylol propionic acid, gather the urethanes of hydroxyl groups reaction gained such as alkane glycol, TriMethylolPropane(TMP), hexane triol; The titration type affixture of these urethanes, isocyanurate ring affixture etc.
As above-mentioned polyvalent alcohol, for example, can enumerate polyoxyethylene glycol, W 166, Vilaterm-third rare (block or random) glycol, gather the butyl ether glycol, gather the hexyl ether glycol, gather polyether glycol such as octyl ether glycol; Dicarboxylicacid (hexanodioic acid, succsinic acid, sebacic acid, pentanedioic acid, toxilic acid, fumaric acid, phthalic acid etc.) and glycol (terepthaloyl moietie, Ucar 35,1; 4-butyleneglycol, 1; 6-pinakon, 3-methyl isophthalic acid; 5-pentanediol, NSC 6366, dihydroxyl methylcyclohexane etc.) condensation and the polyvalent alcohol that obtains, for example polyethyleneglycol adipate, polytetramethylene glycol adipic acid ester, gather pinakon adipic acid ester, PNPGA polyneopentyl glycol adipate, gather-3-methyl amyl adipic acid ester, polyoxyethylene glycol/butyleneglycol adipic acid ester, gather neo-pentyl/polyester polyols such as hexyl adipic acid ester; Polycaprolactone polyol, gather-the 3-methylpent in ester polyol, polycarbonate polyol, terepthaloyl moietie, glycol ether, triglycol, 1; 2-Ucar 35,1; 4-butyleneglycol, butyleneglycol, pinakon, decanediol, ethohexadiol, tristane dihydroxymethyl, Hydrogenated Bisphenol A 99, cyclohexanedimethanol, 1; Low molecular weight diols classes such as 6-pinakon etc. can separately or be united use more than 2 kinds.
As above-mentioned carboxylic glycol, can enumerate for example dihydroxymethyl acetic acid, dimethylol propionic acid, dimethylolpropionic acid etc.
Above-mentioned waterborne polyurethane resin (A2) can be through the neutralizing agent neutralization among the present invention.As neutralizing agent; It is had no particular limits; For example, can enumerate amine compound such as ammonia, ethamine, diethylamine, triethylamine, propylamine, dipropylamine, monoethanolamine, diethylolamine, butylamine, quadrol, Mono Methyl Ethanol Amine, dimethylethanolamine, dimethyl propanol amine.With respect to 1 equivalent carboxyl, neutralizing agent usually can be with the 0.5-2.0 equivalent, and the normal ratio of preferred 0.7-1.3 uses.
The mixture ratio of above-mentioned water-borne acrylic resin (A1) and waterborne polyurethane resin (A2); From the water-fast tack of filming that forms by water-based paint compositions of the present invention, the angle of grinding operation property; Solids component mass ratio in water-borne acrylic resin (A1)/waterborne polyurethane resin (A2); Hope to drop on 1/99～90/10, preferred 1/99～70/30, more preferably 5/95～50/50 scope.
In addition, above-mentioned base coating (A), the water-fast tack angle of filming from forming preferably comprises vinylformic acid Emulgating polymers (A3).
Vinylformic acid Emulgating polymers of the present invention (A3); PEMULEN TR2 is dispersed in the aqueous medium and obtains; For example, can with the polymerizability unsaturated monomer in the presence of the dispersion stabilizer of water and tensio-active agent and so on, carry out emulsion polymerization through a step or multistep and make.
As the polymerizability unsaturated monomer that carries out emulsion polymerization, can be from above-mentioned water-borne acrylic resin (A1), suitably to choose in the illustrative polymerizability unsaturated monomer class.
Aforesaid propylene yogurt fluidized polymer of the present invention (A3); Angle from the tack of filming, water-fast tack and the grinding operation property that form; The second-order transition temperature of the multipolymer that forms by the polymerizability unsaturated monomer that constitutes vinylformic acid Emulgating polymers (A3); Hope to drop on-100～50 ℃ preferred-70～25 ℃ scope.
Suitable copolymerizable composition as aforesaid propylene yogurt fluidized polymer (A3); The polymerizability unsaturated monomer of the alkyl that can to enumerate for example above-mentioned carbon atom quantity be the straight or branched more than 6; When using this monomer,, can be used whole monomeric 10-80 quality % in vinylformic acid Emulgating polymers (A3) preparation as its consumption; Preferred 15-70 quality %, the more preferably scope of 20-60 quality %.
In addition; From the stability of vinylformic acid Emulgating polymers (A3) water and the angle of the water-fast tack of filming that forms by water-based paint compositions of the present invention; This vinylformic acid Emulgating polymers (A3); As copolymer composition, preferably include above-mentioned hydroxyl polymerizability unsaturated monomer and/or contain carboxyl polymerizability unsaturated monomer.
As the consumption of the polymerizability unsaturated monomer of above-mentioned hydroxyl, can be used whole monomeric 1-30 quality % in vinylformic acid Emulgating polymers (A3) preparation, the scope of preferred 1-20 quality %.In addition, as the consumption of carboxylic polymerizability unsaturated monomer, can be used whole monomeric 0.1-10 quality % in vinylformic acid Emulgating polymers (A3) preparation, the scope of preferred 0.1-5 quality %.
In the present invention, vinylformic acid Emulgating polymers (A3) can also comprise above-mentioned phosphorous acidic group the polymerizability unsaturated monomer as copolymer composition.When using the polymerizability unsaturated monomer of this phosphorous acidic group,, can be used whole monomeric 0.1-10 quality % in vinylformic acid Emulgating polymers (A3) preparation, the scope of preferred 0.1-5 quality % as its usage quantity.
Median size as like the above-mentioned vinylformic acid Emulgating polymers (A3) that makes can be 0.01-1.0 μ m, the scope of preferred 0.05-0.5 μ m.
When the above-mentioned base coating (A) among the present invention comprises aforesaid propylene yogurt fluidized polymer (A3); As its content; Consider from the water-fast tack of filming that forms, the harmony of grinding operation property; Solids component 100 mass parts with above-mentioned water-borne acrylic resin (A1) are benchmark, hope the mass parts for 1-200, the scope of preferred 5-180 mass parts.
In the present invention, from the angle of shelf-stable, base coating (A) can comprise tackifier (A4).As this tackifier (A4), known tackifier before can unrestrictedly using particularly, can be enumerated for example mineral-type tackifier such as silicate, metal silicate, smectite, organic montmorillonite, colloidal state alumina; ZX-I, ROHM-polyacrylic tackifier such as (methyl) Yodo Sol GH 28; " UH-814N ", " UH-462 ", " UH-420 ", " UH-472 ", " UH-540 " (above), " SN シ Star Network Na 1 ", " SN シ Star Network Na one 621N ", " SN シ Star Network Na one 625N ", " SN シ Star Network Na one 627N " urethane association type tackifier such as (above) by the production of サ Application ノ プ コ society by the production of rising sun electrification society; Derivatived cellulose class tackifier such as CMC 99.5, methylcellulose gum, hydroxy ethyl cellulose; Protein-based tackifier such as casein, sodium-caseinate, ammonium caseinate; Polyethylene kind tackifier such as marine alga acids tackifier such as sodium-alginate, Z 150PH, Vinylpyrrolidone polymer, Vilaterm benzylic ether multipolymer; Polyethers tackifier such as W 166 and oxyethane addition polymer polyethers, polyethers dialkyl, polyethers dialkyl ether, polyether, epoxy modifier; Copolymer-maleic anhydride class tackifier such as the part ester of vinyl methyl ether-copolymer-maleic anhydride; Polyamide-based tackifier such as polymeric amide amine salt etc., they can separately or make up more than 2 kinds and use.
Above-mentioned tackifier of the present invention (A4) based on contained resin solid composition in the base coating (A), hope to be 0.01-20 quality % usually, are preferably the scope of 0.05-10 quality %.
In the present invention; Good from making with the Combination of following thinner (B); Can improve the rheology control effect of the tackifier in the water-based paint compositions of the present invention; And the angle that can improve formed drying property of filming and film-forming properties is set out, and preferred above-mentioned base coating (A) comprises hydrophilic organic solvent.As this hydrophilic organic solvent, suitably select independent or two or more the use in the compound that can from explanation, enumerate to above-mentioned water-borne acrylic resin (A1).
The reaction solvent that above-mentioned hydrophilic organic solvent can be used as aforesaid resinous principle mixes, and also can directly mix.
The content of hydrophilic organic solvent in the above-mentioned base coating of the present invention (A); From the package stability of base coating (A), the covering with paint operability of water-based paint compositions, the angle of polishability; With water-borne acrylic resin (A1) resin solid composition 100 mass parts is benchmark; Hope to be the 50-400 mass parts, be preferably the scope of 100-300 mass parts.
In addition, from improving the wetting properties of coated article or the angle of film-forming properties, above-mentioned base coating (A) can also comprise hydrophobic organic solvent.Hydrophobic organic solvent of the present invention can be enumerated HLB value less than 7, and has the compound of hydroxyl in the molecule, for example, can enumerate alcoholic solvents such as Pentyl alcohol, n-hexyl alcohol, n-Heptyl alcohol, hexalin, n-Octanol, benzylalcohol; Glycol ethers solvents such as ethylene glycol mono hexyl ether, glycol monomethyl 2-ethylhexyl ether; Propylene glycol kind solvents such as propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether etc., they can separately or select to use more than 2 kinds.N-hexyl alcohol, n-Heptyl alcohol, n-Octanol, glycol monomethyl 2-ethylhexyl ether, ethylene glycol mono hexyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether etc. are more suitable in the middle of them, and particularly ethylene glycol mono hexyl ether and glycol monomethyl 2-ethylhexyl ether are more suitable.
In addition, in this manual, the HLB value adopts the value that is obtained by Davis (デ one ヴ イ ス) installation.Method through Davis's installation calculating HLB value is recorded in Proc.2nd Intern.Congress of Surface Activity, the 1st volume, and (1957) are among the p426.
The content of the hydrophobic organic solvent in the above-mentioned base coating (A); Package stability angle from base coating (A); Resin solid composition 100 mass parts with water-borne acrylic resin (A1) are benchmark, hope the mass parts for 10-400, are preferably the scope of 25-300 mass parts.
Water-based paint compositions of the present invention can be the varnish colour that does not contain pigment in fact, also can be the enamel paint that contains pigment, when being enamel paint, need pigment be included in the base coating (A).As used coating, can unrestrictedly use pigment such as the photoluminescent pigment that uses in the common paint field, tinting pigment, filler pigment.As photoluminescent pigment, can enumerate for example metallic pigment such as aluminium powder, copper bronze, copper powder, glass putty, lead powder, zinc powder, iron phosphide; Pearl pigments such as pearl shape coating metal mica powder, mica shape red stone as tinting pigment, can be enumerated white pigments such as titanium oxide; Black pigments such as carbon black, acetylene carbon black, dim, bone black, graphite, iron oxide black, nigrosine; Yellow ultramarines such as Zh 1, titan yellow, monoazo yellow, condensation azophosphine, azomethine Huang, bismuth vannadate, benzimidazolone, iso-dihydro-indole, isoindoline, Kui phthalein ketone, diarylide yellow, permanent yellow; Consolidate orange pigmentss such as orange forever; Red pigments such as RED IRON OXIDE, naphthols AS azophloxine, anthanthrone is red, anthraquinone is red (ア Application ス ラ キ ノ ニ Le レ Star De), perylene maroon, quinoline a word used for translation ketone red, diketopyrrolo-pyrrole, C lake red CAN'T, permanent bordeaux; Violet pigments such as cobalt violet, quinacridone violet 、 dioxazine violet; Blue pigmentss such as cobalt blue, phthalocyanine blue, indanthrene blue; Veridians such as phthalocyanine green etc.; As filler pigment, can enumerate heavy soil powder, settleability permanent white, barium carbonate, lime carbonate (charcoal acid カ Le シ system), gypsum, clay, silica, white carbon, zeyssatite, talcum, magnesiumcarbonate, white lake, gloss white, mica powder etc.
When using metallic pigment as pigment of the present invention, its shape is had no particular limits, flakey is more suitable, in addition, from suppressing the angle that hydrogen produces, preferably with phosphorous acidic group or the lining of sulfonic treatment agent dispersion treatment.
Phosphorous acidic group or sulfonic treatment agent have no particular limits it, known low molecular compound or multipolymer before can using.
Combined amount as above-mentioned pigment; Can adjust according to the kind of pigment; Usually with respect to solids component 100 mass parts of contained resinous principle in the base coating (A), the 0.1-300 mass parts be can be, 0.5-200 mass parts, the scope of 1-150 mass parts more preferably are preferably.
In above-mentioned base coating (A), the water-soluble and/or water-dispersed resin of other that can also suitably select usually to form as the water-borne coatings film that composition uses carries out coupling.As this water-soluble and/or water-dispersed resin, can enumerate that for example alkyd based resin, polyester resin, cellulosic resin etc. are water-soluble or the resin of water-dispersionization.
In the above-mentioned base coating (A); Can also be as required, normally used other composition during water-borne coatingss adjustment such as mixing UV light absorber, photostabilizer, surface finishing agent, polymer particles, dispersing auxiliary, alkaline neutraliser, sanitas, silane coupling agent, skimmer, curing catalysts.
In the present invention, the viscosity of above-mentioned base coating (A) has no particular limits it, from the package stability angle, can be 100-2000mPasec, is preferably 600-2000mPasec, more preferably the scope of 700-1600mPasec.In this manual, viscosity is at 25 ℃ of modulated samples, is the value of measuring under the condition of 60rpm with " digital PVC ス メ ト ロ Application viscometer VDA type " (trade(brand)name, sesame Pu シ ス テ system Co., Ltd. makes) in speed of rotation.
In addition, above-mentioned base coating (A) is hoped pH regulator 6.0～10.0, in preferred 7.0～9.0 the scope.Drop in this scope through the pH value that makes base coating (A); Can make the Combination of itself and following thinner (B) good; And constantly can make the viscosity of the compo of base coating (A)/thinner (B) in mixing is suitable viscosity, can further improve the covering with paint operability.The adjusting of pH can be used basic cpds such as amine compound such as sodium hydroxide, Pottasium Hydroxide, Trimethylamine 99, dimethylaminoethanol, 2-methyl-2-amino-1-propyl alcohol, triethylamine, ammoniacal liquor.
PH in this specification sheets is with the temperature regulation to 25 of sample ℃, the value of measuring with " HM-40V " (trade(brand)name, electric wave Industrial Co., Ltd in East Asia makes, pH meter).
Thinner (B)
In the present invention, thinner (B) is the thinner that comprises tackifier (B1) and water.
As this tackifier (B1), known tackifier before can unrestrictedly using as its concrete example, for example, can be enumerated mineral-type tackifier such as silicate, metal silicate, smectite, organic montmorillonite, colloidal state alumina; ZX-I, ROHM-polyacrylic tackifier such as (methyl) Yodo Sol GH 28; " UH-814N ", " UH-462 ", " UH-420 ", " UH-472 ", " UH-540 " (above), " SN シ Star Network Na 1 ", " SN シ Star Network Na one 621N ", " SN シ Star Network Na one 625N ", " SN シ Star Network Na one 627N " urethane association type tackifier such as (above) by the production of サ Application ノ プ コ society by the production of rising sun electrification society; Derivatived cellulose class tackifier such as CMC 99.5, methylcellulose gum, hydroxy ethyl cellulose; Protein-based tackifier such as casein, sodium-caseinate, ammonium caseinate; Marine alga acids tackifier such as sodium-alginate; Polyethylene kind tackifier such as Z 150PH, Vinylpyrrolidone polymer, Vilaterm benzylic ether multipolymer; Polyethers tackifier such as W 166 and oxyethane addition polymer polyethers, polyethers dialkyl, polyethers dialkyl ether, polyether, epoxy modifier; Copolymer-maleic anhydride class tackifier such as the part ester of vinyl methyl ether-copolymer-maleic anhydride; Polyamide-based tackifier such as polymeric amide amine salt etc., they can separately or make up more than 2 kinds and use.
The content of above-mentioned tackifier (B 1) in thinner (B) from the viscosity of thinner (B) and the angle of package stability, can be 0.01～10 quality % in the thinner (B), is preferably the scope of 0.05～5 quality %.
In addition, above-mentioned thinner (B), from the Combination of base coating (A), the angle of covering with paint, lacquer, colour wash, etc. operability, polishability, preferably comprise hydrophilic organic solvent.
As above-mentioned hydrophilic organic solvent, suitably select independent or two or more the use in the compound that can from explanation, enumerate to above-mentioned water-borne acrylic resin (A1).
In the present invention; The smoothness equal angles of filming during from covering with paint operability, polishability, secondary coating; As contained hydrophilic organic solvent in the thinner (B), the part of its composition use glycol ether ether organic solvent and/or dipropylene glycol ethers organic solvent are better.As its consumption, can carry out suitable adjustment according to covering with paint, lacquer, colour wash, etc. environment etc., for example, can be 0.01～20 quality % in the thinner (B), be preferably the scope of 0.1～10 quality %.
In addition; From covering with paint, lacquer, colour wash, etc. the blended angle of operability, the drying property of filming, above-mentioned base coating (A) and thinner (B), contained hydrophilic organic solvent is that to be selected from least a organic solvent of alcohol organic solvent, gylcol ether organic solvent, Ucar 35 ethers organic solvent and ester class organic solvent better in the thinner (B).As its consumption, can carry out suitable adjustment according to covering with paint, lacquer, colour wash, etc. environment, can be 0.01～50 quality % in the thinner (B), be preferably the scope of 0.1～30 quality %.
The coating of using always when above-mentioned thinner of the present invention (B) can also comprise water-borne coatingss such as the organic solvent adjustment beyond pigment, UV light absorber, photostabilizer, alkaline neutraliser, sanitas, silane coupling agent, skimmer, surface finishing agent, curing catalysts, the above-mentioned hydrophilic organic solvent as required is with other compositions such as additives.
As above the pH of gained thinner (B) is adjusted in 3.0-11.0, and is particularly better in the scope of 4.0-10.0.
PH through making thinner (B) drops on this scope; Can make the Combination of itself and above-mentioned base coating (A) good; And constantly can make the viscosity of base coating (A)/thinner (B) compo at blended is suitable viscosity, can further improve the covering with paint operability.The adjusting of pH can be used basic cpds such as amine compound such as sodium hydroxide, Pottasium Hydroxide, Trimethylamine 99, dimethylaminoethanol, 2-methyl-2-amino-1-propyl alcohol, triethylamine, ammoniacal liquor.
Water-based paint compositions
Water-based paint compositions of the present invention can be through mixing base coating (A) and thinner (B) and modulation easily before covering with paint, lacquer, colour wash, etc.In addition, in this specification sheets before the so-called covering with paint, for example can enumerate before covering with paint, lacquer, colour wash, etc. 3 hours during.
Mixture ratio as base coating in the aforementioned coating composition (A) and thinner (B); Can suitably adjust according to covering with paint, lacquer, colour wash, etc. environment etc.; For example; From covering with paint, lacquer, colour wash, etc. operability, the polished appearance of filming of formation, the consideration of concealed angle, can make viscosity for being adjusted to 100-400mPasec, the scope of preferred 120-300mPasec.
With respect to the amount of the thinner (B) of base coating (A), for example the amount of thinner (B) can be 30-200 quality % usually with respect to the quality of base coating (A), is preferably the scope of 40-160 quality % when reaching this viscosity.
In the present invention; When base coating (A) comprises tackifier (A4); Tackifier (B1) in these tackifier (A4) and the above-mentioned thinner (B); From the angle of the covering with paint operability of water-based paint compositions of the present invention, the combination that is selected from mineral-type tackifier and polyacrylic tackifier, urethane association type tackifier and polyacrylic tackifier, urethane association type tackifier and mineral-type tackifier is better.
As the coating form of the water-based paint compositions of the invention described above, be preferably the two-component-type compsn that constitutes by base coating (A) and thinner (B).
In addition, water-based paint compositions of the present invention as required, can also further contain solidifying agent such as polyisocyanate curing agent, blocked isocyanate solidifying agent, melamine cured Ji 、 oxazoline solidifying agent, carbodiimide solidifying agent.
When water-based paint compositions contains above-mentioned solidifying agent; Kind according to solidifying agent; The coating form of this water-based paint compositions can suitably be selected three component types of base coating (A), thinner (B) and solidifying agent, and perhaps base coating (A) and solidifying agent are mixed into a liquid, and itself and thinner (B) are combined into two-component-type; Perhaps thinner (B) is mixed into a liquid with solidifying agent, and itself and base coating (A) are combined into two-component-type etc.
As the coated surface that is applicable to that the invention described above water-based paint compositions is covered with paint, lacquer, colour wash, etc., can enumerate metals such as iron, aluminium, flavones, copper coin, stainless steel plate, tinplate, steel plate galvanized, alloy plating zinc (Zn-Al, Zn-Ni, Zn-Fe etc.) steel plate; These metallic surfaces are carried out chemically treated surface-treated metals such as zn phosphate processing, chromate treating; Coated article material surfaces such as plastics, timber, concrete, mortar, perhaps these coated article material surfaces cover with paint, lacquer, colour wash, etc. primary coats with or in be coated with and/or the film coated surface behind the coating etc. outward.
In addition,, can it be had no particular limits,, can be any one method in heat drying, forced drying, the Air drying as drying means for the covering with paint of spraying paint, static covering with paint, mopping covering with paint, roller covering with paint etc. as the covering with paint means.
In addition, after covering with paint, lacquer, colour wash, etc. above-mentioned water-based paint compositions on the coated surface, can also on this is filmed, cover with paint, lacquer, colour wash, etc. outer varnish colour and form varnish and film.
In this case, before covering with paint, lacquer, colour wash, etc. outer varnish colour, can make based on the curing of coating of above-mentioned water-based paint compositions dryly, also can on uncured this filmed, cover with paint, lacquer, colour wash, etc. outer varnish, and make two dried coating films.
As above-mentioned outer varnish colour; Known coating before particularly can unrestrictedly using; For example can suitably use vinyl resin or fluorine resin to be host with bridging property functional groups such as hydroxyls; And contain the curable coating as solidifying agent such as block polyisocyanate, POLYMETHYLENE POLYPHENYLISOCYANATE or melamine resin; Perhaps acrylic resin modified with cellulose acetate butyrate is the paint etc. of staple, can also further contain coating such as pigment class, derivatived cellulose class, additional resin, UV light absorber, photostabilizer, surface finishing agent, curing catalysts as required and use additive.Wherein when use contains the coating of polyisocyanate curing agent; Because the part of polyisocyanate curing agent is filmed from outer varnish the filming of immersion water-based paint compositions; It can with the hydroxyl reaction in filming based on water-based paint compositions; Thereby can use without curing agent component or decrement in the water-based paint compositions, and can improve based on the filming and tack, the water-fast tack of outer varnish between filming of water-based paint compositions, thereby more suitable.
[embodiment]
Next enumerating embodiment explains the present invention more specifically.Here " part " and " % " is represented " mass parts " and " quality % " separately.
The preparation of acrylic resin soln
Preparation example 1
In 4 liters flask, add 550 parts of Ucar 35 list positive propyl ethers, under nitrogen gas stream, be warming up to 115 ℃.After reaching 115 ℃; Added the monomer mixture that 10 parts of Diisopropyl azodicarboxylates are dissolved in gained in 350 parts of TEB 3Ks, 200 parts of n-butyl acrylates, 250 parts of methylacrylic acid 2-(ethyl hexyl) esters, 130 parts of vinylformic acid 4-hydroxyl butyl esters, 60 parts of vinylformic acid, 10 parts " ラ イ ト エ ス テ Le PM " (note 1) through 3 hours, slaking is after 2 hours.After reaction finishes; Neutralize according to equivalent with dimethylethanolamine; Add 450 parts of Ucar 35 list positive propyl ethers again; Regulate pH to 7.5 with dimethylethanolamine, obtaining second-order transition temperature is 5 ℃, and weight-average molecular weight is 45000, solid component content is 55% yellow propylene liquid acid resin solution (A-1).
(note 1) " ラ イ ト エ ス テ Le PM ": trade(brand)name, Kyoeisha Chemical Co., Ltd. produces, (2-methacryloxyethyl) acid phosphoric acid ester.
Prepare routine 2-5
In preparation example 1, except the prescription of monomer mixture according to shown in the table 1, with preparation example 1 operation likewise, obtain each acrylic resin soln (A-2)～(A-5).
Table 1
(note 2) " NF バ イ ソ マ one S20W ": trade(brand)name, the first industrial pharmacy society produces, and (molecular end is a methoxyl group to the methoxy poly (ethylene glycol) monomethacrylates, and intramolecularly contains 45 monomeric unit C
2H
4The methacrylic ester of O base).
The preparation of ester-polyurethane resin emulsion
Preparation example 6
In 4 liters flask, add 115.5 umber average molecular weights and be 2000 polytetramethylene glycol adipic acid ester, 115.5 umber average molecular weights and be 2000 polycaprolactone glycol, 23.2 parts of dimethylol propionic acids, 6.5 part 1; 4-butyleneglycol and 120.1 parts of isophorone diisocyanates; Make it under agitation in nitrogen gas stream; 85 ℃ of down reactions 7 hours, obtain NCO content and be 4.0% prepolymer.Then this prepolymer is cooled to 50 ℃, adds 165 parts of acetone, behind the dissolving homogeneous; Under agitation add 15.7 parts of triethylamines, below keeping 50C in, add 600 parts of deionized waters; The gained water dispersion was kept 2 hours down at 50 ℃, after completion water prolongs reaction, remove acetone in underpressure distillation below 70 ℃; Regulate pH to 8.0 with triethylamine and deionized water, obtaining acid value is that 26mgKOH/g, solid component content are 30%, and median size is the polyurethane resin solution (B-1) of 0.15 μ m.
The preparation of Emulsion acrylic resin
Preparation example 7
(Japanese emulsifying agent society produces in reaction vessel, to add 100 parts of deionized waters, 2.5 parts " Newcol 707SF "; Anionic emulsifier with polyethylene oxide chain; Solid component content is 30%) and monomer mixture (9 parts of vinylbenzene, 40 parts of n-butyl acrylates, 40 parts of 2-ethylhexyl acrylates, 10 parts of vinylformic acid 2-hydroxy methacrylates, 1 part of methylacrylic acid) in 1 part; Under nitrogen gas stream, mix, add 3 part of 3% ammonium persulfate aqueous solution down at 60 ℃.Then; Be warming up to 80 ℃; To join in the reaction vessel through 4 hours with pump of constant delivery type by remaining 99 parts of above-mentioned monomer mixture, " Newcol 707SF " 2.5 parts, 4 parts of 3% ammonium persulphates and 100 parts of pre-emulsion of forming of deionized water, after interpolation finishes, slaking 1 hour.Then, add 33 parts of deionized waters, regulate pH to 7.5 with dimethylethanolamine, obtain second-order transition temperature and be-44 ℃, median size is that 0.1 μ m, solid component content are 30% Emulsion acrylic resin (C-1).
Preparation example 8
In preparation example 7, except the prescription of monomer mixture is as shown in table 2,, obtain Emulsion acrylic resin (C-2) with preparation example 7 operation likewise.
Table 2
The preparation of aluminium pigment mashed prod
Preparation example 9
(Japan ア Le ミ society produces in mixing container, to add 45.5 parts of aluminium pigment mashed prod " WJE7640 "; Metal content is 52%); The resin solution of 35 parts of ethylene glycol monobutyl ethers, 3 parts of phosphorous acidic groups (note 3) mixes, and obtains aluminium pigment mashed prod (D-1).
The resin solution of (note 3) phosphorous acidic group: the mixed solvent that in 4 liters of flasks that whisking appliance, thermoswitch and cold-hot machine are housed, adds 27.5 parts of methoxypropanol, 27.5 parts of isopropylcarbinols; Be heated to 110 ℃; In above-mentioned mixed solvent, added 121.5 parts in the mixture is made up of the polymerizable monomer (note 4) of 25 parts of vinylbenzene, 27.5 parts of n-BMAs, 20 parts " vinylformic acid isooctadecane base ester " (productions of Osaka organic chemistry society), 7.5 parts of vinylformic acid hydroxyl butyl esters, 15 parts of phosphorous acidic groups, 12.5 parts of 2-methacryloxyethyl acid phosphoric acid esters, 10 parts of isopropylcarbinols and 4 parts of tert-butyl hydroperoxide octanoates through 4 hours, warp dropping in 1 hour is by 0.5 part of tert-butyl hydroperoxide octanoate and 20 parts of mixtures that Virahol is formed again.Then, stir and carried out slaking in 1 hour, obtain solid component content and be the resin solution of 50% phosphorous acidic group.
The polymerizable monomer of (note 4) phosphorous acidic group: in 4 liters flask, add 57.5 parts of mono phosphoric acid ester butyl esters, 41.1 parts of isopropylcarbinols, under the condition of bubbling air behind 42.5 parts of SY-Monomer Gs of dropping in 2 hours, restir carried out slaking in 1 hour.Then, add 5.9 parts of Virahols, obtain solid component content and be the polymerizable monomer solution of 50% phosphorous acidic group.
Preparation example 10
In mixing container, add 45.5 parts of aluminium pigment mashed prod " WJE7640 " (trade(brand)name; Japan ア Le ミ society produces, and metal content is 52%), the resin solution of 35 parts of ethylene glycol mono hexyl ether, 3 parts of phosphorous acidic groups (note 3); Mix, obtain aluminium pigment mashed prod (D-2).
The preparation of base coating
Preparation example 11
The acrylic resin soln (A-1) that obtains in 83.5 parts of aluminium pigment mashed prod (D-1) that obtains in the preparation example 9 and the preparation routine 1 joined for 40 parts mix in the container; Stir after 1 hour; With its with preparation example 6 in the Emulsion acrylic resin (C-1) that obtains in 200 parts of ester-polyurethane resin emulsions (B-1) obtaining and the preparation example 7 mix for 66.7 parts; Add " プ ラ イ マ Le ASE60 " (note 5) 17.8 parts, continue again to stir 1 hour, behind dimethylethanolamine adjusting pH; Add deionized water, obtain solid component content and be 20% base coating (I-1).The viscosity of this base coating (I-1), the pH method of middle record to specifications measure, and are respectively 1000mPasec, 8.0.
(note 5) " プ ラ イ マ Le ASE60 ": trade(brand)name, ロ one system ア Application De Ha one ス society produces, the polyacrylic tackifier, acid value is 270mgKOH/g, effective constituent 28%.
Prepare routine 12-20
In preparation example 11, except the prescription composition is as shown in table 3,, obtain base coating (I-2)～(I-10) with preparation example 11 operation likewise.
Table 3
(note 6) " Laponite RD ": trade(brand)name, (RochwoodAdditives Limited produces, mineral-type tackifier, LAPONITE, [Si
8(Mg
5.34Li
0.66) O
20(OH)
4] Na
0.66).
(note 7) " SN シ Star Network Na 1 ": trade(brand)name, サ Application ノ プ コ society produces, polyurethane polyureas ethers tackifier, effective constituent 40%.
The preparation of thinner
Prepare routine 21-23
In mixing container, the compound composition in the below table 4 is mixed, make thinner (II-1)～(II-3)
Table 4
The preparation of water-borne coatings
Embodiment 1
100 parts of 100 parts of base coatings (I-1) and thinners (II-1) are carried out thorough mixing through manual stirring, obtain water-borne coatings (E-1).
Embodiment 2-10 and comparative example 1-4
Except the prescription composition is as shown in table 5, likewise operate with embodiment 1, obtain water-borne coatings (E-2)～(E-14) by base coating and mixing diluents gained.And, listed the viscosity of each water-borne coatings in the table 5 in the lump.The mensuration of the viscosity method of middle record is to specifications carried out, and after base coating and mixing diluents, carries out after 5 minutes excessively.
Table 5
The drying of covering with paint, lacquer, colour wash, etc. and filming
Embodiment 11-20 and comparative example 5-8
With covered with paint, lacquer, colour wash, etc. body of a motor car with the project plate of varnish colour with the #800 wet-strong paper polish, degreasing, as by coated plate.With each water-borne coatings (E-1)～(E-14) of above-mentioned preparation as base coating, under each temperature of table 6 record and each humidity, through pneumatic nebulizer divided for 4 stages (ス テ one ジ) cover with paint, lacquer, colour wash, etc. this by coated plate on, carry out the flow evaluation.Between each stage, produce 50 ℃, the hot blast of 10m/ second through hot air generator, to each test coated plate air-supply, be dried to the state that is not clamminess with the finger contact, obtaining dry film thickness is filming of 30 μ m.(with this to the coated plate that is coated with base coating film by coated plate as test coated plate A).Covering with paint as further extreme trace varnish; Will be to 100 parts of " レ タ Application PG マ Le チ Network リ ヤ one HX (Q) " (trade(brand)names before covering with paint, lacquer, colour wash, etc.; Northwest ペ イ Application ト society produces, and contains the varnish colour of the vinyl resin with hydroxyl) 50 parts of " レ タ Application PG マ Le チ Network リ ヤ one ス タ Application ダ one De solidifying agent " (trade(brand)name, productions of Northwest ペ イ Application ト society of middle mixing; The isocyanuric acid ester type polyisocyanate curing agent of hexamethylene diisocyanate) the outer varnish colour of gained is covered with paint, lacquer, colour wash, etc. on base coating film through pneumatic nebulizer; Making dry film thickness is 40 μ m, makes by the temperature of coated plate with drying machine to remain under 60 ℃ the state rapid drying 20 minutes, obtains the test board coated plate.(filming coated plate that the bilayer formed films as test coated plate B to being coated with by coated plate) by base coating film and outer varnish with this.
Evaluation test
Test coated plate A or B to as above making carry out the and the following evaluation test.The result lists in table 6.
Table 6
(1) flow: divided for 2 stages sprayed and cover with paint, lacquer, colour wash, etc. each water-borne coatings, each stage of visual assessment is by the flow of each water-borne coatings on the coated plate.
Zero: good
Δ: spray and only observe some saggings slightly when covering with paint, lacquer, colour wash, etc.
*: bad (observing significant sagging)
(2) appearance of film: visual assessment is respectively tested the coated surface of coated plate A.
◎: it is level and smooth to be coated with face
Zero: the face that is coated with has some concavo-convex slightly
Δ: the face of being coated with has concavo-convex
*: the face of being coated with has big concavo-convex
(3) polishability: visual assessment is respectively tested the coated surface of coated plate B.
◎: aluminium pigment and homogeneous orientation parallel with the face that is coated with, not thinking fully has the uneven generation of metal.
Zero: thinking has the uneven generation of little metal
Δ: thinking has the uneven generation of a lot of metals
*: thinking has the uneven generation of a lot of metals, and identifies paint film defects such as a lot of crackles, atrophy.
(4) initial stage tack: be cut into cutter and respectively test coated plate B, make 100 grids that size is 1mm * 1mm, on its each surface, stick the viscosity scotch tape, after under 20 ℃ this adhesive tape sharply being peeled off, check the number that remaining grid is filmed to substrate.
◎: remaining 100
Zero: remaining 99-90
Δ: remaining 89-41
*: remaining below 40
The position one that comes off when in addition, grid comes off is listed in the table.
1.: by the interface of coated plate surface with each base coating film.
2.: the interface that each base coating film and outer varnish are filmed.
(5): water tolerance: each test coated plate B was flooded 10 days in 40 ℃ warm water, take out the back and observe the surface of respectively filming.
◎: very good
Zero: good
Δ: find a little albefaction
*: find that protuberance, albefaction etc. are unusual.
(6) water-fast tack: each test coated plate B was flooded 10 days in 40 ℃ hot water, take out, after at room temperature dry 12 hours, according to carrying out the grid test evaluation with the same method of the initial stage tack of above-mentioned (4).
(7) accelerated weathering property: each test coated plate B is supplied in the accelerated weathering test of the accelerated weathering test machine (QUV) that adopts Q パ ネ Le (strain) to make.Test conditions (uviolizing: 70 ℃ following 8 hours～soak into: 4 hours) carry out 100 hours repeatedly after, the coated plate after the test was flooded 2 days in 40 ℃ warm water, as a circulation.With repeating 2 coated plates after this circulation according to carrying out the grid test evaluation with the same method of the initial stage tack of above-mentioned (4).
Claims (11)
1. water-based paint compositions; It is characterized in that it is before covering with paint, lacquer, colour wash, etc., base coating (A) and thinner (B) to be mixed and the water-based paint compositions of the two-component-type that forms; Wherein base coating (A) comprises by containing the composition copolymerization of polymerizability unsaturated monomer and the water-borne acrylic resin (A1) that obtains that 0.1～10 quality % has the polymerizability unsaturated monomer of phosphate; Thinner (B) contains tackifier (B1) and water; And in thinner (B), the content of tackifier (B1) is in the scope of 0.01～10 quality %, and the pH of thinner (B) is in 3.0～11.0 scope.
2. the described water-based paint compositions of claim 1, the polymerizability unsaturated monomer that wherein has phosphate are the compound of formula (1) expression,
In the formula, R
1Expression Wasserstoffatoms or methyl, R
2The expression carbonatoms is 2～4 alkylidene group.
3. the described water-based paint compositions of claim 1, wherein base coating (A) further comprises waterborne polyurethane resin (A2).
4. the described water-based paint compositions of claim 3, wherein the mixture ratio of water-borne acrylic resin (A1) and waterborne polyurethane resin (A2) is counted 1/99～90/10 scope with the solids component mass ratio of water-borne acrylic resin (A1)/waterborne polyurethane resin (A2).
5. each described water-based paint compositions in the claim 1～4, wherein base coating (A) further comprises vinylformic acid Emulgating polymers (A3).
6. each described water-based paint compositions in the claim 1～4, wherein base coating (A) further comprises tackifier (A4).
7. each described water-based paint compositions in the claim 1～4, wherein thinner (B) contains hydrophilic organic solvent.
8. the described water-based paint compositions of claim 7, wherein hydrophilic organic solvent contains glycol ether ether organic solvent and/or dipropylene glycol ethers organic solvent.
9. the described water-based paint compositions of claim 7, wherein hydrophilic organic solvent contains at least a organic solvent that is selected from alcohol organic solvent, gylcol ether organic solvent, Ucar 35 ethers organic solvent and ester class organic solvent.
10. each described water-based paint compositions in the claim 1～4, wherein the consumption of thinner (B) is the scope of 30～200 quality % with respect to the quality of base coating (A).
11. the described water-based paint compositions of claim 6, wherein tackifier (A4) and tackifier (B1) are selected from the combination of combination, urethane association type tackifier and mineral-type tackifier of combination, urethane association type tackifier and the polyacrylic tackifier of mineral-type tackifier and polyacrylic tackifier.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005370062 | 2005-12-22 | ||
| JP2005370062 | 2005-12-22 | ||
| JP2005-370062 | 2005-12-22 | ||
| JP2006-282857 | 2006-10-17 | ||
| JP2006282857A JP5290508B2 (en) | 2005-12-22 | 2006-10-17 | Water-based paint composition |
| JP2006282857 | 2006-10-17 |
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| Publication Number | Publication Date |
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| CN1986665A CN1986665A (en) | 2007-06-27 |
| CN1986665B true CN1986665B (en) | 2012-09-05 |
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| CN2006101617396A Active CN1986665B (en) | 2005-12-22 | 2006-12-19 | Aqueous coating composition |
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| JP (1) | JP5290508B2 (en) |
| CN (1) | CN1986665B (en) |
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| JP5089518B2 (en) * | 2008-07-17 | 2012-12-05 | 本田技研工業株式会社 | Repair painting method |
| JP5751657B2 (en) * | 2008-08-08 | 2015-07-22 | 関西ペイント株式会社 | Water-based paint composition |
| EP2166044B1 (en) | 2008-09-19 | 2012-02-01 | Rohm and Haas Company | Thickened compositions and method for thickening aqueous polymer compositions |
| CN101358101B (en) * | 2008-09-22 | 2012-04-25 | 立邦涂料（中国）有限公司 | Water-soluble varnish and method of preparing the same |
| US8815066B2 (en) | 2008-12-29 | 2014-08-26 | Basf Coatings Gmbh | Coating composition with phosphorous-containing resins and organometallic compounds |
| US8702943B2 (en) | 2008-12-29 | 2014-04-22 | Basf Coatings Gmbh | Electrocoat composition and process replacing phosphate pretreatment |
| US9206284B2 (en) | 2008-12-29 | 2015-12-08 | Basf Coatings Gmbh | Coating compositions with branched phosphorous-containing resin |
| JPWO2011099639A1 (en) * | 2010-02-10 | 2013-06-17 | 関西ペイント株式会社 | Water-based coloring paint composition |
| JP5447846B2 (en) * | 2010-03-29 | 2014-03-19 | 大日本塗料株式会社 | Water-based coating composition |
| JP5865372B2 (en) * | 2011-06-30 | 2016-02-17 | 関西ペイント株式会社 | Multi-component water-based base coat coating composition |
| JP5674592B2 (en) * | 2011-08-18 | 2015-02-25 | 関西ペイント株式会社 | Multi-component base coat paint, toning method and repair coating method |
| JP5979745B2 (en) * | 2011-12-29 | 2016-08-31 | 関西ペイント株式会社 | Multi-component water-based base coat coating composition |
| JP5979746B2 (en) * | 2012-04-25 | 2016-08-31 | 関西ペイント株式会社 | Multi-component water-based base coat coating composition |
| CN102690592A (en) * | 2012-06-01 | 2012-09-26 | 安徽省金盾涂料有限责任公司 | Water-borne coating composition |
| CN103289012B (en) * | 2013-06-24 | 2016-01-20 | 上海诺恰化工有限公司 | The preparation method of oiliness aluminium-silver slurry Water-borne modification auxiliary agent and prepared water-borne coatings |
| JP2016525154A (en) * | 2013-06-24 | 2016-08-22 | ベーイプシロンカー ヘミー ゲゼルシャフト ミット ベシュレンクター ハフトゥング | Adhesion enhancing additive and coating composition containing the same |
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| WO2019233980A1 (en) * | 2018-06-07 | 2019-12-12 | Akzo Nobel Coatings International B.V. | Aqueous binder composition, coating composition comprising such aqueous binder composition, process for coating a substrate, and coated substrate |
| CN109354989B (en) * | 2018-08-29 | 2021-04-27 | 雅图高新材料股份有限公司 | High-performance stable water-based yellow automobile refinishing paint and preparation method thereof |
| EP3838992A1 (en) * | 2019-12-20 | 2021-06-23 | Daw Se | Aqueous coating material system, use thereof and internal paint, facade paint, splicing mass, plaster, primer, adhesive mass, coating, glaze or pigment paste containing the aqueous coating material system |
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| CN1986665A (en) | 2007-06-27 |
| JP2007191686A (en) | 2007-08-02 |
| JP5290508B2 (en) | 2013-09-18 |
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