CN1329463C - Aqueous resin composition and aqueous paint composition containing the same - Google Patents
Aqueous resin composition and aqueous paint composition containing the same Download PDFInfo
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- CN1329463C CN1329463C CNB2004100074092A CN200410007409A CN1329463C CN 1329463 C CN1329463 C CN 1329463C CN B2004100074092 A CNB2004100074092 A CN B2004100074092A CN 200410007409 A CN200410007409 A CN 200410007409A CN 1329463 C CN1329463 C CN 1329463C
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Abstract
The aqueous resin composition is characterized in that it comprises (I) a fatty acid-modified acrylic resin composed of a copolymer of (a) 0.5-40 wt.% of a dry oil fatty acid and/or semi-dry oil fatty acid, (b) 0.5-20 wt.% of an epoxy group-containing polymerizable unsaturated monomer, (c) 0.5-25 wt.% of a polymerizable unsaturated monomer having at least one group selected from the group consisting of a sulfonic acid group, a sulfonate group, a phosphoric acid group and a phosphonate group, (d) 10-60 wt.% of a polymerizable unsaturated monomer having not less than 4C alkyl groups, and (e) 0-88.5 wt.% of the other polymerizable unsaturated monomer, and (II) an aqueous medium, and in that (I) is finely dispersed in (II).
Description
Technical field
The present invention relates to form the good aqueous resin composition of filming such as excellent processability with high thickness sense, high gloss etc. and weathering resistance, water tolerance, alkali resistance and contain the water-based paint compositions of this aqueous resin composition.
Background technology
In recent years,, consider, just carry out from the conversion of organic solvent type hydrotropisms type from saving aspects such as resource, environmental health, nuisanceless, non-dangerous materialization in fields such as coating, printing ink, tackiness agents.
The aqueous coating Synolac have usually form that solidity to corrosion is good, the filming of the excellent processability of high gloss, high thickness sense, but, the weathering resistance or the alkali resistance of filming are poor, in addition, the aqueous coating based acrylic resin forms weathering resistance or good the filming of alkali resistance, but the processibility or the solidity to corrosion of filming are poor.
As the aqueous resin composition of the advantage that has both such Synolac and acrylic resin, the fatty acid modified acrylic resin of water-based has been carried out all research (for example referring to Patent Document 1 and 2).
Usually, during the fatty acid modified acrylic resin of emulsion polymerization prepared of the mixture of the polymerizability unsaturated monomer by the fatty acids modified monomer, because fatty acid modified monomeric hydrophobicity is strong, poor with the copolymerization of other polymerizability unsaturated monomer in letex polymerization, the fatty acid modified acrylic resin that is difficult to obtain having the performance of being expected sometimes.Moreover, at first acrylic resin modified by solution polymerization synthetic fatty acid in organic solvent, follow resin combination by the method formation of water-dispersion, in order to ensure the stability of storing, need moisturize loose base acid mono the copolymerization resultant or for resulting multipolymer being carried out the amount of neutral neutralizing agent, therefore, there are the problems such as poor water resistance of filming that form with the aqueous resin composition that obtains.
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Summary of the invention
The inventor addresses these problems found that of further investigation repeatedly, specifically, by will be as forming polymerizability unsaturated monomer one of copolymerization monomer composition that fatty acid modified acrylic resin uses, that have specific acidic group other polymerizability insatiable hunger combination of monomers use with specified proportion, can solve the above problems, thereby finish the present invention.
Therefore, the invention provides aqueous resin composition, it is characterized in that containing by:
(a) 0.5-40 weight % drying oil fatty acid and/or semi-drying oil lipid acid;
(b) 0.5-20 weight % contains the epoxy-based polymerization unsaturated monomer;
(c) 0.5-25 weight % has the polymerizability unsaturated monomer that is selected from least a group in sulfonic group, sulphonate-base, phosphate, the phosphate base;
(d) 10-60 weight % has the polymerizability unsaturated monomer of carbon number 4 or above alkyl; With
(e) the fatty acid modified acrylic resin (I) and the aqueous medium (II) that constitute of other the multipolymer of polymerizability unsaturated monomer of 0-88.5 weight % is dispersed in the aqueous medium (II) fatty acid modified acrylic resin (I) is fine.
The present invention also provides water-based paint compositions, it is characterized in that containing above-mentioned aqueous resin composition.
Below, illustrate in greater detail aqueous resin composition of the present invention and water-based paint compositions.
Fatty acid modified acrylic resin (I):
Fatty acid modified acrylic resin of the present invention (I) is by making following explanation
(a) drying oil fatty acid and/or semi-drying oil lipid acid;
(b) contain the epoxy-based polymerization unsaturated monomer;
(c) has the polymerizability unsaturated monomer that is selected from least a acidic group in sulfonic group, sulphonate-base, phosphate, the phosphate base;
(d) has the polymerizability unsaturated monomer of carbon number 4 or above alkyl; With
(e) other polymerizability unsaturated monomer copolymerization and the multipolymer that obtains.
Drying oil fatty acid and/or semi-drying oil lipid acid (a):
Drying oil fatty acid and/or semi-drying oil lipid acid (a) be have from the iodine number of siccative oil and/or semi-drying oil usually 90 or more than,, be to give the monomer component that oxidative cure is used preferably to fatty acid modified acrylic resin (I) 100 or the lipid acid of the polymerizability unsaturated group of above oxidative cure type.This lipid acid (a) for example can be enumerated fish oil fatty acid, dehydrated castor oil fatty acid, Thistle oil lipid acid, linseed oil fatty acid, soya fatty acid, the acid of sesame oil fat, poppy seed oil lipid acid, perilla oil lipid acid, flaxseed oil lipid acid, raisin seed oil lipid acid, corn oil fatty acid, ready denier oil acid, sunflower oil lipid acid, cottonseed oil fatty acid, Walnut oil. lipid acid, hevea seed fatty acid oil etc.
As required, drying oil fatty acid and/or semi-drying oil lipid acid (a) can with for example nondrying oil lipid acid of coco-nut oil fatty acid, hydrogenated coconut fatty acid oil, palm oil fatty acid etc.; The lipid acid of other of caproic acid, capric acid, lauric acid, tetradecanoic acid, hexadecanoic acid, stearic acid etc. mixes use.The usage quantity of other lipid acid when mix using is generally 80 weight % or following in the total amount of drying oil fatty acid and/or semi-drying oil lipid acid (a) and this other lipid acid, is preferably 20-60 weight %.
The polymerizability unsaturated monomer (b) that contains epoxy group(ing):
The polymerizability unsaturated monomer (b) that contains epoxy group(ing) is the compound that contains 1 epoxy group(ing) and 1 polymerizability unsaturated link(age) in 1 molecule, for example can enumerate (methyl) acrylic acid epoxy propyl diester, (methyl) vinylformic acid Beta-methyl epoxypropyl ester, (methyl) vinylformic acid 3,4-epoxy dicyclohexyl methyl ester, (methyl) vinylformic acid 3,4-epoxy dicyclohexyl ethyl ester, (methyl) vinylformic acid 3,4-epoxy dicyclohexyl propyl diester, allyl group glycidyl ethers etc.In these compounds, preferred (methyl) acrylic acid epoxy propyl diester.
Have be selected from least a kind of group in sulfonic group, sulphonate-base, phosphate, the phosphate base polymerizability not
Saturated monomer (c):
The polymerizability unsaturated monomer (c) with at least a kind of group that is selected from sulfonic group, sulphonate-base, phosphate, the phosphate base of Shi Yonging is to give the monomer component that water dispersible is used to fatty acid modified acrylic resin (I) in the present invention, is included in the monomer that contains at least 1, preferred 1 this group and 1 polymerizability unsaturated link(age) in 1 molecule.By using this monomer component, the existence that the fatty acid modified acrylic resin (I) that obtains can be stable in aqueous medium, and can improve the rerum naturas such as water tolerance of filming of final formation.And, when using carboxylic monomers such as vinylformic acid, methacrylic acid to replace this monomer (c), in order to make the fatty acid modified acrylic resin that obtains can water-dispersion, must use this carboxylic monomer in a large number, the consequently final water tolerance of filming that forms is difficult to compatible mutually with the package stability of resin in water.
Salt in sulphonate-base or the phosphate base can be enumerated an alkali metal salts such as sodium, potassium; Alkaline earth salt such as calcium, magnesium; The amine salt of ammonium salt, primary amine-quaternary amine etc. etc.
But,, for example can enumerate the compound of following formula (1)-(5) expression as polymerizability unsaturated monomer (c) with at least a kind of group that is selected from sulfonic group, sulphonate-base, phosphate, the phosphate base.
Change 1
In the formula,
R
1Expression hydrogen or methyl;
R
2Represent to have replacement or unsubstituted C according to occasion
2-4Alkylidene group;
R
2' represent to have replacement or unsubstituted C according to occasion
1-20Unsaturated alkylene;
R
3Represent to have replacement or unsubstituted C according to occasion
1-6Alkylidene group;
R
4According to the 1 valency organic radical that occasion is represented to have replacement or unsubstituted saturated or undersaturated alkyl or contained oxyalkylene group, preferred C
1-6Alkyl;
X represents to be selected from the acidic group in sulfonic group, sulphonate-base, phosphate and the phosphate base;
N is an integer, the integer of preferred 1-20;
n
1Be integer, the integer of preferred 1-20.
C is arranged
4Or the polymerizability unsaturated monomer (d) of above alkyl:
Has C
4Or the polymerizability unsaturated monomer (d) of above alkyl is to give water-proof monomer component to fatty acid modified acrylic resin (I), comprises (methyl) acrylic acid C
4Or above, C particularly
6-10Straight chain shape, chain or cyclic alkyl ester.Specifically, can enumerate (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, the just own ester of (methyl) vinylformic acid, (methyl) Octyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) vinylformic acid stearyl, (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate etc.
Other polymerizability unsaturated monomer (e):
Other polymerizability unsaturated monomer (e) is and above-mentioned monomer (b), (c) and/or (d) copolymerizable monomer component for example to enumerate the lower alkyl esters of the methacrylic acid of (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate etc.; (methyl) vinylformic acid 1,2,2,6,6-pentamethyl-piperidyl ester, (methyl) vinylformic acid 2,2,6,6-tetramethyl-piperidyl ester, 2-(2 '-hydroxyl-5 '-the methacryloxypropyl phenyl)-the 2H-benzotriazole; Vinyl aromatic compounds such as vinylbenzene, alpha-methyl styrene, Vinyl toluene; Vinyl pyrrolidone, ethene, divinyl, chloroprene, vinyl propionate base ester, vinyl-acetic ester, (methyl) vinyl cyanide etc.
As other polymerizability unsaturated monomer (e), also can use the monomer of possess hydrophilic property group, preferably the water tolerance of filming is not being produced dysgenic scope use.Monomer with such hydrophilic radical for example can be enumerated carboxylic polymerizability unsaturated monomers such as (methyl) vinylformic acid, Ba Dousuan, methylene-succinic acid, toxilic acid, fumaric acid, β-propyloic acrylic ester; The nitrogenous polymerizability unsaturated monomers such as affixture of (methyl) acrylamide, dimethylaminopropyl (methyl) acrylamide, (methyl) vinylformic acid dimethyl aminoethyl ester, (methyl) acrylic acid epoxy propyl diester and amine; (methyl) acrylate with polyoxyethylene chain; (methyl) acrylic acid C of (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid hydroxypropyl ester etc.
2-8The polymerizability unsaturated monomer of the hydroxyl of hydroxy alkyl ester and so on etc.
In the present invention, for the fatty acid modified acrylic resin water tolerance that improves the mutual copolymerization of monomer and give generation, other polymerizability unsaturated monomer (e), by composition (a) and (b), (c), (d) and gross weight (e), contain 5-40 weight %, preferred 10-35 weight %, the more preferably vinylbenzene of 15-30 weight %.
In addition, as other polymerizability unsaturated monomer (e), the polymerizability unsaturated monomer that contains carbonyl by use, formation contains the fatty acid modified acrylic resin of carbonyl, the ambient cure raising of filming that forms by the resin combination that makes this carbonyl reaction of hydrazine derivative and this resin, make the water-base resin coating that obtains to be used.As polymerizability unsaturated monomer, for example can enumerate propenal, diacetone (methyl) acrylamide, methacrylic acid acetoacetyl oxygen ethyl ester, formyl radical vinylbenzene, the vinyl alkyl ketone (for example ethenyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) of 4-7 carbon atom etc. is arranged with this carbonyl.
As above-mentioned hydrazine derivative, for example can enumerate C such as ethylene acid hydrazide, propanedioic acid two hydrazides, pentanedioic acid two hydrazides, amber acid dihydrazide, adipic dihydrazide, sebacic dihydrazide
2-18Saturated carboxylic acid two hydrazides; Monoolefine unsaturated dicarboxylic acid two hydrazides such as Malaysia acid dihydrazide, fumaric acid two hydrazides, methylene-succinic acid two hydrazides; Two hydrazides of phthalic acid, terephthalic acid or isophthalic dihydrazide, Pyromellitic Acid, three hydrazides or four hydrazides; Nitrilo three hydrazides, citric acid three hydrazides, 1,2,4-benzene three hydrazides, ethylenediamine tetraacetic acid (EDTA) four hydrazides, 1,4,5,8-naphthoic acid four hydrazides, the polyhydrazide that rudimentary polymkeric substance with carboxylic acid low alkyl group ester group and hydrazine or hydrazine hydrate (hydrazine hydrate) reaction are generated; Carbonic acid two hydrazides etc. contain the compound of hydrazide group; Two Urea,amino-; Vulcabond such as hexamethylene diisocyanate or isophorone diisocyanate or by its deutero-polymeric polyisocyanate and N, the N of N-dimethylhydrazine etc., hydrazine that N-replaces or the polyfunctional Urea,amino-that obtains with above-mentioned illustrative hydrazide derivatives excessive response; The multifunctional Urea,amino-of water system that isocyanate group in the reactant of the active dydrogen compounds reaction that contains hydrophilic radical of this polyisocyanate compounds and polyether polyol class or polyoxyethylene glycol one alkyl ether etc. and two hydrazide derivatives excessive responses of above-mentioned example obtain, contain this multifunctional Urea,amino-and the multifunctional Urea,amino-of water system the compound that contains amino urea groups of mixture etc.; Contain compound with hydrazone group of diacetyl dihydrazone etc. etc.
Fatty acid modified acrylic resin of the present invention (I) by with above-mentioned drying oil fatty acid and/or semi-drying oil lipid acid (a), contain epoxy-based polymerization unsaturated monomer (b), have at least a kind of group that is selected from sulfonic group, sulphonate-base, phosphate, the phosphate base polymerizability unsaturated monomer (c), have C
4Or the polymerizability unsaturated monomer (d) of above alkyl and other polymerizability unsaturated monomer (e) copolymerization and obtain.
This moment each composition usage rate, be to be benchmark with composition (a) and (b), (c), (d) and total amount (e), can use following amount.
Composition (a): 0.5-40 weight %, preferred 3-33 weight %, more preferably 7-27 weight %;
Composition (b): 0.5-20 weight %, preferred 1-18 weight %, more preferably 3-15 weight %;
Composition (c): 0.5-25 weight %, preferred 1-20 weight %, more preferably 2-5 weight %;
Composition (d): 10-60 weight %, preferred 20-55 weight %, more preferably 30-40 weight %;
Composition (e): 0-88.5 weight %, preferred 1-75 weight %, more preferably 5-58 weight %.
According to the present invention, fatty acid modified acrylic resin (I), preferably at first by drying oil fatty acid and/or semi-drying oil lipid acid (a) with contain epoxy-based polymerization unsaturated monomer (b) and carry out addition reaction, the fatty acid modified polymerizability unsaturated monomer (A) that then makes gained with polymerizability unsaturated monomer (c) with at least a kind of group that is selected from sulfonic group, sulphonate-base, phosphate and the phosphate base, have C
4Or the polymerizability unsaturated monomer (d) of above alkyl and other polymerizability unsaturated monomer (e) carry out copolymerization and prepare.
In the preparation of above-mentioned fatty acid modified monomer (A), for drying oil fatty acid and/or semi-drying oil lipid acid (a) with contain for the epoxy-based polymerization unsaturated monomer (b), carboxyl in drying oil fatty acid and/or the semi-drying oil lipid acid (a) and the equivalence ratio that contains the epoxy group(ing) in the epoxy-based polymerization unsaturated monomer (b), be generally 0.25: 1-1.25: 1, be in particular 0.5: 1-1.1: the 1st, suit.
Carboxyl in above-mentioned drying oil fatty acid and/or the semi-drying oil lipid acid (a) carries out according to usual method with the reaction that contains the epoxy group(ing) in the epoxy-based polymerization unsaturated monomer (b), for example can be at the polymerization retarder and/or the N of quinhydrones etc., the catalyst for esterification reaction of quaternary ammonium salts such as the tertiary amine of N-dimethylaminoethanol etc., tetraethylammonium bromide, Tetrabutylammonium bromide etc. carries out under existing, and this reaction can be to carry out in the organic solvent inert to above-mentioned functional group.The reaction conditions of this moment, only otherwise can cause problem in the reaction such as gelation, carboxyl in the fatty acid component can carry out addition reaction with the epoxy group(ing) in the polymerizability unsaturated monomer that contains epoxy group(ing), then this is not particularly limited, but, usually preferably under about 100 ℃-Yue 180 ℃ temperature, carry out.
Fatty acid modified acrylic resin (I), for example, can be in organic solvent, in the presence of polymerization starter, use the above-mentioned fatty acid modified monomer (A) that obtains with polymerizability unsaturated monomer (c) with at least a kind of group that is selected from sulfonic group, sulphonate-base, phosphate, the phosphate base, have C
4Or the polymerizability unsaturated monomer (d) of above alkyl and other polymerizability unsaturated monomer (e), carry out solution polymerization by usual method and prepare.
The ratio that this moment, each monomer used is a benchmark with monomeric total amount, usually, can be in following ranges, fatty acid modified monomer (A) is 1-60 weight %, is preferably 5-50 weight %, more preferably 10-40 weight %;
Monomer (c) is 0.5-25 weight %, is preferably 1-20 weight %, more preferably 2-5 weight %;
Monomer (d) is 10-60 weight %, is preferably 20-55 weight %, more preferably 30-40 weight %;
Monomer (e) is 0-88.5 weight %, is preferably 5-84 weight %, more preferably 5-58 weight %.The usage rate of fatty acid modified monomer (A) is during less than 1 weight %, and filming after the coating do not carried out oxypolymerization after coating, in addition, the thickness sense of filming is often poor, on the other hand, and when surpassing 60 weight %, film hardening and crisp when dry, and weathering resistance and alkali resistance often reduce.The ratio that monomer (c) uses is during less than 0.5 weight %, and fatty acid modified acrylic resin (I) is difficult to stable dispersion in water, and on the other hand, when surpassing 25 weight %, the water tolerance of filming of formation often reduces.
In addition, according to the present invention, at first can with contain epoxy-based polymerization unsaturated monomer (b) with have at least a kind of group that is selected from sulfonic group, sulphonate-base, phosphate, the phosphate base polymerizability unsaturated monomer (c), have C
4Or the polymerizability unsaturated monomer (d) of above alkyl and other polymerizability unsaturated monomer (e), for example carry out copolymerization and prepare the acrylic resin that contains epoxy group(ing) by common solution polymerization process, then the epoxy group(ing) of this resin and drying oil fatty acid and/or semi-drying oil lipid acid (a) carry out addition reaction under above-mentioned reaction conditions, also can obtain fatty acid modified acrylic resin (I) thus.
The number-average molecular weight of the fatty acid modified acrylic resin (I) that obtains like this is generally 2000-120000, be preferably 5000-90000,10000-50000 more preferably, fatty acid modified acrylic resin (I) by use has this number-average molecular weight can obtain forming the resin composition for aqueous coating material of filming with high gloss.Number-average molecular weight in present specification is to use tetrahydrofuran (THF) as solvent, will press the value that the molecular weight of polystyrene converts and to get by the molecular weight of gel permeation chromatography.
In addition, the oil length of fatty acid modified acrylic resin (I) is generally 0.5-40%, is preferably 3-33%, more preferably 7-27%.Usually, the oil length of fatty acid modified acrylic resin (I) is less than 0.5%, and filming after the coating do not carried out oxypolymerization, otherwise surpasses 40%, the hardening and crisp of filming when dry, and, the tendency that the weathering resistance of filming of formation and alkali resistance have reduction.
Aqueous medium (II):
Disperse the employed aqueous medium of above-mentioned fatty acid modified acrylic resin (I) (II), can enumerate water or water and be the mixing solutions etc. of the water-organic solvent that is dissolved with organic solvents such as water-miscible organic solvent therein of main body.
Aqueous resin composition:
Aqueous resin composition of the present invention can prepare by fatty acid modified acrylic resin (I) is dispersed in the aqueous medium (II).This water-dispersion for example, can as required, neutralize with neutralizing agent by with the contained acidic groups of fatty acid modified acrylic resin (I), makes its emulsification voluntarily in aqueous medium.In addition, fatty acid modified acrylic resin (I) can not neutralize under the situation that contains sulphonate-base or phosphate base, by the effect emulsification voluntarily of itself.
As neutralizing agent, can enumerate sodium hydroxide, potassium hydroxide, Trimethylamine, dimethylaminoethanol, 2-methyl-2-amino-1-propyl alcohol, triethylamine, ammoniacal liquor etc., these neutralizing agents can join in the fatty acid modified acrylic resin (I) in advance, neutralization acidic group wherein, perhaps, also can join in the aqueous medium (II), at the dispersive fatty acid modified acrylic resin (I) that neutralizes simultaneously.
The dispersion of fatty acid modified acrylic resin (I) hydrotropisms medium, from further raising water dispersible, the aspect that further reduces particle diameter considers that the preferred high-pressure emulsification device with high energy shear ability that uses carries out.For example, with in the neutralizing agent and fatty acid modified acrylic resin (I), carry out pre-emulsification while adding water with dispersion machine etc., then, the pre-emulsification that obtains carries out emulsive method etc. with the high-pressure emulsification device under the high pressure conditions about 50MPa-250MPa be proper.Such high-pressure emulsification device for example can be enumerated " microjet emulsor " (マ イ Network ロ Off Le イ デ ッ Network society system)." nanometer mixing tank (Na ノ マ イ ザ one) " (Jitian's mechanical industry Co., Ltd. system) etc.In addition, the rotary-type super mixer of film that " T.K. Off イ Le ミ Star Network ス " (special machine chemical industry society system) enumerated also can use.By using the high-pressure emulsification device, can reduce the content that is included in the necessary acidic-group of water-dispersion in the fatty acid modified acrylic resin (I), therefore the performance of the water tolerance of filming that forms etc. can be improved.
By the of the present invention fatty acid modified acrylic resin (I) of solution polymerization, when it was disperseed in aqueous medium, the dispersion liquid that obtains can carry out desolventizing as requested to be handled.When using above-mentioned high-pressure emulsification device to carry out emulsification, preferably when pre-emulsification, carry out desolventizing, maybe will carry out desolventizing with the dispersion liquid that this device carries out after the emulsification.In addition, also can be dispersed in the aqueous medium behind fatty acid modified acrylic resin (I) desolventizing.
The above-mentioned aqueous resin composition of the present invention that obtains, the median size of fatty acid modified acrylic resin (I) is usually in 1000 nanometers or following, preferably in 500 nanometers or following, more preferably in 350 nanometers or following.In the application's specification sheets, median size is to use " SALD-3100 " (trade(brand)name, society of Shimadzu Seisakusho Ltd. system, laser diffraction formula particle size distribution device) to measure the measured value that is diluted to the proper concn test portion in deionized water.
The aqueous resin composition of the present invention that obtains like this, have simultaneously that common formation solidity to corrosion is good, high gloss, have the thickness sense excellent processability the aqueous coating Synolac of filming characteristic and form weathering resistance usually or the characteristic of the aqueous coating based acrylic resin of filming that alkali resistance is good, can be formed with the excellent processability of high thickness sense, high gloss etc. for preparation, and the good water-based paint compositions of filming such as weathering resistance, water tolerance, alkali resistance are useful.
Water-based paint compositions:
Water-based paint compositions of the present invention is to contain above-described aqueous resin composition of the present invention to form the based one-pack-type coating of composition as filming.
Water-based paint compositions of the present invention can prepare with additive by hybrid pigment in aqueous resin composition of the present invention, other coating.As pigment, can use normally used various tinting pigments, filler pigment, rust-stabilising pigment etc. in the coating, still,, preferably contain in pigment volume concentration (PVC) (PVC) 5-25%, the titanium white of 7-22% more preferably as pigment component.In this " pigment volume concentration (PVC) " is that this pigment component accounts for all resins component and whole volume ratios of the total solid of pigment component in the coating.Less than 5%, the disguise of filming is poor in PVC for this titanium white, surpasses 25%, and gloss and weathering resistance often reduce.
In addition, water-based paint compositions of the present invention in PVC, preferably contains 1-10%, the more preferably phosphoric acid series pigments of 2-8%.The PVC of phosphoric acid series pigments is less than 1%, and the corrosion of filming is often not enough, surpasses 10%, and gloss often reduces in initial stage gloss and the drying process.
And, water-based paint compositions of the present invention, whole pigment volume concentration (PVC)s are 10-30% in the coating, are preferably 15-25%.In this whole pigment volume concentration (PVC)s is that whole pigment component account for all resins component and the whole volume ratios of pigment total solids in the coating.These whole pigment volume concentration (PVC)s are less than 10%, and the disguise and the obdurability of filming usually are poor, surpass 30%, and initial stage gloss might reduce.
From the weather viewpoint, the preferred rutile-type of titanium white, in addition, and the phosphoric acid series pigments, from corrosion and glossy viewpoint, preferred dispersive phosphoric acid series pigments easily in the presence of polymeric surface active agent.This phosphoric acid series pigments, for example, zinc phosphate, phosphorus zinc silicate, aluminum phosphate zinc, calcium phosphate zinc, calcium phosphate, aluminum pyrophosphate, Calcium Pyrophosphate, aluminium dihydrogen tripolyphosphate, aluminium metaphosphate, calcium metaphosphate, phospho-molybdic acid zinc, phospho-molybdic acid aluminium etc.
And as required, as pigment, with the pigment beyond above-mentioned titanium white and the phosphoric acid series pigments, for example to mix use also passable with tinting pigment beyond the titanium white.In addition, for example, also can with filler pigments such as lime carbonate, hydrous magnesium silicate, talcum, mica, clay, barium oxide or for example the rust proof paint of zinc chromate etc. mix use.
Water-based paint compositions of the present invention by the composition or the concentration of suitable adjustment pigment, can obtain the coating of desired glossiness coating or delustring.
In addition, water-based paint compositions of the present invention also can mix use with metal drier, can promote the drying of filming thus.This metal drier can be used the metallic soap of aliphatic carboxylate or naphthenate etc. usually, still, considers that environmental optimization uses lead-free siccative.Metal drier is except that as the metals such as the cobalt of primary drying agent effect, manganese, also can use metal as 2 siccative effects, for example the metal drier of baric, zirconium, calcium, zinc, iron, copper etc. can improve all rapid-drying properties of filming that comprise the inside of filming thus.But solvent be the siccative that uses in the coating also former state be applicable to as metal drier, still, consider stability, the solvability of water and aqueous dispersion type resin, preferably use the water-borne coatings siccative.In addition, for improving the effect of siccative, also can add two pyridines etc.The usage quantity of above-mentioned siccative, the resin of water-based paint compositions forms branch admittedly relatively, is fit in the scope of 1-5 weight % usually.
Water-based paint compositions of the present invention further preferably contains at least a kind of compound that is selected from nitrite, phytate, tannate and the polyamine compounds.By adding this compound to water-based paint compositions, thereby on metal covering directly during this water-based paint compositions of coating, to produce aspect such as some rust useful preventing rust on the metal covering to infiltrate film coated surface.Above-mentioned nitrite for example can be enumerated Sodium Nitrite, calcium nitrite, strontium nitrite, barium nitrite, ammonium nitrite etc.; Phytate for example can be enumerated sodium phytate, POTASSIUM PHYTATE; Tannate for example can be enumerated sodium tannate, tannic acid potassium; Polyamine compounds for example can be enumerated an alkali metal salt, an alkylamine or the polyamines of N-(2-hydroxyethyl) ethylenediamine triacetic acid (HEDTA), ethylenediamine tetraacetic acid (EDTA) (EDTA), diethylene triaminepentaacetic acid(DTPA) (DTPA), trimethylene diamine tetraacethyl (PDTA), iminodiethanoic acid, nitrilotriacetic acid (NTA), diethylenetriamine pentamethylenophosphonic acid(DTPP) (DTPMP) and these compounds, quaternary ammonium ion etc. be embedded in the layered phosphates of aluminium dihydrogen tripolyphosphate etc. and the intercalation compound that forms etc., hydrazide compound, semicarbazide compound, hydrazone compound etc.These compounds can use separately, also can be used in combination.The content of these basic cpds by water-based paint compositions, is generally 0.02-2 weight %, preferred 0.05-1 weight %.
Water-based paint compositions of the present invention as required, except that mentioned component, also can contain the modifying resin of the acrylic resin, Synolac, Resins, epoxy, carbamate resins, silicone resin, fluorine resin, vibrin etc. of water-soluble or aqueous dispersion type; Stratiform viscosity mineral, powdery or the coating additives such as particulate gac, photocatalyst oxidizes titanium of tensio-active agent, dispersion agent, defoamer, thickening material, film coalescence aid, sanitas, mould inhibitor, frostproofer, pH regulator agent, sudden strain of a muscle rust (Off ラ Star シ ュ ラ ス ト) inhibitor, aldehyde trapping agent, sepiolite, zeolite etc., they can suitably be selected and make up.
Water-based paint compositions of the present invention can for example can use known utensils such as roller coat device, aerial spraying device, vacuum spraying device, リ シ Application ガ Application (centrifugal spray gun), omnipotent spray gun, hairbrush to be coated with by well-known method.
Applied, for example can enumerate alkaline base materials such as concrete, plaster, slabstone, asbestos tile; Ceramic industry is substrate surfaces such as metals such as building materials, iron, plastics or is coated with old coating film face that is contained on these base materials etc.On this substrate surface, water-based or solvent type priming paint can be coated with in advance, behind this priming paint of coating, water-based paint compositions of the present invention can be coated with as required as investment precoat.Priming paint for example can be enumerated the protective layer or the primer base of acrylic resin, acrylic rubber system, chlorinated rubber system, styrene butadiene rubbers system, epoxy system etc.; Material is studied for a second time courses one has flunked in the substrate that the water-based rust of fatty acid modified epoxy system etc. prevents agent or contains the cement part; The material that substrate adjusts material, thicken etc.On the other hand, water-based paint compositions of the present invention also can be coated with many known water-based investment precoats after being coated with as priming paint.
Water-borne coatings resin combination of the present invention though be one-pack type, easily solidifies at normal temperatures, because weathering resistance, the excellent processability of filming, so be particularly suitable for the surfaces externally and internally of application buildings, or the application of bridge, boats and ships etc.
The invention effect
Hydrophilic radical or emulsifying agents such as fatty acid modified acrylic acid resin composition of water-based of the present invention and use carboxyl, compare according to the resin combination in the past that the method for water-dispersionization obtains, owing to contain specific acidic group, the water tolerance of filming of package stability and formation is all good.In addition, the fatty acid modified acrylic acid resin composition of water-based of the present invention carries out emulsification by the high-pressure emulsification device that uses high energy shear power, and it is littler that the particle diameter of latex can become, and can further improve and form the water tolerance of filming.Fatty acid modified acrylic resin of the present invention, have the characteristic of Synolac and acrylic resin concurrently, by filming that the coating composition that contains this resin forms, easily solidify at normal temperatures, high gloss, have the excellent processability of high thickness etc., and the film performance of weathering resistance, alkali resistance etc. is also good.
Embodiment
Below, specifically describe the present invention by embodiment.And [portion], [%] are respectively weight part and weight %.
Fatty acid modified monomeric preparation:
Preparation example 1
Following compositions is added reaction vessel, react, obtain fatty acid modified monomer (e-1) while stir 170 ℃ temperature.Carry out the addition reaction of epoxy group(ing) and carboxyl on one side, on one side the residual carboxyl amount of tracking and measuring.Finished reaction needed about 3 hours.
280 parts of soya fatty acids
142 parts of glycidyl methacrylate
0.4 part of quinhydrones
0.2 part of tetraethylammonium bromide
Preparation example 2
Change over following compositions, other is identical with preparation example 1, obtains fatty acid modified monomer (e-2).
237 parts of linseed oil fatty acid
149 parts of glycidyl methacrylate
0.4 part of quinhydrones
0.2 part of tetraethylammonium bromide
The preparation of fatty acid modified acrylic resin:
Preparation example 3
472 parts [MFG] (annotating 1) adding is provided with in 4 mouthfuls of flasks of stirrer, thermometer, return line and rare gas element ingress pipe, stirs intensification up to 120 ℃ while feed nitrogen.After this, continue to remain on 120 ℃ temperature, in 3 hours, drip
152 parts of vinylbenzene
86 parts of n-BMAs
86 parts of Propenoic acid, 2-methyl, isobutyl esters
90 parts of 2-ethylhexyl acrylates
100 parts of glycidyl methacrylate
56 parts of [An tox MS-2N] (annotating 2) 50% aqueous solution
The mixture that azo diisobutyl nitrile is 1.6 parts.After this, after 2 hours, be warmed up to 140 ℃ 120 ℃ of slakings, add 158 parts of soya fatty acids and 0.4 part of catalysts N, the N-dimethylaminoethanol carries out the addition reaction of lipid acid.The acid value of resin is with KOH volumetry tracking and measuring, and the acid value of resin is carried out terminal point for reacting 1.0 when following.Therefore, obtaining nonvolatile component is 58% the transparent fatty acid modified acrylic resin soln (I-1) of brown.
(annotate 1) [MFG]: trade(brand)name, Japanese emulsifying agent society system, methyl proxitol
(annotate 2) [An tox MS-2N]: trade(brand)name, Japanese emulsifying agent society system, the compound of representing with following formula (6) is as main component
[changing 2]
Preparation example 4
500 parts [ス ワ ゾ one Le 310] (annotating 3) adding is provided with in 4 mouthfuls of flasks of stirrer, thermometer, return line and rare gas element ingress pipe, stirs intensification up to 120 ℃ while feed nitrogen.After this, continue to remain on 120 ℃ temperature, in 3 hours, drip
260 parts of fatty acid modified monomers (e-1)
150 parts of vinylbenzene
86 parts of n-BMAs
86 parts of Propenoic acid, 2-methyl, isobutyl esters
90 parts of 2-ethylhexyl acrylates
28 parts of [TBAS-Q] (annotating 4)
The mixture that azo diisobutyl nitrile is 2.1 parts.After this, 120 ℃ of slakings after 2 hours, obtain nonvolatile component and be 58% the transparent fatty acid modified acrylic resin soln (I-2) of brown.
(annotating 3) [ス ワ ゾ one Le 310]: trade(brand)name, コ ス モ oil society system, mineral turpentine
(annotate 4) [TBAS-Q]: trade(brand)name, MRC ユ two テ ッ Network society systems, the compound of representing with following formula (7) is as main component
[changing 3]
Preparation example 5
472 parts [MFG] (annotating 1) adding is provided with in 4 mouthfuls of flasks of stirrer, thermometer, return line and rare gas element ingress pipe, stirs intensification up to 120 ℃ while feed nitrogen.After this, continue to remain on 120 ℃ temperature, in 3 hours, drip
260 parts of fatty acid modified monomers (e-2)
150 parts of vinylbenzene
86 parts of n-BMAs
86 parts of Propenoic acid, 2-methyl, isobutyl esters
90 parts of 2-ethylhexyl acrylates
56 parts of [An tox MS-2N] (annotating 2) 50% aqueous solution
The mixture that azo diisobutyl nitrile is 2.1 parts.After this, 120 ℃ of slakings after 2 hours, obtain nonvolatile component and be 58% the transparent fatty acid modified acrylic resin soln (I-3) of brown.
Preparation example 6
500 parts [MFG] (annotating 1) adding is provided with in 4 mouthfuls of flasks of stirrer, thermometer, return line and rare gas element ingress pipe, stirs intensification up to 120 ℃ while feed nitrogen.After this, continue to remain on 120 ℃ temperature, in 3 hours, drip
260 parts of fatty acid modified monomers (e-1)
40 parts of vinylbenzene
50 parts of n-BMAs
40 parts of Propenoic acid, 2-methyl, isobutyl esters
150 parts of 2-ethylhexyl acrylates
160 parts of [TBAS-Q] (annotating 4)
The mixture that azo diisobutyl nitrile is 2.1 parts.After this, 120 ℃ of slakings after 2 hours, obtain nonvolatile component and be 58% the transparent fatty acid modified acrylic resin soln (I-4) of brown.
Preparation example 7
500 parts [ス ワ ゾ one Le 310] (annotating 3) adding is provided with in 4 mouthfuls of flasks of stirrer, thermometer, return line and rare gas element ingress pipe, stirs intensification up to 120 ℃ while feed nitrogen.After this, continue to remain on 120 ℃ temperature, in 3 hours, drip
260 parts of fatty acid modified monomers (e-1)
150 parts of vinylbenzene
86 parts of n-BMAs
86 parts of Propenoic acid, 2-methyl, isobutyl esters
90 parts of 2-ethylhexyl acrylates
28 parts of [TBAS-Q] (annotating 4)
The mixture that azo diisobutyl nitrile is 1.1 parts.After this, 120 ℃ of slakings after 2 hours, obtain nonvolatile component and be 58% the transparent fatty acid modified acrylic resin soln (I-5) of brown.
Preparation example 8
500 parts [ス ワ ゾ one Le 310] (annotating 3) adding is provided with in 4 mouthfuls of flasks of stirrer, thermometer, return line and rare gas element ingress pipe, stirs intensification up to 120 ℃ while feed nitrogen.After this, continue to remain on 120 ℃ temperature, in 3 hours, drip
260 parts of fatty acid modified monomers (e-1)
150 parts of vinylbenzene
100 parts of n-BMAs
91 parts of Propenoic acid, 2-methyl, isobutyl esters
90 parts of 2-ethylhexyl acrylates
9 parts in vinylformic acid
The mixture that azo diisobutyl nitrile is 2.1 parts.After this, 120 ℃ of slakings after 2 hours, obtain nonvolatile component and be 58% the transparent fatty acid modified acrylic resin soln (I-6) of brown.
Preparation example 9
500 parts [ス ワ ゾ one Le 310] (annotating 3) adding is provided with in 4 mouthfuls of flasks of stirrer, thermometer, return line and rare gas element ingress pipe, stirs intensification up to 120 ℃ while feed nitrogen.After this, continue to remain on 120 ℃ temperature, in 3 hours, drip
240 parts of vinylbenzene
146 parts of n-BMAs
146 parts of Propenoic acid, 2-methyl, isobutyl esters
140 parts of 2-ethylhexyl acrylates
28 parts of [TBAS-Q] (annotating 4)
The mixture that azo diisobutyl nitrile is 2.1 parts.After this, 120 ℃ of slakings after 2 hours, obtain nonvolatile component and be 58% the transparent fatty acid modified acrylic resin soln (I-7) of brown.
Following table 1 shows the monomer of fatty acid modified acrylic resin (I-1)～(I-7) and forms and character value.
Table 1
| Fatty acid modified acrylic resin | Preparation example | ||||||||
| 3 | 4 | 5 | 6 | 7 | 8 | 9 | |||
| 1-1 | 1-2 | 1-3 | 1-4 | 1-5 | 1-6 | 1-7 | |||
| Form (A) | Fatty acid modified monomer | e-1 | 260 | 260 | 260 | 260 | |||
| e-2 | 260 | ||||||||
| Vinylbenzene | 152 | 150 | 150 | 40 | 150 | 150 | 240 | ||
| N-BMA | 86 | 86 | 86 | 50 | 86 | 100 | 146 | ||
| Propenoic acid, 2-methyl, isobutyl ester | 86 | 86 | 86 | 40 | 86 | 91 | 146 | ||
| The acrylic acid-2-ethyl polyhexamethylene | 90 | 90 | 90 | 50 | 90 | 90 | 140 | ||
| Vinylformic acid | 9 | ||||||||
| Glycidyl methacrylate | 100 | ||||||||
| 「TBAS-Q」 (annotating 4) | 28 | 160 | 28 | 28 | |||||
| 「Antox MS-2N」 (annotating 3) | 28 | 28 | |||||||
| Soya fatty acid | 158 | ||||||||
| Character value | The number molecular-weight average | 30,000 | 30,000 | 30,000 | 30,000 | 60,000 | 30,000 | 30,000 | |
| Oil length | 23 | 25 | 23 | 25 | 25 | 25 | 0 | ||
| Carboxyl/epoxy group(ing) | 0.8/1 | 1/1 | 0.8/1 | 1/1 | 1/1 | 1/1 | |||
The preparation of resin composition for aqueous coating material:
Embodiment 1
Fatty acid modified acrylic resin (I-1) is carried out reduced pressure treatment except that desolvating, on one side 700 parts of deionized waters slowly to be joined 875 parts nonvolatile component on one side be in 80% the resin to high-speed stirring, obtains nonvolatile component and be 44% aqueous resin composition (A-1).The median size of the latex that obtains is 300 nanometers.
Embodiment 2
Make in the high-pressure emulsification device that fluid collides mutually applying the ultra-high voltage energy, under the high pressure of 130MPa, the aqueous resin composition (A-1) that will obtain in the foregoing description 1 carries out emulsification.Through 2 times, the median size that obtains dispersed particle is the aqueous resin composition (A-2) of 200 nanometers.
Embodiment 3
Fatty acid modified acrylic resin (I-2) is carried out reduced pressure treatment except that desolvating, to nonvolatile component is that 875 parts of resins of 80% add 10.9 gram triethylamines as neutralizing agent, after this, slowly add 700 parts of deionized waters on one side, high-speed stirring on one side obtains nonvolatile component and is 44% aqueous resin composition (A-3).
Embodiment 4-10 and comparative example 1-2
According to composition and the condition shown in the following table 2, identical with embodiment 3, obtain nonvolatile component and be 44% aqueous resin composition (A-4)-(A-12).
Table 2
| Aqueous resin composition | Embodiment | Comparative example | |||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 1 | 2 | ||
| A-1 | A-2 | A-3 | A-4 | A-5 | A-6 | A-7 | A-8 | A-9 | A-10 | A-11 | A-12 | ||
| Fatty acid modified acrylic resin | 1-1 | 875 | 875 | ||||||||||
| 1-2 | 875 | 875 | |||||||||||
| 1-3 | 875 | 875 | |||||||||||
| 1-4 | 875 | 875 | |||||||||||
| 1-5 | 875 | 875 | |||||||||||
| 1-6 | 875 | ||||||||||||
| 1-7 | 875 | ||||||||||||
| Triethylamine | Use level | 0 | 0 | 10.9 | 10.9 | 0 | 0 | 31.2 | 31.2 | 10.9 | 10.9 | 10.1 | 10.9 |
| Equivalence ratio | 0.8 | 0.8 | 0.4 | 0.4 | 0.8 | 0.8 | 0.8 | 0.8 | |||||
| Deionized water | 700 | 700 | 700 | 700 | 700 | 700 | 700 | 700 | 700 | 700 | 700 | 700 | |
| High-pressure emulsification is handled | Do not have | Have | Do not have | Have | Do not have | Have | Do not have | Have | Do not have | Have | Do not have | Do not have | |
| The solid substance composition | 44％ | 44％ | 44％ | 44％ | 44％ | 44％ | 44％ | 44％ | 44％ | 44％ | 44％ | 44％ | |
| Median size/nm | 300 | 200 | 300 | 200 | 300 | 200 | 150 | 140 | 300 | 200 | 1100 | 300 | |
The preparation of water-based paint compositions:
Embodiment 11-20 and comparative example 3-4
Each composition of the composition (B) of following table 3 expression is added container in proper order, till evenly, continue to stir and obtain the pigment mashed prod by dispersion machine effect 30 minutes.After this, table 3 is formed each composition shown in (C) sequentially add in this each pigment paste, obtain each water-based paint compositions.And (notes) in the table 3 are as described below
(annotate 5) [ス ラ オ Off 72N]: military field medicine society system, sanitas
(annotating 6) [ノ プ コ サ Application ト K]: サ Application ノ プ コ society system, pigment dispersing agent
(annotating 7) [ア デ カ ノ one Le UH-438]: ア デ カ society system, thickening material
(annotating 8) [titanium white JR-600A]: テ イ カ society system, titanium white
(annotating 9) [SN デ Off オ one マ 1]: サ Application ノ プ コ society system, defoamer
(annotating 10) [DICNATE3111]: big Japanese ink chemical industry society system, siccative
(annotating 11) [LF ボ ウ セ イ P-W-2]: キ Network チ カ ラ one society's system, zinc phosphate is a rust-stabilising pigment
Table 3
| Water-based paint compositions | Embodiment | Comparative example | ||||||||||||
| 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | 3 | 4 | |||
| Form (B) | Tap water | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 | |
| Ethylene glycol | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | ||
| 「スラォフ72N」 (annotating 5) | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | ||
| 「ノフコサントK」 (annotating 6) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | ||
| 「アデカノ-ルUH-438」 (annotating 7) | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | ||
| " the white JR-600A of チ Application " (annotating 8) | 25.6 | 25.6 | 25.6 | 25.6 | 25.6 | 25.6 | 25.6 | 25.6 | 25.6 | 25.6 | 25.6 | 25.6 | ||
| 「LFボウセイP-W-2」 (annotating 11) | 3.5 | 3.5 | ||||||||||||
| 「SNデフォ-マ-380」 (annotating 9) | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | ||
| Form (C) | Aqueous resin composition | Kind | A-1 | A-2 | A-3 | A-4 | A-5 | A-6 | A-7 | A-8 | A-9 | A-10 | A-11 | A-12 |
| Amount | 57 | 57 | 57 | 57 | 57 | 57 | 57 | 57 | 57 | 57 | 57 | 57 | ||
| Texanol | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | ||
| 「SNデフォ-マ-380」 (annotating 9) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | ||
| 「アデカノ-ルUH-438」 (annotating 7) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | ||
| 「DICNATE3111」 (annotating 10) | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | ||
| Sodium Nitrite | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | ||
| Character value | Titanium white PVC | 19.9 | 19.9 | 19.9 | 19.9 | 19.3 | 19.3 | 19.9 | 19.9 | 19.9 | 19.9 | 19.9 | 19.9 | |
| Phosphoric acid series pigments PVC | 0 | 0 | 0 | 0 | 3.1 | 3.1 | 0 | 0 | 0 | 0 | 0 | 0 | ||
| Whole pigment PVC | 19.9 | 19.9 | 19.9 | 19.9 | 22.4 | 22.4 | 19.9 | 19.9 | 19.9 | 19.9 | 19.9 | 19.9 | ||
Above-mentioned each water-based paint compositions that obtains is offered following test.Outcome record is at table 4.
Table 4
| Water-based paint compositions | Embodiment | Comparative example | ||||||||||
| 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | 3 | 4 | |
| The thickness sense | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × |
| 60 degree gloss | 83 | 87 | 84 | 86 | 81 | 82 | 87 | 88 | 77 | 79 | 71 | 84 |
| Weathering resistance | 8 points | 8 points | 8 points | 8 points | 8 points | 8 points | 8 points | 8 points | 8 points | 8 points | 8 points | 8 points |
| Water tolerance | ○ | ○ | ○ | ○ | ○ | ○ | △ | △ | ○ | ○ | ○ | ○ |
| Alkali resistance | ○ | ○ | ○ | ○ | ○ | ○ | △ | △ | ○ | ○ | ○ | ○ |
| The package stability of heating | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | ○ |
Method for testing performance
(
*1)
The thickness sense: being coated with a scraper machine (6 ミ Le De Network , one プ レ, one De) with 6, embodiment and each water-borne coatings of comparative example are coated on the sheet glass, is 20 ℃ at temperature, and relative humidity is under 60% the condition, to carry out drying, is respectively tested coated plate.Visual observation appearance of film after 1 day.
Zero: the thickness sense is good
*: the thickness sense is poor
(
*2)
60 degree gloss: measure with above-mentioned (
*1) 60 of the identical test board that obtains degree gloss.Value is the bigger the better.
(
*3)
Weathering resistance: the steel plate (150 * 70 * 0.8 millimeter) of JIS K5410 regulation carries out degreasing in dimethylbenzene, application thereon [ザ ウ Le ス EX] (trade(brand)name, one ペ Application dilution type epoxy rust-proof paint, Northwest coating society system) forming bottom films, with tap water each water-borne coatings is diluted to about 70KU, be coated with thereon with hairbrush, making glue spread is 150g/m
2, 20 ℃ of temperature, relative humidity is respectively tested coated plate under 60% the condition in dry 1 week.Each tests the promotion weather test of coated plate according to the 9.8.1 (sun-proof carbon-arc lamp formula) of JIS K 5400, shines after 1000 hours, and each coated plate face is estimated according to the 9.6 efflorescence degree of JIS K 5400.Mark is low more, and it is many more that the expression efflorescence is carried out.
(
*4)
Water tolerance:The steel plate (150 * 70 * 0.8 millimeter) of JIS K 5410 regulations carries out degreasing in dimethylbenzene, with tap water each water-borne coatings is diluted to about 70KU, is coated with thereon with hairbrush, and making glue spread is 150g/m
2, 20 ℃ of temperature, relative humidity is respectively tested coated plate under 60% the condition in dry 1 week.Each is tested coated plate and carries out water tolerance test (flooding 96 hours) according to 8.19 of JIS K 5400.The face that respectively is coated with after the test is estimated by following benchmark.
Zero: break, do not peel off, perhaps gloss retention is more than 60%.
△: do not have 1 to meet above-mentioned standard.
(
*5)
Alkali resistance:According to 8.21 of JIS K 5400, will with above-mentioned (
*4) coated plate of equally making of respectively testing carries out alkaline resistance test (test period 96 hours).By the face that respectively is coated with after the following benchmark evaluation test.
Zero: break, do not peel off, perhaps gloss retention is more than 60%.
△: do not have 1 to meet above-mentioned standard.
(
*6)
The heating package stability:Each water-borne coatings that adds 1 kilogram of embodiment and comparative example in 1 liter inner face coating jar is with storing 30 at 40 ℃ after the nitrogen-sealed.After this, get back to room temperature, the state in the visual observation container.Estimate by following benchmark.
Zero: remarkable tackify, the pigment sedimentation does not have the separation of resin and separates out.
*: there is not 1 to meet above-mentioned standard.
Claims (14)
1. aqueous resin composition is characterized in that containing by (a) 0.5-40 weight % drying oil fatty acid and/or semi-drying oil lipid acid; (b) 0.5-20 weight % contains the polymerizability unsaturated monomer of epoxy group(ing); (c) 0.5-25 weight % has the polymerizability unsaturated monomer of at least a group that is selected from sulfonic group, sulphonate-base, phosphate, the phosphate base; (d) 10-60 weight % has fatty acid modified acrylic resin (I) and the aqueous medium (II) that multipolymer that other the polymerizability unsaturated monomer of polymerizability unsaturated monomer and (e) 0-88.5 weight % of the alkyl of 4 or above carbon become constitutes, and is dispersed in the aqueous medium (II) fatty acid modified acrylic resin (I) is fine.
2. press the aqueous resin composition of claim 1 record, wherein, fatty acid modified acrylic resin (I) is by by drying oil fatty acid and/or semi-drying oil lipid acid (a) with contain fatty acid modified polymerizability unsaturated monomer that the reaction of the polymerizability unsaturated monomer (b) of epoxy group(ing) obtains and have the sulfonic group of being selected from, sulphonate-base, phosphate, the polymerizability unsaturated monomer (c) of at least a group in the phosphate base, have the polymerizability unsaturated monomer (d) of carbon number 4 or above alkyl and other the resulting fatty acid modified acrylic resin of polymerizability unsaturated monomer (6) copolymerization.
3. press the aqueous resin composition of claim 1 record, wherein, fatty acid modified acrylic resin (I) is by by containing the polymerizability unsaturated monomer (b) of epoxy group(ing), has the sulfonic group of being selected from, sulphonate-base, phosphate, the polymerizability unsaturated monomer (c) of at least a group in the phosphate base, have that the epoxy group(ing) of the resulting acrylic resin that contains epoxy group(ing) of the polymerizability unsaturated monomer (d) of alkyl of 4 or above carbon and other polymerizability unsaturated monomer (e) copolymerization and drying grease acid-proof and/or semi-drying oil lipid acid (a) carry out addition reaction and the fatty acid modified acrylic resin that obtains.
4. press the aqueous resin composition of each record of claim 1-3, wherein other polymerizability unsaturated monomer (e) in composition (a) and (b), (c), (d) and total amount (e), contains the vinylbenzene of 5-40 weight %.
5. press the aqueous resin composition of each record of claim 1-3, the number-average molecular weight of wherein fatty acid modified acrylic resin (I) is 2000-120000.
6. press the aqueous resin composition of each record of claim 1-3, wherein fatty acid modified acrylic resin (I) uses the high-pressure emulsification device, under the pressure of 50-250MPa, is dispersed in the aqueous medium (II).
7. press the aqueous resin composition of each record of claim 1-3, wherein fatty acid acrylic resin modified (I) is dispersed in the aqueous medium (II) with 1000 nanometers or following median size.
8. water-based paint compositions is characterized in that containing the aqueous resin composition that right requires each record of 1-7.
9. by the water-based paint compositions of claim 8 record, wherein the pigment volume concentration (PVC) with 5-25% contains titanium white, and all the volumetric concentration of pigment is 10-30%.
10. by the water-based paint compositions of claim 8 or 9 records, wherein the pigment volume concentration (PVC) with 1-10% contains the phosphoric acid series pigments.
11. the water-based paint compositions by claim 8 or 9 records wherein contains at least a compound that is selected from nitrite, phytate, tannate and the polyamine compounds.
12. the water-based paint compositions by claim 10 record wherein contains at least a compound that is selected from nitrite, phytate, tannate and the polyamine compounds.
The formation method 13. film is characterized in that on coated surface the water-based paint compositions of each record of coating claim 8-12.
14. the coated article that the method for putting down in writing according to claim 13 obtains.
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| JP2003061226 | 2003-03-07 | ||
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| US11866524B2 (en) | 2016-08-12 | 2024-01-09 | Rohm And Haas Company | Water-based pressure sensitive adhesive compositions and methods of making same |
| US11926770B2 (en) | 2016-08-12 | 2024-03-12 | Rohm And Haas Company | Water-based pressure sensitive adhesive compositions and methods of making same |
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| JP5290508B2 (en) * | 2005-12-22 | 2013-09-18 | 関西ペイント株式会社 | Water-based paint composition |
| CN100447212C (en) * | 2006-09-05 | 2008-12-31 | 英志祥 | Water industrial paint based on organosilicon acrylic acid epoxy ester water dispersion and preparation method thereof |
| EP2277930A1 (en) * | 2009-06-30 | 2011-01-26 | Cytec Surface Specialties, S.A. | Radiation curable compositions |
| JP5633792B2 (en) * | 2009-08-31 | 2014-12-03 | 大日精化工業株式会社 | Pigment dispersion and colorant |
| CN102020759B (en) * | 2010-10-27 | 2012-09-05 | 中国科学院长春应用化学研究所 | Preparation method of waterborne resin and water-based paint composition |
| CN103820794B (en) * | 2014-02-24 | 2018-04-03 | 深圳市宝骏环保涂料有限公司 | Water-based band embroiders rust-removing and-preventing agent and production method |
| CN104194449B (en) * | 2014-08-29 | 2016-08-17 | 苏州圣谱拉新材料科技有限公司 | A kind of water soluble paint |
| CN106188357A (en) * | 2016-07-05 | 2016-12-07 | 无锡华东锌盾科技有限公司 | A kind of water-based fluorocarbon resin emulsion and its preparation method and application |
| CN108250865A (en) * | 2017-12-28 | 2018-07-06 | 上海三恩化工有限公司 | Bi-component waterborne self-drying paint and preparation method thereof |
| CN109709635B (en) * | 2019-01-16 | 2021-01-01 | 安徽硕明安全科技有限公司 | Full-prism reflecting material and processing technology thereof |
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| JPS59152965A (en) * | 1983-02-21 | 1984-08-31 | Nippon Paint Co Ltd | Water-based rust-proofing coating composition |
| WO1997026303A1 (en) * | 1996-01-18 | 1997-07-24 | Akzo Nobel Industrial Coatings Ab | Water-borne hybrid binder composition and use thereof |
| CN1272854A (en) * | 1997-08-12 | 2000-11-08 | 伊斯曼化学公司 | Acrylic modified waterborne sulfonated alkyd dispersions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59152965A (en) * | 1983-02-21 | 1984-08-31 | Nippon Paint Co Ltd | Water-based rust-proofing coating composition |
| WO1997026303A1 (en) * | 1996-01-18 | 1997-07-24 | Akzo Nobel Industrial Coatings Ab | Water-borne hybrid binder composition and use thereof |
| CN1272854A (en) * | 1997-08-12 | 2000-11-08 | 伊斯曼化学公司 | Acrylic modified waterborne sulfonated alkyd dispersions |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11866524B2 (en) | 2016-08-12 | 2024-01-09 | Rohm And Haas Company | Water-based pressure sensitive adhesive compositions and methods of making same |
| US11926770B2 (en) | 2016-08-12 | 2024-03-12 | Rohm And Haas Company | Water-based pressure sensitive adhesive compositions and methods of making same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1523071A (en) | 2004-08-25 |
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