CN1307270C - Extinction anion type electrophoresis paint - Google Patents
Extinction anion type electrophoresis paint Download PDFInfo
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- CN1307270C CN1307270C CNB031272681A CN03127268A CN1307270C CN 1307270 C CN1307270 C CN 1307270C CN B031272681 A CNB031272681 A CN B031272681A CN 03127268 A CN03127268 A CN 03127268A CN 1307270 C CN1307270 C CN 1307270C
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Abstract
The present invention provides an extinction anion type electrophoresis paint which has excellent storage stability, finishability and invisibility of mould traces. The extinction anion type electrophoresis paint contains emulsion obtained by the following steps: in the reaction of a first period, copolymerization of free radical is carried out to an unsaturated monomer (a) containing a hydroxyl group, an unsaturated monomer (b) containing a hydroxyl group and other unsaturated monomers (c) of free radical, and ethylene copolymer resin (A) of water dispersivity is obtained; in the reaction of a second period, the ethylene copolymer resin (A) of water dispersivity and an epoxy compound (d) of which one molecule has more than one epoxy group and more than one silyl group of hydroxy are heated and mixed, and waterborne resin (I) is obtained; and subsequently, the waterborne resin (I) and a cross-linking agent (II) are matched with an alkaline compound, and the emulsion is formed by water dispersion.
Description
Technical field
The present invention relates to storage stability, the processibility of coating, the extinction anion electrophoretic coating of various excellent propertys.
Background technology
In the past, aluminium was all better than many metals (iron and steel etc.) aspect high temperature process, so utilize hot extrusion can more easily obtain having the section bar of all section shapes.Aluminium, in light weight, processibility is easy, utilizes the advantageous property of the script aluminium of so-called excellent corrosion resistance, and is especially many as the material relevant with building materials.
The hot-extrusion method of this aluminium is usually with columniform aluminium ingot bar heating and melting, then this melts is packed in the extrusion machine, is pressed in the mould with regulation section shape hole, obtains having the method for regulation shape section bar by the hole with the bean jelly style.
Aluminium self covers one deck stable state film from the teeth outwards, seawater etc. are difficult to corrosion, but because alkali resistance materials such as mortar are easy to corrosion, so after usually aluminium being carried out anodic oxidation treatment, it is general utilizing the transparent coating of the covering delustrings such as electrodeposition coating composition of delustring.
Anion electrophoretic coating as this delustring, for example, have in the water dispersible vinyl copolymer that has the alcoxyl silyl on side chain, cooperation constitutes (opening flat 2-255871 communique with reference to the spy) with the melamine resin that this multipolymer does not have intermiscibility fully.
But on carrying out the aluminium section bar that anodic oxidation coating handles the time, the mold-mart that exists so-called aluminium section bar is very showy, causes the inferior problem of commodity value with the anion electrophoresis coating electrodeposited coating of delustring.
In addition, also can lift in the presence of silicate compound, by contain the monomer that will have the alcoxyl silyl, the unsaturated monomer of hydroxyl, carboxylic unsaturated monomer, and other unsaturated monomers carry out the water dispersible vinyl polymerization resin that the radical copolymerization obtains, and the emulsion that the linking agent water-dispersion is constituted causes extinction anion electrophoresis coating (opening flat 11-315254 communique with reference to the spy).
Also have, can lift the monomer that will have the alcoxyl silyl, the unsaturated monomer of hydroxyl, carboxylic unsaturated monomer, and other unsaturated monomers carry out the water dispersible vinyl polymerization resin that the radical copolymerization obtains, and adjust the solvability parameter of linking agent and carry out water-dispersion and constitute the extinction anion electrophoretic coating (spy opens the 2001-131494 communique) that emulsion obtains.
Here, in foregoing invention, will have the monomer of alcoxyl silyl, for example, divinyl dimethoxy silane, (CH
2=CH)
2Si (OCH
3)
2, divinyl two-beta-methoxy-ethoxy silane, (CH
2=CH)
2Si (OCH
2CH
2OCH
3)
2, ethene trimethoxy silane, CH
2=CHSi (OCH
3)
3, ethene three ethoxy silane, CH
2=CHSi (OC
2H
5)
3, ethene three-beta-methoxy-ethoxy silane, CH
2=CHSi (OCH
2CH
2OCH
3)
2, γ-methacrylic oxygen propyl group trimethoxy silane, γ-methacrylic oxygen propyl group three ethoxy silane, γ-isocyanic ester propyl group three ethoxy silane etc., carry out the water dispersible vinyl copolymer resin that the radical copolymerization obtains with other monomers, during long storage, there is problems such as producing gel particles in the resin, use the anion electrophoresis coating of this emulsion, finishability and mold-mart disguise are insufficient.For this reason, behind the manufacturing water dispersible vinyl copolymer resin, add linking agent, other additives, basic cpd at once, obtain the emulsion that the extinction anion electrophoresis coating is used by water-dispersion.
Thus, from making water dispersible ethene is that the copolymerization resin forms emulsion to water-dispersion, must carry out a series of operation, adjust manufacturing equipment space, carrying pipe arrangement, the hold tank of emulsion and containing storehouse etc., need expense and time, so require the package stability of a kind of water dispersible vinyl copolymer resin of exploitation, the finishability of filming, the disguised good extinction anion electrophoretic coating of mold-mart.
Summary of the invention
Present inventors are in order to address the above problem, through further investigation repeatedly, found that the package stability that can obtain water dispersible vinyl copolymer resin, the finishability of filming, the disguised good extinction anion electrophoretic coating of mold-mart, finish this invention.
That is, the present invention about:
1. the extinction anion electrophoretic coating contains the emulsion of following formation: as the reaction in the 1st stage, will contain hydroxyl unsaturated monomer (a), contain carboxyl unsaturated monomer (b), and other radical polymerization unsaturated monomers (c) carry out the radical copolymerization and obtain water dispersible ethylene copolymer resin (A); As the reaction in the 2nd stage, the epoxy compounds (d) that has 1 above epoxy group(ing) and hydroxyl silylation in this water dispersible ethylene copolymer resin (A) and 1 molecule is heated mixing, obtain water-base resin (I); Then cooperate this water-base resin (I), linking agent (II) and basic cpd, carry out water-dispersion and form emulsion.
2, according to the 1st extinction anion electrophoretic coating, wherein, the acid value of water-base resin (I) is 30～200mgKOH/g, and hydroxyl value is 15～150mgKOH/g.
3, according to the extinction anion electrophoretic coating of record in the 1st or the 2nd, wherein, linking agent (II) is aminoresin stiffening agent and/or block isocyanic acid ester compound.
The working of an invention form
Below the present invention is elaborated.
Water-base resin (I) is that the unsaturated monomer (c) of the unsaturated monomer (a) that will contain hydroxyl, the unsaturated monomer (b) that contains carboxyl and other radical polymerizations carries out the radical copolymerization, again the water dispersible ethylene copolymer resin (A) that obtains is carried out polymerization, then, in the presence of water dispersible ethylene copolymer resin (A), heat the water-dispersed resin that mixes to obtain with the epoxy compounds (d) that has 1 above epoxy group(ing) and hydroxyl silylation in the molecule (the following abbreviation sometimes made epoxy silane monomer (d)).
The unsaturated monomer of hydroxyl (a), hydroxyethyl (methyl) acrylate is for example arranged, hydroxypropyl (methyl) acrylate, hydroxyl butyl (methyl) acrylate, (gathering) glycol monomethyl (methyl) acrylate, (gathering) propylene glycol list (methyl) acrylate, the hydroxyl butyl vinyl ether, (methyl) vinyl carbinol, and above-mentioned unsaturated monomer class and the β-propine lactone that contains hydroxyl, dimethyl propine lactone, butyrolactone, γ-Wu Neizhi, γ-Ji Neizhi, γ-Xin Neizhi, γ-lauryl lactone, 6-caprolactone, the reactant of lactone compounds such as δ-caprolactone etc., as trade(brand)name, プ ラ Network セ Le FM1 (ダ ィ セ Le chemistry society system is arranged, trade(brand)name, caprolactone modification (methyl) vinylformic acid hydroxyl ester class), プ ラ Network セ Le FM2 (with a left side), プ ラ Network セ Le FM3 (with a left side), プ ラ Network セ Le FA1 (with a left side), プ ラ Network セ Le FA2 (with a left side), プ ラ Network セ Le FA3 (with a left side) etc.
Carboxylic unsaturated monomer (b), for example have (methyl) vinylformic acid, toxilic acid, プ ラ Network セ Le FM1A (below, ダ ィ セ Le chemistry society system, caprolactone modification contains carboxyl (methyl) Acrylic Acid Monomer, trade(brand)name), プ ラ Network セ Le FM4A, プ ラ Network セ Le FM10A etc.
Other radical polymerization unsaturated monomer (c) for example has (methyl) acrylic acid C such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) lauryl acrylate, (methyl) cyclohexyl acrylate
1～C
18(methyl) acrylic acid amides and derivatives class, (methyl) acrylonitrile compound classes etc. such as aromatic vinyl monomer classes such as alkyl ester or cycloalkyl ester class, vinylbenzene, (methyl) acrylic acid amides, N-fourth oxygen methyl (methyl) acrylic acid amides, N-methyl (methyl) acrylic acid amides.
Other for example have polyether-modified acrylic acid series unsaturated monomers such as polyoxyethylene glycol mono acrylic ester, polyethylene glycol monomethacrylate, polypropylene glycol mono acrylic ester, polypropylene glycol monomethacrylate, poly glycol monomethyl ether mono acrylic ester, polyethyleneglycol ether metacrylic acid ester.
These monomeric cooperation ratios, with respect to hydroxyl unsaturated monomer (a), contain the solids component sum total metering of carboxyl unsaturated monomer (b), other radical polymerization unsaturated monomers (c), the hydroxyl unsaturated monomer is 3～50 weight %, be preferably 5～40 weight %, containing the carboxyl unsaturated monomer is 2～40 weight %, be preferably 4～30 weight %, other unsaturated monomers are 10～90 weight %, be preferably 20～70 weight %.
The manufacture method of ethylene copolymer resin (A), known manufacture method is carried out before can utilizing, for example, solution polymerization process, outstanding turbid polymerization, emulsion polymerization etc., preferably following solution polymerization process.
As the organic solvent that uses in the radical copolymerization, for example preferably use ethers such as alcohols such as n-propyl alcohol, Virahol, n-butanols, t-butanols, isopropylcarbinol, match fine jade Suo Fu, methyl match fine jade Suo Fu, butyl match fine jade Suo Fu, methyl carbitol, 2-methyl cellosolve, cellosolvo, 2-isopropoxide ethanol, butoxy ethanol, Diethylene Glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, 1-methoxyl group-2-propyl alcohol, 1-oxyethyl group-2-propyl alcohol, dipropylene glycol monomethyl ether etc.
In addition, as required, for example can also and use the fragrant same clans such as dimethylbenzene, toluene, ketones such as acetone, methylethylketone, 2 pentanone, methyl-n-butyl ketone, mibk, isophorone, pimelinketone, ester classes such as ritalin, vinyl acetic monomer, propyl acetate, N-BUTYL ACETATE, isobutyl acetate, amyl acetate-n, 3-methoxyl group butylacetic acid ester, 2-ethylhexyl acetic ester, Benzyl Acetate, cyclohexyl acetate, methyl propionate, ethyl propionate.
As the radical polymerization initiator that uses in the radical copolymerization, benzoyl peroxide, two t-butyl hydroperoxide, t-butyl hydroperoxide, Three methyl Benzene superoxide, cumene hydroperoxide, diisopropyl benzene hydroperoxide, t-butyl peroxy benzoic ether, lauryl peroxide, acetyl pexoxide, t-butyl peroxy-superoxide such as 2-Ethylhexyl Alcohol ester are for example arranged, α, azo-compounds such as acyl cyanide, azo bis cyclohexane carbonyl nitrile in α '-azobis isobutyronitrile, the two dimethyl-pentens of azo.
Solution polymerization, by in above-mentioned organic solvent, with hydroxyl unsaturated monomer (a), contain the mixture of carboxyl unsaturated monomer (b), other unsaturated monomers monomer classes such as (c), radical polymerization initiator, for example, at 50～200 ℃, under preferred 60～180 ℃ temperature, reacted 1～24 hour, preferred 2～10 hours, can obtain.
The vinyl polymerization resin (A) that herein obtains, storage property is stable good, can be round can, drum, Oil Tank etc. in long storage, even also can be in open air placement for some time in summer.
Then, with vinyl polymerization resin (A) on one side 40～120 ℃ of heating, on one side hybrid epoxidized silane monomer (d), obtain water-base resin (I) thus.
As epoxy silane monomer (d), the epoxy silane monomer with following formula (1)～(7) expression is for example arranged.
Formula (1)
Formula (2)
Formula (3)
Formula (4)
Formula (5)
Formula (6)
Formula (7)
The cooperation ratio of epoxy silane monomer (d) is 0.1～20 weight % in the solids component of vinyl polymerization resin (A), is preferably 1～15 weight %.Epoxy silane monomer (d) is during less than 0.1 weight %, and the extinction effect of filming is insufficient, when surpassing 20 weight %, impairs the stability of extinction anion electrophoretic coating.As the blended Heating temperature is 40～120 ℃, is preferably 60～100 ℃ scope, by with stirrings such as dispersion rod 0.1～12 hour, obtains water-base resin (I).
The hydroxyl value of water-base resin (I) is the scope of 30～200mgKOH/g, the scope, the acid value that are preferably 50～180mgKOH/g are the scope of 15～150mgKOH/g, be preferably the scope of 20～130mgKOH/g, the number molecular-weight average is 10000～100000, is preferably 20000～60000 scope.
The number molecular-weight average was less than 10000 o'clock, and film performance is insufficient, and the number molecular-weight average surpasses at 100000 o'clock, and the viscosity increased of water-base resin during water-dispersion, is difficult to form uniform emulsion.
As the aminoresin of linking agent (II), known aminoresin before can using.As aminoresin, the methylolation aminoresin that has amino components such as melamine, urea, phenyl diamino triazine, methyl guanamines, ス テ ロ グ Na ミ Application, spiral shell diamino triazine, dicyan diamide and aldehyde reaction to obtain.As aldehydes, formaldehyde, Paraformaldehyde 96, acetaldehyde, phenyl aldehyde etc. are arranged.Can use by the etherate of suitable alcohol,, methyl alcohol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butanols, i-butanols, 2-ethyl butanol, 2-Ethylhexyl Alcohol etc. be arranged as the alcohol that uses in the etherificate with this methylolation ammonia resin formation.
As the block polyisocyanate compound of linking agent (II), known before can using with the material of block agent with the isocyanate group block of polyisocyanate compounds.
As polyisocyanate compounds, the aliphatic diisocyanate class of HDI or trimethyl-hexamethylene diisocyanate one class is for example arranged; The annular aliphatic diisocyanates of hydrogenation xylylene vulcabond or isophorone diisocyanate one class; Tolylene diisocyanate or 4, the organic diisocyanate of aromatic diisocyanate class one class of 4 '-diphenylmethanediisocyanate, one class himself, perhaps, these organic diisocyanates and multivalence alcohol, the affixture of low molecular weight polyester resin or water etc., or as above-mentioned each organic diisocyanate cyclized polymer each other, and then isocyanic ester biuret thing etc., as these representational commercially available products, have " バ one ノ ッ Network D-750 ;-800; DN-950 ;-970 or 15-455 " [more than, big Japanese ink chemical industry goods], " テ ス モ ヅ ュ-Le L; N; HL; IL or N3390 " [German バ ィ エ Le society goods], " ケ ネ-ト D-102 ;-202 ;-110N or 123N " [military field pharmaceutical industries goods], " コ ロ ネ-ト L; HL; EH or 203 " [Japanese Port リ ゥ レ Application mechanicals] or " デ ュ ラ ネ-ト 24A-90CX " [Asahi Chemical Industry's mechanicals] etc.
In these, preferably aliphatic diisocyanate class or annular aliphatic diisocyanates.As the block agent, for example can use phenol system, lactan system, active methylene system, alcohol system, mercaptan system, sour acid amides system, imide series, amine system, imidazoles system, urea system, carbamate, imines to be or block agent such as sulphite system.
Among the present invention, the cooperation ratio of water-base resin (I) and linking agent (II), water-base resin (I) are 30～90 weight %, and linking agent (II) is 70～10 weight %, and preferably water-base resin (I) is 35～80 weight %, and linking agent (II) is 65～20 weight %.When linking agent (II) was lower than 10 weight %, film performances such as weathering resistance, scuff resistance, the processibility of filming worsened, and when surpassing 70 weight %, film performances such as weathering resistance, the processibility of filming also worsen.
Used basic cpd in the neutralization of water-base resin (I) has first step monoamines such as ethamine, propylamine, butylamine, benzylamine, monoethanolamine, neopentyl alcohol amine, 2-aminopropanol, 3-aminopropanol; Second stage monoamines such as diethylin diethanolamine, two-n-or diisopropanolamine (DIPA), N-Mono Methyl Ethanol Amine, N-ehtylethanolamine; Third stage monoamines such as dimethylethanolamine, Trimethylamine 99, triethylamine, tri-isopropyl amine, methyldiethanolamine, dimethylamino-ethanol; Polyamine triethylamines such as diethylenetriamine, hydroxyethylamine ethamine, ethylamino-ethamine, methylamino propylamine etc.
In the extinction anion electrophoretic coating, the cooperation ratio of basic cpd, be preferably 0.1～1.2 normal scope in equivalent, sum total metering with respect to the solids component of water-base resin (I), linking agent (II), basic cpd is 0.01～10 weight %, is preferably 0.05～5 weight %.When basic cpd was lower than 0.01 weight %, the water dispersible of water-based emulsion was inferior, and when surpassing 10 weight %, film performance worsens.
In extinction anion electrophoretic coating of the present invention, can add UV light absorber, photostabilizer.
As UV light absorber, salicyclic acid derivatives such as the hot phenyl salicylic acid esters of phenyl salicylic acid esters, P-, 4-t-butylbenzene base salicylate are arranged; 2, the 4-dihydric benzophenone, 2-hydroxyl-4-methoxyl group benzophenone, 2,2 '-dihydroxyl-4-methoxyl group benzophenone, 2-hydroxyl-4-methoxyl group-2 '-carboxyl benzophenone, 2-hydroxyl-4-methoxyl group-5-sulfo group benzophenone three hydroxyl esters, 2,2 '-dihydroxyl-4,4 '-dimethoxy benzophenone, 2-hydroxyl-4-octyloxy benzophenone, 2-hydroxyl-4-octadecane oxygen base benzophenone, sodium 2,2 '-dihydroxyl-4,4 '-dimethoxy-5-sulfo group benzophenone, 2,2 ', 4,4 '-tetrahydroxy benzophenone, 4-dodecyloxy-2-hydroxyl benzophenone, 5-chloro-2-hydroxyl benzophenone, Resorcinol list benzophenone, 2,4-dibenzoyl Resorcinol, 4,6-dibenzoyl Resorcinol, hydroxyl dodecyl benzophenone, 2, benzophenones such as 2 '-dihydroxyl-4-(3-metacryloxy-2-hydroxyl third oxygen) benzophenone system; The compound of 124 Triazoles such as 2-(2 '-hydroxyl-5 '-tolyl) 124 Triazole system and other (oxalic acid anilide, cyanoacrylates etc.) etc.
As the photostabilizer that uses in the mixed system, be the hindered amine derivative, specifically have two-(2,2 '; 6,6 '-tetramethyl-4-piperidines acyl group) sebate, 4-benzoyloxy group-2,2 '-; 6,6 '-tetramethyl piperidine etc. can suitably use more than a kind or 2 kinds in these.
The emulsion of extinction anion electrophoretic coating is basic cpd (e), deionized water to be joined water-base resin (II), linking agent (II) limit stir the limit with splash bar and make.
The extinction anion electrophoretic coating as required, can add pigment, dyestuff, hardening catalyst, flowing regulator, carries out PH and adjusts, and adds deionized water, and obtaining solids component is the extinction anion electrophoretic coating of 5 weight %～20 weight %.As the coated article of this extinction anion electrophoretic coating, preferably electrodeposited coating is on the anodic oxidation aluminum of painted or non-coloring.
Use this electrophoretic paint to form when filming, be that the above-mentioned anion electrophoresis coating that obtains is formed body lotion, after aluminium flooded in this body lotion, carry out anaphoresis and cover with paint, lacquer, colour wash, etc., form the thick desciccator diaphragm of 5～30 μ, do not wash (non-drip washing), or wash (drip washing), then, after room temperature is placed, form by sintering (for example, about 160～200 ℃ about 20～40 minutes) and to film.
The invention effect
In the past, because there is the problem of stability in water-base resin, carry out water-dispersion from being fabricated onto of water-base resin and form emulsion, must carry out a succession of operation, space at producing apparatus, carry the pipeline of emulsion, need cost funds and time in the adjustment in hold tank and warehouse etc., but according to the present invention, the ethylene copolymer (A) that the radical copolymerization is obtained, heat the water-base resin (I) that mixes to obtain with the epoxy compounds (d) that has 1 above epoxy group(ing) and silicol base in 1 molecule, because fine properties, so the operation of being easy to or manufacturing, resin is stored, and can reduce equipment, cost, expenses such as manufacturing.
Embodiment
Below enumerate embodiment and illustrate in greater detail the present invention.But the present invention is not limited, wherein " part " and " % " expression " weight part " and " weight % ".
Production Example 1 (embodiment uses)
The 280g Virahol is packed in the reaction vessel, remain on 80 ℃, in 3 hours to wherein dripping 40g vinylbenzene, 96g methyl methacrylate, 40gn-butyl acrylate, 120g ethyl propenoate, 48g vinylformic acid 2-hydroxyl ethyl ester, 28g vinylformic acid, and the mixture of the two methyl pentane nitriles of 8g azo, then, add the two methyl pentane nitriles of 4g azo, kept 1 hour at 80 ℃, react, obtain ethylene copolymer resin No.1.
In above-mentioned ethylene copolymer resin No.1, add 20g KBM-402 (the シ リ コ of SHIN-ETSU HANTOTAI-Application society system, trade(brand)name, γ-Racemic glycidol oxygen propyl group methyl diethoxy silane), mixed 1 hour at 60 ℃, add Virahol, obtaining solids component is the water-base resin No.1 of 65 weight %.
This water-base resin No.1, weight-average molecular weight is 25000, and acid value is 55mgKOH/g, and hydroxyl value is 58mgKOH/g.
Production Example 2 (embodiment uses)
In reaction vessel, add the 275g Virahol, remain on 80 ℃, in 3 hours to wherein dripping 75g vinylbenzene, 155g methyl methacrylate 155g, 95g n-butyl acrylate, 50g ethyl propenoate, 75g vinylformic acid 2-hydroxyl ethyl ester, 35g vinylformic acid, and the mixture of the two methyl pentane nitriles of 1g azo, then add the two methyl pentane nitriles of 3g azo, kept 1 hour at 80 ℃, react, obtain ethylene copolymerization resin No.2.
In above-mentioned ethylene copolymer resin No.2, add 35g KBM-403 (the シ リ コ of SHIN-ETSU HANTOTAI-Application society system, trade(brand)name, γ-Racemic glycidol oxygen propyl group trimethoxy silane), mixed 1 hour at 50 ℃, add Virahol, obtain the water-base resin No.2 of solids component 65 weight %.
This water-base resin No.2, weight-average molecular weight is 30000, and acid value is 53mgKOH/g, and hydroxyl value is 72mgKOH/g.
Production Example 3 (comparative example is used)
In reaction vessel, add the 280g Virahol, remain on 80 ℃, in 3 hours to wherein dripping 40g vinylbenzene, 96g methyl methacrylate, 28g KBM-503 (the シ リ コ of SHIN-ETSU HANTOTAI-Application society system, trade(brand)name, γ-methacrylic acid oxygen propyl group trimethoxy silane), 40g n-butyl acrylate, 120g ethyl propenoate, 48g vinylformic acid 2-hydroxyl ethyl ester, 28g vinylformic acid, and the mixture of the two methyl pentane nitriles of 8g azo, then add the two methyl pentane nitriles of 4g azo, kept 1 hour at 80 ℃, react, make the water-base resin No.3 of solids component 65 weight %.
This water-base resin No.3, weight-average molecular weight is 25000, and acid value is 55mgKOH/g, and hydroxyl value is 58mgKOH/g.
Production Example 4 (comparative example is used)
In reaction vessel, add the 275g Virahol, remain on 80 ℃, in 3 hours to wherein dripping 75g vinylbenzene, 155g methyl methacrylate, 15g KBM-503 (the シ リ コ of SHIN-ETSU HANTOTAI-Application society system, trade(brand)name, γ-methacrylic acid oxygen propyl group trimethoxy silane), 95g n-butyl acrylate, 50g ethyl propenoate, 75g vinylformic acid 2-hydroxyl ethyl ester, 35g vinylformic acid, and the mixture of the two methyl pentane nitriles of 1g azo, then add the two methyl pentane nitriles of 3g azo, kept 1 hour at 80 ℃, react, make the water-base resin No.4 of solids component 65 weight %.
This water-base resin No.4, weight-average molecular weight is 30000, and acid value is 53mgKOH/g, and hydroxyl value is 72mgKOH/g.
The cooperation content of water-base resin No.1～No.4 has been shown in the table 1.
Table 1
| Production Example 1 | Production Example 2 | Production Example 3 | Production Example 4 | ||
| Water-base resin | No.1 | No.2 | No.3 | No.4 | |
| Monomer cooperates content | Vinylbenzene | 40 | 75 | 40 | 75 |
| The methacrylic methyl esters | 96 | 155 | 96 | 155 | |
| KBM-503 (annotating 1) | 28 | 15 | |||
| N-butyl acrylate | 40 | 95 | 40 | 95 | |
| Ethyl propenoate | 120 | 50 | 120 | 50 | |
| Vinylformic acid 2-hydroxyl ethyl ester | 48 | 75 | 48 | 75 | |
| Vinylformic acid | 28 | 35 | 28 | 35 | |
| The two methyl pentane nitriles of azo | 8 | 1 | 8 | 1 | |
| The two methyl pentane nitriles of azo | 4 | 3 | 4 | 3 | |
| KBM-402 (annotating 2) | 35 | ||||
| KBM-403 (annotating 3) | 20 | ||||
(annotating 1) KBM-503: γ-first vinylformic acid oxygen propyl group trimethoxy silane
(annotating 2) KBM-402: γ-Racemic glycidol oxygen propyl group methyl diethoxy silane
(annotating 3) KMB-403: γ-Racemic glycidol oxygen propyl group trimethoxy silane
With the water-base resin No.1～No.4 that makes in the above-mentioned Production Example 1～4, preserved 10 days down for 30 ℃, make the emulsion that the extinction anion electrophoretic coatings are used according to following Production Example 5～8.
The Production Example of Production Example 5 emulsion No.1
Carboxyl with respect to the water-base resin No.1 170 parts (solids components) that makes in the Production Example 1, after cooperating 0.4 normal triethylamine, carry out blending dispersion, then, behind 30 parts of ニ カ of blending dispersion ラ Star Network MX430 in this thing (annotating 4), slowly drip deionized water while stirring, add triethylamine again, making PH is 7.5, obtains the emulsion No.1 of solids component 10%.
Production Example 6～12
The same with Production Example 5, by cooperating emulsion No.2～8 that obtain solids component 10% shown in the table 2.
Table 2
| Production Example 5 | Production Example 6 | Production Example 7 | Production Example 8 | Production Example 9 | Production Example 10 | Production Example 11 | Production Example 12 | |
| Emulsion | No.1 | No.2 | No.3 | No.4 | No.5 | No.6 | No.7 | No.8 |
| Water-base resin No.1 forms branch 65% admittedly | 107.7 (70) | 107.7 (70) | 107.7 (70) | |||||
| Water-base resin No.2 forms branch 65% admittedly | 107.7 (70) | |||||||
| Water-base resin No.3 forms branch 65% admittedly | 107.7 (70) | 107.7 (70) | 107.7 (70) | |||||
| Water-base resin No.4 forms branch 65% admittedly | 107.7 (70) | |||||||
| Trihexylamine | 0.4 equivalent branch | ← | ← | ← | ← | ← | ← | ← |
| ニ カ ラ Star Network MX-430 (annotating 4) | 30 (30) | 30 (30) | 30 (30) | 30 (30) | 30 (30) | 30 (30) | 30 (30) | 30 (30) |
| デ ュ ラ ネ-ト 24A-90CX (annotating 5) | 12.5 (10) | 12.5 (10) | ||||||
| チ ス PVC Application 328 (annotating 6) | 2 | 2 | ||||||
| チ ス PVC Application 328 (annotating 7) | 1 | 1 | ||||||
| Triethylamine | Adjust pH=7.51 | |||||||
| Break away from son | Adjust solid formation and divide 10% | |||||||
(annotate 4) ニ カ ラ ッ Network MX-430: three and ケ ミ カ Le Co., Ltd. system, trade(brand)name, fourth oxidation melamine resin, solids component 100%
(annotating 5) デ ュ ラ ネ-ト 24A-90CX: rising sun chemical industry Co., Ltd. system, trade(brand)name, block polymeric polyisocyanate, solids component 80%
(annotating 6) チ ス PVC Application 328: チ バ ガ ィ ギ-Co., Ltd.'s system, trade(brand)name, UV light absorber
(annotating 7) チ ス PVC Application 292: チ バ ガ ィ ギ-Co., Ltd.'s system, trade(brand)name, photostabilizer.
Embodiment 1
Adding triethylamine in 2000 parts above-mentioned 10% emulsion No.1, make pH is 8.5, obtains extinction anion electrophoretic coating No.1.
Embodiment 2～4, comparative example 1～4
Utilize and embodiment 1 identical operations, obtain embodiment 2～4, extinction anion electrophoretic coating No.2～8 of comparative example 1～4.
Make test board
The anion electrophoresis coating that obtains in embodiment and the comparative example is made body lotion, as coated article, with the re-electrolysis of having implemented degreasing-corrode-neutralize-be anodizing to processing-sealing of hole handle (silver color: size is 150 * 70 * 0.5mm) to flood in this body lotion by the anodic oxidation aluminium of film thickness 10 μ m, carry out electrodeposited coating, form the thick enamel series anion electrophoretic paint desciccator diaphragm of 18 μ m, after the washing, 180 ℃ of sintering 30 minutes.
Its test-results is shown in table 3.
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | ||||
| Anion electrophoretic coating has been given birth in delustring | No.1 | No.2 | No.3 | No.4 | No.5 | No.6 | No.7 | No.8 | |||
| Cooperate | Emulsion | No.1 | No.2 | No.3 | No.4 | No.5 | No.6 | No.7 | No.8 | ||
| Triethylamine | Adjust PH=8.5 | ← | ← | ← | ← | ← | ← | ← | |||
| Film performance | Paint stability (annotating 8) | ◎ | ◎ | ◎ | ◎ | △ | △ | × | × | ||
| Be coated with face smoothness (annotating 9) | ◎ | ◎ | ◎ | ◎ | ○ | ○ | △ | △ | |||
| Mold mark disguise (annotating 10) | Visual | ○ | ○ | ○ | ○ | × | △ | × | △ | ||
| The L value | 10 | 50 | 53 | 52 | 51 | 40 | 41 | 40 | 41 | ||
| 30 | 76 | 78 | 78 | 75 | 89 | 90 | 88 | 90 | |||
| 45 | 122 | 125 | 124 | 123 | 127 | 130 | 128 | 132 | |||
| 90 | 21 | 20 | 20 | 20 | 3 | 2 | 3 | 2 | |||
| Gloss | 45 | 11 | 10 | 10 | 10 | 9 | 8 | 9 | 8 | ||
| 60 | 14 | 13 | 13 | 14 | 13 | 14 | 13 | 14 | |||
| 85 | 43 | 40 | 45 | 45 | 65 | 68 | 60 | 69 | |||
| Weathering resistance (annotating 11) | 93 | 93 | 92 | 96 | 89 | 88 | 86 | 88 | |||
(annotate 8) paint stability: coating is filled in the test tube (height 20cm, capacity 20ml), 20 ℃ leave standstill 7 days after, the height of research container bottom precipitation residue.
◎: residue is good below 0.5mm
Zero: residue at 0.6～5mm for good slightly
△: residue at 6～10mm for poor slightly
*: be poor more than 11mm.
The smoothness that (annotate 9) films: with the naked eye comment rank film coated surface (shaddock skin, concavo-convex etc.)
◎: good
Zero: good slightly
△: poor slightly
*: poor
The disguise of (annotating 10) mold-mart: naked eyes evaluation and gloss, L value are estimated.
Naked eyes:
Zero: mold-mart is disguised good
△: mold-mart is disguised poor
*: the disguised extreme difference of mold-mart
L value: use angle spectrophotometer GCMS-4 (society of color technical institute system in the village, trade name),, change acceptance angle by 10 degree, 30 degree, 45 degree (positive and negative firing angle), 90 degree and measure with respect to input angle 45 degree.Filming that the L value is big is the gonorrhoea look, and mold-mart is disguised good, utilizes the preferred change of L value of being penetrated with forming little.
Gloss: use varied-angle glossmeter UGV-50 (ス ガ trier Co., Ltd. system, trade name) to measure.Measure the angle and be taken as 45 degree, 60 degree, 85 degree.Cause that by angle the glossy change is preferably little.
(annotating 11) weathering resistance: utilize Exposure to Sunlight weather look rate degree instrument, estimate according to 2000 hours gloss retention (%) of irradiation.
Claims (5)
1, a kind of extinction anion electrophoretic coating, it contains the following emulsion that obtains: as the reaction in the 1st stage, the unsaturated monomer (c) that will contain the unsaturated monomer (a) of hydroxyl, the unsaturated unit (b) that contains carboxyl and other radical polymerizations carries out the radical copolymerization and obtains water dispersible ethylene copolymer resin (A); As the 2nd elementary reaction, the epoxy silane monomer (d) that has 1 above epoxy group(ing) in this water dispersible ethylene copolymer resin (A) and 1 molecule is heated mixing, obtain water-base resin (I); Then this water-base resin (I), linking agent (II) and basic cpd are cooperated, water-dispersion forms emulsion;
Wherein, the unsaturated monomer (a) that contains hydroxyl, the unsaturated monomer (b) that contains carboxyl, the cooperation ratio of the unsaturated monomer of other radical polymerizations (c) is with respect to the unsaturated monomer that contains hydroxyl (a), the unsaturated monomer (b) that contains carboxyl, the solids component sum total metering of the unsaturated monomer of other radical polymerizations (c), the unsaturated monomer (a) that contains hydroxyl is 3～50 weight %, the unsaturated monomer (b) that contains carboxyl is 2～40 weight %, the unsaturated monomer of other radical polymerizations (c) is 10～90 weight %
The cooperation ratio of epoxy silane monomer (d) is 0.1～20 weight % in the solids component of vinyl polymerization resin (A),
The cooperation ratio of water-base resin (I) and bridging property (II) is that water-base resin (I) is 30～90 weight %, and linking agent (II) is 70～10 weight %,
The cooperation ratio of basic cpd is 0.01～10 weight % with respect to the solids component sum total metering of water-base resin (I) and linking agent (II).
2, according to the extinction anion electrophoretic coating of claim 1 record, wherein, the acid value of water-base resin (I) is 30～200mgKOH/g, and hydroxyl value is 15～150mgKOH/g.
3, according to the extinction anion electrophoretic coating of claim 1 or 2 records, wherein, linking agent (II) is aminoresin stiffening agent and/or block isocyanate compound.
4, according to the extinction anion electrophoretic coating of claim 1 record, wherein, epoxy silane monomer (d) is γ-Racemic glycidol oxygen propyl group methyl diethoxy silane.
5, according to the extinction anion electrophoretic coating of claim 1 record, wherein, epoxy silane monomer (d) is γ-Racemic glycidol oxygen propyl group trimethoxy silane.
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| CNB031272681A CN1307270C (en) | 2003-09-29 | 2003-09-29 | Extinction anion type electrophoresis paint |
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| CNB031272681A CN1307270C (en) | 2003-09-29 | 2003-09-29 | Extinction anion type electrophoresis paint |
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| CN1307270C true CN1307270C (en) | 2007-03-28 |
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| CN102337073B (en) * | 2011-08-18 | 2013-12-25 | 中科院广州化学有限公司 | Water-soluble nonluminous anionic electrophoretic coating and preparation method and application thereof |
| CN103132117B (en) * | 2011-12-02 | 2015-12-09 | 关西涂料株式会社 | For the formation of the method for film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1107871A (en) * | 1993-12-21 | 1995-09-06 | 帝国化学工业公司 | Aqueous coating composition |
| JPH0940835A (en) * | 1995-07-31 | 1997-02-10 | Kurimoto Ltd | Penetrable waterproof composition and waterproof structure |
| JPH11315254A (en) * | 1998-05-06 | 1999-11-16 | Kansai Paint Co Ltd | Aqueous matte coating composition |
| JP2001131494A (en) * | 1999-11-04 | 2001-05-15 | Kansai Paint Co Ltd | Anionic-type matte electrodeposition coating composition |
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2003
- 2003-09-29 CN CNB031272681A patent/CN1307270C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1107871A (en) * | 1993-12-21 | 1995-09-06 | 帝国化学工业公司 | Aqueous coating composition |
| JPH0940835A (en) * | 1995-07-31 | 1997-02-10 | Kurimoto Ltd | Penetrable waterproof composition and waterproof structure |
| JPH11315254A (en) * | 1998-05-06 | 1999-11-16 | Kansai Paint Co Ltd | Aqueous matte coating composition |
| JP2001131494A (en) * | 1999-11-04 | 2001-05-15 | Kansai Paint Co Ltd | Anionic-type matte electrodeposition coating composition |
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