CN105038516A - Cationic electrodeposition paint composition - Google Patents
Cationic electrodeposition paint composition Download PDFInfo
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Abstract
To provide a cationic electrodeposition paint composition excellent in throwing power, electrodeposition coatability on an alloyed hot-dip galvanized steel sheet, finished appearance, corrosion resistance and mechanical stability. The cationic electrodeposition paint composition contains (A) an amino group-containing modified epoxy resin produced by reacting (a1) a >=8C monocarboxylic acid, (a2) an epoxy resin having two or more epoxy groups in one molecule thereof and having an epoxy equivalent of 300-2,500 and (a3) an amino group-containing compound, (B) a xylene formaldehyde resin modified amino group-containing epoxy resin produced by reacting (b1) an epoxy resin having an epoxy equivalent of 180-2,500, (b2) a xylene formaldehyde resin having a phenolic hydroxyl group and (b3) an amino group-containing compound, and (C) a blocked polyisocyanate curing agent, each in a predetermined amount.
Description
The divisional application that the application is the applying date is on April 2nd, 2010, application number is 201010154497.4, denomination of invention is the patent application of " cation electric deposition paint composition ".
Technical field
The present invention relates to the cation electric deposition paint composition of electrodeposition coating suitability, finishability (on bodyguard リ), non-corrosibility and the mechanical stability excellence on spreadability (つ I ま わ り), alloy galvanized steel plate.
Background technology
Cation electrodeposition coating, because application operability is excellent and erosion resistance good, is therefore widely used as the bottom-coating of the metal products of body of a motor car etc.In recent years, in the metal products of body of a motor car etc., use with the alloy galvanized steel plate rising to object of erosion resistance more, and, improve from the viewpoint of the crashworthiness of body of a motor car, the structure using reinforcing member overlap in bag structural portion etc. more.Such bag structural portion electric current when electrodeposition coating is difficult to flowing, and current density reduces, and be therefore difficult to form electrodeposition coating, spreadability reduces sometimes.
Erosion resistance is obtained in order to ensure the inner panel thickness of such bag structure, have studied all electrodeposition coating conditions, if but the voltage of electrodeposition coating is increased in order to ensure inner panel thickness (such as, 10 μm), outer plate surface then on alloy galvanized steel plate produces pore-forming (Network レ タ リ Application グ) (gas pin hole), on the other hand, if setting electrodeposition coating voltage do not produce shrinkage cavity to make the outer plate surface on alloy galvanized steel plate, then exist can not guarantee inner panel thickness such problem points.
At present, disclose by containing xylene formaldehyde resin modification containing aminoepoxy resin as the cationic coating composition of color spreading agent composition the electrodeposition coating suitability of corrodibility, tack, Rustproof Steel Plate and paint stability excellent, described xylene formaldehyde resin modification containing aminoepoxy resin for making xylene formaldehyde resin (B) and generating (patent documentation 1) containing the epoxy resin (A) that aminocompound (C) and epoxy equivalent (weight) are 180 ~ 2500 reacts.
In addition, also disclose with the amount of 10 ~ 26 % by weight contain polyalkylene oxide hydrocarbon chain, its end with 0.5 ~ 3.0 % by weight amount contain long-chain fat acidic group the cationic composition epoxy resin with number-average molecular weight 2000 ~ 3500 and containing its finishability excellence (patent documentation 2) of cation electric deposition paint composition.
But the balance of the electrodeposition coating suitability on the alloy galvanized steel plate of the cation electric deposition paint composition described in patent documentation 1 and 2, spreadability, finishability, non-corrosibility is insufficient, any one performance above-mentioned all has problems.
Prior art document
Patent documentation
Patent documentation 1: JP 2003-221547 publication
Patent documentation 2: JP 2008-24893 publication
Summary of the invention
The problem that invention will solve
Problem of the present invention is, provides the cation electric deposition paint composition of the electrodeposition coating suitability on a kind of spreadability, alloy galvanized steel plate, finishability, non-corrosibility and mechanical stability excellence.
For solving the means of problem
The present inventor etc. have carried out wholwe-hearted research to solve above-mentioned problem, found that a kind of cation electric deposition paint composition, it contains specific containing amino-modified epoxy resin (A), specific xylene formaldehyde resin modification is containing aminoepoxy resin (B) and end-blocking (Block ロ ッ Network) polyisocyanate curing agent (C), it is characterized in that, the total mass of dividing with their solid is benchmark, respectively containing 40 ~ 70 quality %, 1 ~ 40 quality % and 10 ~ 40 quality % contains amino-modified epoxy resin (A), xylene formaldehyde resin modification is containing aminoepoxy resin (B) and end-blocking polyisocyanate curing agent (C), thus complete the present invention.
That is, the present invention is as follows.
[mode 1]
Cation electric deposition paint composition, it is the cation electric deposition paint composition containing following composition:
Make, in the monocarboxylic acid of carbon number more than 8 (a1), 1 molecule, there are more than 2 epoxy group(ing) and epoxy equivalent (weight) be 300 ~ 2500 epoxy resin (a2) and containing aminocompound (a3) reaction generates contain amino-modified epoxy resin (A);
Make epoxy equivalent (weight) be 180 ~ 2500 epoxy resin (b1), have phenolic hydroxyl group xylene formaldehyde resin (b2) and react containing aminocompound (b3) the xylene formaldehyde resin modification that generates and contains aminoepoxy resin (B); And
End-blocking polyisocyanate curing agent (C);
It is characterized in that, the total mass of dividing with their solid is benchmark, and what contain 40 ~ 70 quality %, 1 ~ 40 quality % and 10 ~ 40 quality % respectively contains aminoepoxy resin (B) and end-blocking polyisocyanate curing agent (C) containing amino-modified epoxy resin (A), xylene formaldehyde resin modification.
[mode 2]
Cation electric deposition paint composition described in mode 1, wherein, be the resin making to generate containing aminocompound (a3) and modified epoxy (A1) react containing amino-modified epoxy resin (A), described modified epoxy (A1) is generated by monocarboxylic acid (a1) and epoxy resin (a2) reaction.
[mode 3]
Cation electric deposition paint composition described in mode 2, wherein, modified epoxy (A1) is that the ratio making monocarboxylic acid (a1) and epoxy resin (a2) reach 0.05 ~ 0.5 with the equivalence ratio of [carboxyl in monocarboxylic acid (a1)]/[epoxy group(ing) in epoxy resin (a2)] carries out reacting and the resin obtained.
[mode 4]
Cation electric deposition paint composition according to any one of mode 1 ~ 3, wherein, monocarboxylic acid (a1) is selected from least one in the group that is made up of saturated and unsaturated aliphatic monocarboxylic acid and hydroxy monocarboxylic acids.
[mode 5]
Cation electric deposition paint composition according to any one of use-pattern 1 ~ 4 and the article be coated with.
The effect of invention
Electrodeposition coating suitability, finishability and non-corrosibility on the spreadability of cation electric deposition paint composition of the present invention, alloy galvanized steel plate are excellent.And then, even if cation electric deposition paint composition of the present invention uses for a long time in paint line, mechanical stability is also excellent, and do not occur the unfavorable condition of painting face abnormal (upspring, cave in, pit (Block Star) etc.), finishability is good.
By in cation electric deposition paint composition of the present invention containing amino-modified epoxy resin (A), the weldability of precipitation film during galvanic deposit becomes good.In addition, be hydrophobicity owing to separating out film, therefore polarization resistance value uprises.Specifically, because the weldability of electrodeposition coating is good, therefore can apply high-voltage, because polarization resistance value is also high, therefore " spreadability " improves.
And then, by the xylene formaldehyde resin modification in cation electric deposition paint composition of the present invention containing aminoepoxy resin (B), the adaptation of film to coated article becomes good, therefore can form the solid precipitation film that can tolerate the spark that alloy galvanized steel plate occurs when electrodeposition coating, " the electrodeposition coating suitability of alloy galvanized steel plate " excellent and finishability and the good coated article of non-corrosibility can be obtained.
And then, because the consistency containing aminoepoxy resin (B) containing amino-modified epoxy resin (A) and xylene formaldehyde resin modification is good, therefore the paint stability of cation electric deposition paint composition of the present invention is excellent, can obtain the film of finishability excellence.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of 4 ボ ッ Network ス method cover butter fixtures.
Fig. 2 is the schematic diagram of cover butter device.
Fig. 3 is the schematic diagram of laboratory UF device.
The explanation of symbol
14 ボ ッ Network ス method spreadability test fixtures
The hole of 2 circles
3 cover butter devices
4 electrocoating paint baths
5 opposite electrodes
6UF device
7 baths
8 circulation engines
9UF film
The supply pipe arrangement of 10 electrocoating paints
The discharge pipe arrangement of 11 separated coating
The discharge pipe arrangement of 12 separated filtrates
Embodiment
Cation electric deposition paint composition of the present invention, contain: containing amino-modified epoxy resin (A), xylene formaldehyde resin modification containing aminoepoxy resin (B) and end-blocking polyisocyanates (C), it is characterized in that, the total mass of dividing with their solid is benchmark, and what contain 40 ~ 70 quality %, 1 ~ 40 quality % and 10 ~ 40 quality % respectively contains aminoepoxy resin (B) and end-blocking polyisocyanate curing agent (C) containing amino-modified epoxy resin (A), xylene formaldehyde resin modification.
Below, each composition is described in detail.
< is containing amino-modified epoxy resin (A) >
Make the epoxy equivalent (weight) in the monocarboxylic acid of carbon number more than 8 (a1), 1 molecule with more than 2 epoxy group(ing) be the epoxy resin (a2) of 300 ~ 2500 and react the resin generated containing aminocompound (a3) containing amino-modified epoxy resin (A).Specifically, can make containing aminocompound (a3), with the epoxy resin (a2) in the monocarboxylic acid of carbon number more than 8 (a1) and 1 molecule with more than 2 epoxy group(ing) is reacted and the modified epoxy (A1) that generates reacts to obtain.
[monocarboxylic acid (a1)]
Monocarboxylic acid (a1) has the carbon number of more than 8.As monocarboxylic acid (a1), for per molecule has the compound of 1 carboxyl, be not particularly limited, such as can enumerate the compound being bonded with 1 carboxyl on hydrocarbon chain such as aromatic series chain or aliphatic chain (such as representative examples of saturated aliphatic chain, unsaturated aliphatic chain etc.), above-mentioned hydrocarbon chain also can be optionally substituted by a hydroxyl group.Specifically, as monocarboxylic acid (a1), can enumerate: aromatic monocarboxylate, saturated and unsaturated aliphatic monocarboxylic acid and hydroxycarboxylic acid.
If the carbon number of monocarboxylic acid (a1) is less than 8, then there is the raising effect that is low, spreadability such as weldability, polarization resistance value and become insufficient tendency.
As above-mentioned aromatic monocarboxylate, such as, can enumerate: ethyl benzoate, p-tert-butyl benzoic acid etc.As above-mentioned saturated and unsaturated aliphatic monocarboxylic acid, such as can enumerate: sad, n-nonanoic acid, capric acid, undecanoic acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, elaidic acid, brassidic acid, linolic acid, linolenic acid etc., and by being selected from by fish oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid, linseed fatty acid, soya fatty acid, sesame oil lipid acid, tori seed oil lipid acid, perilla oil lipid acid, hempseed oil lipid acid, rapeseed oil fatty acid, corn oil fatty acid, ready denier oil acid, Trisun Oil R 80 lipid acid, continuous seed oil fatty acid, walnut oil fat acid, and the drying oil fatty acid that at least a kind of natural fats and oils in the group of coco-nut oil fatty acid composition obtains, semi-drying oil lipid acid etc.As above-mentioned hydroxycarboxylic acid, such as, can enumerate: sabinic acid, 12-oxystearic acid, ricinolic acid etc.As monocarboxylic acid (a1), except above-mentioned carboxylic acid, other aromatic monocarboxylate, cycloaliphatic monocarboxylic, aliphatic monocarboxylic acid etc. suitably can also be used.
[epoxy resin (a2)]
Epoxy resin (a2) is that every 1 molecule has more than 2 epoxy group(ing) and epoxy equivalent (weight) is the resin of 300 ~ 2500.Above-mentioned epoxy equivalent (weight) is preferably 300 ~ 2000.Epoxy resin (a2) preferably has 600 ~ 4000, more preferably has the number-average molecular weight of 600 ~ 3500.Epoxy resin (a2) obtains preferably by the reaction of polyphenolic substance and epoxyhalopropane.
If the epoxy equivalent (weight) of epoxy resin (a2) is less than 300, then non-corrosibility has the tendency of reduction, and if epoxy equivalent (weight) more than 2500, then the electrodeposition coating of alloy galvanized steel plate has the tendency of reduction.
It should be noted that, in this manual, " number-average molecular weight " is the method based on recording in JISK0124-83, by eluant tetrahydrofuran (THF), flow velocity 1.0ml/ minute, measure the value that the number-average molecular weight that recorded by GPC at temperature 40 DEG C obtained for basis conversion with the number-average molecular weight of polystyrene.As GPC device, use " HLC8120GPC " (East ソ ー Co., Ltd. system, trade(brand)name), as separator column, use " TSKgelG-4000HXL ", " TSKgelG-3000HXL ", " TSKgelG-2500HXL ", " TSKgelG-2000HXL " (Jun be East ソ ー Co., Ltd. system) 4 pillars.
As the polyphenolic substance of the manufacture for epoxy resin (a2), such as can enumerate: two (4-hydroxy phenyl)-2, 2-propane [dihydroxyphenyl propane], two (4-hydroxy phenyl) methane [Bisphenol F], two (4-hydroxy-cyclohexyl) methane [A Hydrogenated Bisphenol A F], 2, two (4-hydroxy-cyclohexyl) propane [Hydrogenated Bisphenol A] of 2-, 4, 4 '-dihydroxy benaophenonel, two (4-hydroxy phenyl)-1, 1-ethane, two (4-hydroxy phenyl)-1, 1-Trimethylmethane, two (4-hydroxyl-2 or 3-tert-butyl-phenyl)-2, 2-propane, two (2 hydroxy naphthalene base) methane, four (4-hydroxy phenyls)-1, 1, 2, 2-ethane, 4, 4 '-dihydroxy diphenylsulphone, phenol novolacs (phenolnovolac), cresol novolak (cresolnovolac) etc.
In addition, as epoxy resin (a2), be preferably following formula, by the epoxy resin be obtained by reacting of dihydroxyphenyl propane and epoxy chloropropane.
Change 1
(in formula, n=0 ~ 8)
As the commercially available product of above-mentioned epoxy resin, such as, can enumerate: by ジ ャ パ Application エ Port キ シ レ ジ Application (strain) with the commercially available commercially available product of the trade(brand)name of jER828EL, jER1001.
It should be noted that, modified epoxy (A1) can manufacture as follows: mixing monocarboxylic acid (a1) and epoxy resin (a2), under the existence as the tertiary amine such as dimethyl benzylamine, tributylamine of desired catalysts or the quaternary ammonium salt such as tetraethylammonium bromide, Tetrabutyl amonium bromide etc., reaction 1 ~ 6 hour, preferably 1 ~ 5 hour at the temperature of 80 ~ 200 DEG C, preferably 90 ~ 180 DEG C.
In order to electrodeposition coating suitability, finishability and non-corrosibility on spreadability, alloy galvanized steel plate, preferred modified epoxy (A1) makes monocarboxylic acid (a1) and epoxy resin (a2) obtain with the ratio reaction that the equivalence ratio of [carboxyl in monocarboxylic acid (a1)]/[epoxy group(ing) in epoxy resin (a2)] is 0.05 ~ 0.5.
In the manufacture of modified epoxy (A1), solvent can be used.As used solvent, such as, can enumerate: the hydrocarbon systems such as toluene, dimethylbenzene, hexanaphthene, normal hexane; The ester systems such as methyl acetate, ethyl acetate, butylacetate; The ketone systems such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), Methyl amyl ketone; The acid amides such as dimethyl formamide, N,N-DIMETHYLACETAMIDE system; The alcohol systems such as methyl alcohol, ethanol, n-propyl alcohol, Virahol; The aromatic alkyl such as phenyl methanol, methyl phenyl carbinol alcohols; The ether alcohol such as ethylene glycol monobutyl ether, diethylene glycol monoethyl ether based compound or their mixture etc.
[containing aminocompound (a3)]
What use in the present invention is for giving composition by the cationic of modified epoxy (A1) cationization containing aminocompound (a3), be at least containing 1 with the composition of the active hydrogen of epoxy reaction.Contain aminocompound (a3) as such, such as, can enumerate: the list-such as MMA, dimethylamine, mono aminoethane, diethylamine, single Isopropylamine, Diisopropylamine, dibutyl amine, dibutylamine or two-alkylamine; The alkanolamine such as monoethanolamine, diethanolamine, list (2-hydroxypropyl) amine, two (2-hydroxypropyl) amine, mono-methyl amino ethanol, single ethyl amido alcohol; The ketoimine compound of the alkylene polyamines such as quadrol, propylene diamine, butanediamine, hexamethylene-diamine, tetren, penten, diethyl amino propylamine, diethylenetriamine, Triethylenetetramine (TETA) and these polyamines; The alkylene imine such as ethylenimine, propylidene imines; The cyclic amine etc. such as piperazine, morpholine, pyrazine.In these amine, the amine obtained by primary amine ketoimine can be used in the lump.
What use in cation electric deposition paint composition of the present invention can be manufactured containing aminocompound (a3) by addition reaction in above-mentioned modified epoxy (A1) containing amino-modified epoxy resin (A).
The usage ratio of each composition in above-mentioned addition reaction is not considered critical, can according to appropriate changes such as the purposes of electrodeposition coating composition, usually, with the total mass of dividing containing the modified epoxy (A1) that uses in the manufacture of amino-modified epoxy resin (A) and the solid containing aminocompound (a3) for benchmark, modified epoxy (A1) is 70 ~ 95 quality %, is preferably 75 ~ 93 quality %, and is 5 ~ 30 quality % containing aminocompound (a3), is preferably 7 ~ 25 quality %.
It should be noted that, above-mentioned addition reaction, usually in preferred solvent, carries out 1 ~ 6 hour, preferably 1 ~ 5 hour at the temperature of 80 ~ 170 DEG C, preferably 90 ~ 150 DEG C.
As the solvent in above-mentioned reaction, current known organic solvent can be used, such as: the hydrocarbon system of toluene, dimethylbenzene, hexanaphthene, normal hexane etc.; The ester system of methyl acetate, ethyl acetate, butylacetate etc.; The ketone system of acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), Methyl amyl ketone etc.; The acid amides system of dimethyl formamide, N,N-DIMETHYLACETAMIDE etc.; The alcohol system of methyl alcohol, ethanol, n-propyl alcohol, Virahol etc.; The aromatic alkyl alcohols of phenyl methanol, methyl phenyl carbinol etc.; The ether alcohol based compound of ethylene glycol monobutyl ether, diethylene glycol monoethyl ether etc. or their mixture etc.
The modification of < xylene formaldehyde resin is containing aminoepoxy resin (B) >
Xylene formaldehyde resin modification containing aminoepoxy resin (B) be by make epoxy equivalent (weight) be 180 ~ 2500 epoxy resin (b1), have phenolic hydroxyl group xylene formaldehyde resin (b2) and react the resin generated containing aminocompound (b3).
[epoxy resin (b1)]
Epoxy resin (b1) is the resin of epoxy equivalent (weight) in the scope of 180 ~ 2500, and is at least have 1, the resin of preferred more than 2 epoxy group(ing) in 1 molecule.Above-mentioned epoxy equivalent (weight) is preferably in the scope of 400 ~ 1500.Epoxy resin (b1) has the number-average molecular weight in the scope of preferably 400 ~ 4000 and more preferably 800 ~ 2500.As epoxy resin (b1), the epoxy resin identical with epoxy resin (a2) can be used, particularly preferably by the epoxy resin be obtained by reacting of polyphenolic substance and epoxyhalopropane.
In epoxy resin (b1), if epoxy equivalent (weight) is less than 180, then non-corrosibility has the tendency of reduction, and if epoxy equivalent (weight) more than 2500, then the electrodeposition coating of alloy galvanized steel plate has the tendency of reduction.
[xylene formaldehyde resin (b2)]
Xylene formaldehyde resin (b2) has phenolic hydroxyl group, and this phenolic hydroxyl group can with the epoxy reaction in epoxy resin (b1), by xylene formaldehyde resin modification containing aminoepoxy resin (B) plasticized (modification).
Xylene formaldehyde resin (b2) such as manufactures by making dimethylbenzene, formaldehyde and phenols carry out condensation reaction under the existence of an acidic catalyst.As above-mentioned formaldehyde, the formaldehydogenic compound of product etc. of the facile formalin of industrial appearance, paraformaldehyde, trioxane etc. can be illustrated.
And then, above-mentioned phenols comprises 1 yuan or 2 yuan of phenoloids with 2 or 3 reaction site, specifically, such as can enumerate: phenol, cresols class (ortho-cresol, meta-cresol and p-cresol), paraoctyl phenol, nonylphenol, diphenylol propane, Bi-phenolic Methan e, Resorcinol, pyrocatechol, quinhydrones, p-tert-butylphenol, bisphenol S (bisphenolsulfone), diphenylol ether, p-phenyl phenol or their combination etc.As above-mentioned phenols, particularly preferably phenol, cresols class.
An acidic catalyst used in condensation reaction as above-mentioned dimethylbenzene, formaldehyde and phenols, such as, can enumerate: sulfuric acid, hydrochloric acid, tosic acid, oxalic acid etc., particularly preferably sulfuric acid.The usage quantity of above-mentioned an acidic catalyst is diluted with the water in formalin usually, with the densitometer in the aqueous solution in the scope of 10 ~ 50 quality %.
The temperature that above-mentioned condensation reaction such as can be refluxed by the dimethylbenzene, phenols, water, formalin etc. being heated to exist in reaction system, the temperature of usual 80 ~ 100 DEG C are carried out, and usually, can terminate at 2 ~ 6 hours.
Under these conditions, under the existence of an acidic catalyst, heat dimethylbenzene, formaldehyde and phenols, make it react, can xylene formaldehyde resin be obtained thus.In addition, xylene formaldehyde resin (b2) also can obtain by making the xylene formaldehyde resin obtained by dimethylbenzene and formaldehyde in advance react under the existence of an acidic catalyst with phenols further.
Xylene formaldehyde resin (b2) have preferred 20 ~ 50000mPas (25 DEG C), more preferably 25 ~ 30000 and also preferred 30 ~ 15000mPas (25 DEG C) further scope in viscosity.In addition, the phenolic hydroxyl group value of xylene formaldehyde resin (b2) is preferably 1 ~ 560mgKOH/g, is more preferably 2 ~ 380mgKOH/g, and more preferably 5 ~ 280mgKOH/g.
[containing aminocompound (b3)]
Containing aminocompound (b3) be to import in epoxy resin (b1) amino, give composition for the cationic of cationization, can be with containing uses in amino-modified epoxy resin (A) containing aminocompound (a3) identical contain aminocompound.
Xylene formaldehyde resin modification uses as resinous principle in cation electric deposition paint composition of the present invention containing aminoepoxy resin (B), can by making xylene formaldehyde resin (b2) by their self known methods and carrying out reacting manufacturing containing aminocompound (b3) and epoxy resin (b1).
Xylene formaldehyde resin (b2) and can carrying out in any order the reaction of epoxy resin (b1) containing aminocompound (b3).
Xylene formaldehyde resin (b2) and usually in the solvent be applicable to, 1 ~ 6 hour, preferably 1 ~ 5 hour can be carried out at the temperature of 80 ~ 170 DEG C, preferably 90 ~ 150 DEG C containing the addition reaction to epoxy resin (b1) of aminocompound (b3).As above-mentioned applicable solvent, known organic solvent can be enumerated, such as: the hydrocarbon system of toluene, dimethylbenzene, hexanaphthene, normal hexane etc.; The ester system of methyl acetate, ethyl acetate, butylacetate etc.; The ketone system of acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), Methyl amyl ketone etc.; The acid amides system of dimethyl formamide, N,N-DIMETHYLACETAMIDE etc.; The alcohol system of methyl alcohol, ethanol, n-propyl alcohol, Virahol etc.; The aromatic alkyl alcohols of phenyl methanol, methyl phenyl carbinol etc.; The ether alcohol based compound of ethylene glycol monobutyl ether, diethylene glycol monoethyl ether etc. or their mixture etc.
The usage ratio of each reacted constituent in above-mentioned addition reaction does not have considered critical, can, according to appropriate changes such as the purposes of coating composition, be that benchmark is preferably in following scope with the total mass that epoxy resin (b1), xylene formaldehyde resin (b2) and the solid containing 3 kinds of compositions of aminocompound (b3) divide.
Epoxy resin (b1) is 50 ~ 90 quality %, is preferably 50 ~ 85 quality %, is more preferably 53 ~ 83 quality %, xylene formaldehyde resin (b2) is 5 ~ 45 quality %, is preferably 6 ~ 43 quality %, is more preferably 6 ~ 40 quality %, and is 5 ~ 25 quality % containing aminocompound (b3), is preferably 6 ~ 20 quality %, is more preferably 6 ~ 18 quality %.
< end-blocking polyisocyanate curing agent (C) >
By being combined containing aminoepoxy resin (B) with containing amino-modified epoxy resin (A) and xylene formaldehyde resin modification by end-blocking polyisocyanate curing agent (C), the cation electrodeposition coating of Thermocurable can be modulated.
The addition reaction product that end-blocking polyisocyanate curing agent (C) is polyisocyanate compound (c1) and end-capping reagent.As polyisocyanate compound (c1), known polyisocyanate compound can be used, such as can enumerate: tolylene diisocyanate, Xylene Diisocyanate, phenylene diisocyanate, ditan-2, 2 '-vulcabond, ditan-2, 4 '-vulcabond, ditan-4, 4 '-vulcabond, thick MDI [polymethylene multi-phenenyl isocyanate], two (isocyanatomethyl) hexanaphthene, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, the aromatic series of isophorone diisocyanate etc., aliphatics or alicyclic polyisocyanates compound, the cyclized polymer of these polyisocyanate compounds or biuret body, or their combination.
In order to non-corrosibility, the more preferably aromatic polyisocyanate of tolylene diisocyanate, Xylene Diisocyanate, phenylene diisocyanate, ditan-2,4 '-vulcabond, ditan-4,4 '-vulcabond, thick MDI etc.
On the other hand, above-mentioned end-capping reagent is that addition is in the isocyanate group of polyisocyanate compound, by the material of this isocyanate-terminatedization, and the end-blocking polyisocyanate compound to be generated by addition is stable at normal temperatures, but when wishing sintering temperature (usual 100 ~ 200 DEG C) being heated to film, end-capping reagent dissociation, can produce free isocyanate group again.
As the end-capping reagent used in end-blocking polyisocyanate curing agent (C), such as, can enumerate: the oxime compound of methyl ethyl ketoxime, cyclohexanone-oxime etc.; The phenol system compound of phenol, p-tert-butylphenol, cresols etc.; The aliphatics alcohols of propyl carbinol, 2-Ethylhexyl Alcohol etc.; The aromatic alkyl alcohols of phenyl methanol, methyl phenyl carbinol etc.; The ether alcohol based compound of ethylene glycol monobutyl ether, diethylene glycol monoethyl ether etc.; The lactan based compound etc. of ε-caprolactam, butyrolactam etc.
Good in order to obtain mechanical stability, and spreadability, electrodeposition coating suitability on alloy galvanized steel plate, finishability, the coated article of non-corrosibility excellence, cation electric deposition paint composition of the present invention is for containing amino-modified epoxy resin (A), xylene formaldehyde resin modification is containing aminoepoxy resin (B) and end-blocking polyisocyanate curing agent (C), the total mass of dividing with the solid of these materials is needed to contain 40 ~ 70 quality % (preferably 50 ~ 70 quality %) for benchmark, 1 ~ 40 quality % (preferably 2 ~ 30 quality %) and 10 ~ 40 quality % (preferably 15 ~ 35 quality %).If outside above-mentioned scope, sometimes damage any one in coating characteristic and coating property, therefore not preferred.
Cation electric deposition paint composition of the present invention can contain the various additive and organic solvent etc. of curing catalysts, tensio-active agent, surface conditioner etc. further.Above-mentioned curing catalysts is effective to promoting as the amine addition epoxy resin (A) of matrix resin, xylene formaldehyde resin modification containing the crosslinking reaction of aminoepoxy resin (B) and end-blocking polyisocyanate curing agent (C).
The manufacture method of cation electric deposition paint composition of the present invention is not particularly limited, such as, can manufacture by the following: aminoepoxy resin (B) will be contained containing amino-modified epoxy resin (A) and xylene formaldehyde resin modification, and tensio-active agent as required, surface conditioner, the various additive of the tin alkyl ester cpds of aromatic carboxylic acid etc. and organic solvent etc. be mixing fully, obtain resin compound, then, usually, with the above-mentioned blending resin in water-soluble organic carboxyl acid neutralized aqueous medium, by above-mentioned resin compound water-solubleization or moisture dispersion, obtain emulsion.It should be noted that, generally speaking the neutralization of above-mentioned resin compound can use known acid, but particularly preferably acetic acid, formic acid, lactic acid or their mixture.
In addition, as above-mentioned tensio-active agent, such as, can enumerate: the nonionic system tensio-active agent of the acetylenic glycol system, polyoxyethylene glycol system, polyvalent alcohol system etc. of hydrophile-lipophile balance value (HLB) in the scope of 8 ~ 18, preferably 10 ~ 15.
In addition, as above-mentioned organic solvent, such as, can enumerate: alcohol system, such as methyl alcohol, ethanol, propyl carbinol, Virahol, 2-Ethylhexyl Alcohol, benzylalcohol, ethylene glycol, propylene glycol; Ether system, such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol ether, ethylene glycol list-2-ethyl hexyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monophenyl ether, 3-methyl-3-methoxybutanol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; Ketone system, such as acetone, methyl iso-butyl ketone (MIBK), pimelinketone, isophorone, methyl ethyl diketone; Ester system, such as ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate or their mixture.
Cation electric deposition paint composition, carries out mixing manufacturing with the pigment dispersion paste manufactured in addition containing the emulsion of aminoepoxy resin (B) and end-blocking polyisocyanates (C) etc. containing aminoepoxy resin (A), xylene formaldehyde resin modification preferably by by being dispersed with.
Tinting pigment, rust-stabilising pigment and pigment extender etc. are dispersed in minuteness particle and obtain by above-mentioned pigment dispersion paste in advance, and such as can pass through to coordinate colo(u)rant dispersion resin, neutralizing agent and pigment class and bismuth compound as required, then by title complex is carried out dispersion treatment to modulate in the dispersing mixer of ball mill, sand mill, pebble mill etc.
As above-mentioned colo(u)rant dispersion resin, known colo(u)rant dispersion resin can be enumerated, such as, can enumerate: the resin with the matrix resin of hydroxyl and cationic groups, tensio-active agent etc. and tertiary amine-type, quaternary, tertiary sulfonium (tertiarysulfonium) salt form etc.The usage quantity of pigment dispersing agent preferably every 100 mass parts pigment in the scope of 1 ~ 150 mass parts, particularly preferably 10 ~ 100 mass parts.
Above-mentioned pigment is not particularly limited, such as, can enumerate: the tinting pigment of titanium oxide, carbon black, red iron oxide etc.; The pigment extender of clay, mica, barium oxide, calcium carbonate, silicon-dioxide etc.; The rust-stabilising pigment of phospho-molybdic acid aluminium, aluminium triphosphate, zinc oxide (zinc white) etc.
And then, by suppress corrosion or antirust for the purpose of, above-mentioned pigment dispersion paste can contain bismuth compound.As above-mentioned bismuth compound, such as, can enumerate: bismuth oxide, bismuth hydroxide, alkaline carbonic acid bismuth, Bismuth trinitrate, bismuth silicate and organic acid bismuth etc.
In addition, rise to object with solidified nature, the organo-tin compound of di-n-octyltin oxide, dibutyltin oxide etc. can be added in above-mentioned pigment dispersion paste.But, by adopting and/or increasing the rust-stabilising pigment of above-mentioned zinc oxide (zinc white) etc. and/or the amount of bismuth compound and carry out miniaturization (nanometer) as required, even if not containing above-mentioned organo-tin compound, the solidified nature of cation electric deposition paint composition of the present invention also can be improved.
The total use level of above-mentioned pigment composition and bismuth compound and/or organo-tin compound, preferably every 100 mass parts are divided, in the scope of 1 ~ 100 mass parts, particularly preferably 10 ~ 50 mass parts containing the total solid of aminoepoxy resin (B) and end-blocking polyisocyanate curing agent (C) containing amino-modified epoxy resin (A), xylene formaldehyde resin modification.
As the coated article of cation electric deposition paint composition of the present invention, as long as metal is just not particularly limited, such as, can enumerate: the metal foil used in body of a motor car, two wheeler parts, home-use equipment, miscellaneous equipment etc.
As above-mentioned metal foil, can enumerate: cold-rolled steel sheet, alloy galvanized steel plate, electrogalvanizing steel plate, zinc-iron double-layer electroplating steel plate, organic composite plated steel sheet, Al starting material, Mg starting material and these metal sheets are cleaned as required alkali degreasing etc. surface after carry out phosphatization and become the surface treatments such as process, chromic salt process and the plate that obtains.
Cation electric deposition paint composition of the present invention can be coated with by electrodeposition coating and be contained in desired metallic surface.Generally speaking electrodeposition coating can carry out as follows: carrying out with deionized water etc. diluting, solid point concentration is adjusted to 5 ~ 40 quality %, is adjusted to by pH in the scope of 5.5 ~ 9.0 and is adjusted in the electrodeposition bath be made up of electrodeposition coating composition of 15 ~ 35 DEG C by bath temperature, under the condition of load voltage 100 ~ 400V, using coated article as cathodal closing.After electrodeposition coating, usually, in order to make the cation electrodeposition coating of unnecessary attachment come off, the article of electrodeposition coating are fully washed through water (RO water), process water, pure water etc. with ultrafiltrated (UF filtrate), reverse osmosis.The thickness of the film of electrodeposition coating is not particularly limited, and generally speaking, based on dry coating, can be set in 5 ~ 40 μm, preferably in the scope of 12 ~ 30 μm.
In addition, the sintering drying of the film of electrodeposition coating is carried out as follows: the drying plant using electric hot-air drying machine, gas and hot air drying machine etc., with the temperature on painting object surface be 110 DEG C ~ mode of 200 DEG C, preferably 140 ~ 180 DEG C heats electrodeposition coating 10 minutes ~ 180 minutes, preferably 20 minute ~ 50 minutes.Dry by above-mentioned sintering, the curing of coating of galvanic deposit can be made.
It should be noted that, cation electric deposition paint composition of the present invention forms the cured coating film of electrodeposition coating suitability, finishability and non-corrosibility excellence on spreadability, alloy galvanized steel plate, such as, be useful as the coating in body of a motor car, trolley part, family's electrical article, building materials and steel structure etc.
Embodiment
Below, enumerate embodiment to be described in more detail the present invention.The present invention is not limited thereto.It should be noted that, " part " and " % " represents " mass parts " and " quality % " respectively.
The manufacture of [Production Example 1] substrate resin solution No.1
In jER828EL (ジ ャ パ Application エ Port キ シ レ ジ Application Inc., trade(brand)name, epoxy resin, epoxy equivalent (weight) 190, molecular weight 350) add dihydroxyphenyl propane 400 parts and Tetrabutyl amonium bromide 0.5 part in 1000 parts, at 160 DEG C, make it react reach 800 to epoxy equivalent (weight), obtain product a
1.Then, at product a
1in add soya fatty acid (acid number 200mgKOH/g) 170 parts and Tetrabutyl amonium bromide 0.5 part, at 140 DEG C, make it react reach 1370 to epoxy equivalent (weight), obtain product a
2.
It should be noted that, soya fatty acid and jER828EL are coordinated with the ratio that the equivalence ratio of [carboxyl in soya fatty acid]/[epoxy group(ing) in epoxy resin] is 0.34, makes it react.
Then, at product a
2in add the ketoimine compound 95 parts (effective constituent 84%) of ethylene glycol monobutyl ether 210 parts, diethanolamine 80 parts and diethylenetriamine, after making it react 4 hours at 120 DEG C, add methyl iso-butyl ketone (MIBK) 145 parts, obtain containing amino-modified epoxy resin (A) the i.e. substrate resin solution No.1 of resin solids 80 quality %.Substrate resin solution No.1 has the amine value of 45mgKOH/g and the number-average molecular weight of 1900.
The manufacture of [Production Example 2] substrate resin solution No.2
In jER828EL (ジ ャ パ Application エ Port キ シ レ ジ Application Inc., trade(brand)name, epoxy resin, epoxy equivalent (weight) 190, molecular weight 350) add dihydroxyphenyl propane 400 parts and Tetrabutyl amonium bromide 0.5 part in 1000 parts, at 160 DEG C, make it react reach 800 to epoxy equivalent (weight), obtain product b
1.Then, at product b
1in add coco-nut oil fatty acid (acid number 267mgKOH/g) 125 parts and Tetrabutyl amonium bromide 0.5 part, at 140 DEG C, make it react reach 1300 to epoxy equivalent (weight), obtain product b
2.
It should be noted that, coco-nut oil fatty acid and jER828EL are coordinated with the ratio that the equivalence ratio of [carboxyl in coco-nut oil fatty acid (monocarboxylic acid)]/[epoxy group(ing) in epoxy resin] is 0.34, makes it react.
Then, at product b
2in add the ketoimine compound 95 parts (effective constituent 84%) of ethylene glycol monobutyl ether 200 parts, diethanolamine 80 parts and diethylenetriamine, after making it react 4 hours at 120 DEG C, add methyl iso-butyl ketone (MIBK) 145 parts, what obtain resin solids 80 quality % contains amino-modified epoxy resin and substrate resin solution No.2.Substrate resin solution No.2 has the amine value of 46mgKOH/g and the number-average molecular weight of 1900.
The manufacture of [Production Example 3] substrate resin solution No.3
In jER828EL (ジ ャ パ Application エ Port キ シ レ ジ Application Inc., trade(brand)name, epoxy resin, epoxy equivalent (weight) 190, molecular weight 350) add dihydroxyphenyl propane 400 parts and Tetrabutyl amonium bromide 0.5 part in 1000 parts, at 160 DEG C, make it react reach 800 to epoxy equivalent (weight), obtain product c
1.Then, at product c
1in add Castor Oil Fatty Acid (acid number 190mgKOH/g) 150 parts and Tetrabutyl amonium bromide 0.5 part, at 140 DEG C, make it react reach 1240 to epoxy equivalent (weight), obtain product c
2.
It should be noted that, Castor Oil Fatty Acid and jER828EL are coordinated with the ratio that the equivalence ratio of [carboxyl in Castor Oil Fatty Acid]/[epoxy group(ing) in epoxy resin] is 0.29, makes it react.
Then, at product c
2in add the ketoimine compound 95 parts (effective constituent 84%) of ethylene glycol monobutyl ether 200 parts, diethanolamine 90 parts and diethylenetriamine, after making it react 4 hours at 120 DEG C, add methyl iso-butyl ketone (MIBK) 155 parts, what obtain resin solids 80 quality % contains amino-modified epoxy resin and substrate resin solution No.3.Substrate resin solution No.3 has the amine value of 49mgKOH/g and the number-average molecular weight of 2000.
The manufacture of [Production Example 4] substrate resin solution No.4
In the removable flask of internal volume 2 liters possessing thermometer, reflux cooler and stirrer, add 50% formalin 480 parts, phenol 110 parts, 98% commercial sulphuric acid 202 parts and m-xylene 424 parts, at 84 ~ 88 DEG C, make it react 4 hours.After reaction terminates, leave standstill, the xylene solution being dissolved with resin-phase is separated with aqueous sulfuric acid phase, wash resin-phase with water 3 times, then process 20 minutes under the condition of 20 ~ 30mmHg/120 ~ 130 DEG C, distillation removing unreacted m-xylene, obtains the phenol-modified xylene formaldehyde resin 480 parts of viscosity 1050mPas (25 DEG C).
JER828EL (ジ ャ パ Application エ Port キ シ レ ジ Application Inc. is filled in other flask, trade(brand)name, epoxy resin, epoxy equivalent (weight) 190, molecular weight 350) 1000 parts, dihydroxyphenyl propane 400 parts and dimethyl benzylamine 0.2 part, make it react to epoxy equivalent (weight) at 130 DEG C and reach 750.
Then, the ketoimine compound 95 parts (effective constituent 84%) of above-mentioned phenol-modified xylene formaldehyde resin 300 parts, diethanolamine 137 parts and diethylenetriamine is added in above-mentioned other flask, at 120 DEG C, make it react 4 hours, then add ethylene glycol monobutyl ether 250 parts, methyl iso-butyl ketone (MIBK) 153 parts further, obtain the xylene formaldehyde resin modification of resin solids 80 quality % containing aminoepoxy resin and substrate resin solution No.4.Substrate resin solution No.4 has the amine value of 57mgKOH/g and the number-average molecular weight of 2000.
The manufacture of [Production Example 5] substrate resin solution No.5
In the removable flask of internal volume 2 liters possessing thermometer, reflux cooler and stirrer, filling jER828EL, (ジ ャ パ Application エ Port キ シ レ ジ Application (strain) makes, trade(brand)name, epoxy resin) 1010 parts, dihydroxyphenyl propane 390 parts and dimethyl benzylamine 0.2 part, make it react to epoxy equivalent (weight) at 130 DEG C and reach 800.Then, the ketoimine compound 95 parts (effective constituent 84%) of diethanolamine 147 parts and diethylenetriamine is added in above-mentioned flask, at 120 DEG C, make it react 4 hours, then add ethylene glycol monobutyl ether 200 parts, methyl iso-butyl ketone (MIBK) 155 parts, obtain the substrate resin solution No.5 of resin solids 80 quality %.Substrate resin solution No.5 has the amine value of 71mgKOH/g and the number-average molecular weight of 2000.
The manufacture of [Production Example 6] curing agent solution No.1
In reaction vessel, fill コ ス モ ネ ー ト M-200 (trade(brand)name, Mitsui Chemicals, Inc.'s system, thick MDI) 270 parts and methyl iso-butyl ketone (MIBK) 130 parts, be warming up to 70 DEG C.Dripped ethylene glycol monobutyl ether 240 parts to above-mentioned reaction vessel with 1 hour, be then warming up to 100 DEG C, keep.Through time sampling, measured by infrared absorption spectrum and confirm not have the absorption of unreacted isocyanate group, obtain the curing agent solution No.1 that solid is divided into 80%.
The manufacture of [Production Example 7] curing agent solution No.2
In reaction vessel, fill isophorone diisocyanate 222 parts and methyl iso-butyl ketone (MIBK) 100 parts, be warming up to 50 DEG C.Slowly add methyl ethyl ketoxime 174 parts wherein, be then warming up to 60 DEG C.Keep this temperature, simultaneously through time sampling, measured the absorption confirming not have unreacted isocyanic ester by infrared absorption spectrum, obtain the curing agent solution No.2 that solid is divided into 80%.
The manufacture > of < emulsion
The manufacture of [Production Example 8] emulsion No.1
By the substrate resin solution No.162.5 part (solid divides 50 parts) obtained by Production Example 1, the substrate resin solution No.425.0 part (solid divides 20 parts) obtained by Production Example 4, the curing agent solution No.137.5 part (solid divides 30 parts) obtained by Production Example 6 and 10% acetic acid, 13 parts of uniform stirrings, generate mixture.Then in said mixture on one side violent stirring, on one side with about 15 minutes dropping deionized waters 156.0 parts, obtain emulsion No.1.
The manufacture of [Production Example 9 ~ 17] emulsion No.2 ~ No.10
Except the cooperation being set as following table 1, all the other are same with Production Example 8, obtain emulsion No.2 ~ No.10.
[table 1]
Numeral solid in () divides.
The manufacture of [Production Example 18] colo(u)rant dispersion resin
In jER828EL (ジ ャ パ Application エ Port キ シ レ ジ Application Co., Ltd. system, trade(brand)name, epoxy resin) add dihydroxyphenyl propane 390 parts, プ ラ Network セ Le 212 (polycaprolactone glycol in 1010 parts, ダ イ セ Le chemical industry Co., Ltd., trade(brand)name, weight-average molecular weight about 1250) 240 parts and dimethyl benzylamine 0.2 part, at 130 DEG C, make it react reach about 1090 to epoxy equivalent (weight), obtain product d
1.
Then, at product d
1in add the lactic acid aqueous solution 150 parts of dimethylethanolamine 134 parts and concentration 90%, make it react 4 hours at 120 DEG C, then add methyl iso-butyl ketone (MIBK), adjustment solid divides, and obtains the colo(u)rant dispersion resin that solid divides the ammonium salt type resin system of 60%.The colo(u)rant dispersion resin of ammonium salt type resin system has ammonium salt concentration 0.78mmol/g.
The manufacture of [Production Example 19] pigment dispersion paste No.1
The solid obtained by Production Example 18 is divided the colo(u)rant dispersion resin 8.3 parts (solid divides 5 parts) of 60%, titanium oxide 14.5 parts, refining clay 7.0 parts, carbon black 0.3 part, di-n-octyltin oxide 1 part, bismuth hydroxide 1 part and deionized water 20.3 parts mixing, disperse 20 minutes with ball mill, obtain the pigment dispersion paste No.1 that solid divides 55%.
The manufacture > of < cation electrodeposition coating
[embodiment 1]
By emulsion No.1294 part (solid divides 100 parts), 55% pigment dispersion paste No.152.4 part (solid divides 28.8 parts) and deionized water 297.6 parts mixing, manufacture solid divide 20% cation electrodeposition coating No.1.
[embodiment 2 ~ 6]
Except being set as the cooperation shown in following table 2, all the other manufacture cation electrodeposition coating No.2 ~ No.6 similarly to Example 1.
[table 2]
Numeral solid in () divides.
[comparative example 1 ~ 4]
Except being set as the cooperation shown in following table 3, all the other manufacture cation electrodeposition coating No.7 ~ No.10 similarly to Example 1.
[table 3]
Numeral solid in () divides.
making of test board:
By each cation electrodeposition coating electrodeposition coating obtained by embodiment and comparative example is changed into process (パ Le バ Application De #3020 (Japanese PARKERIZING Inc. implementing, trade(brand)name, zinc phosphate treatment agent)) cold-rolled steel sheet (0.8mm × 150mm × 70mm) or implement on the same alloy galvanized steel plate (0.8mm × 150mm × 70mm) changing into process, make test board.The test board obtained is tested according to following evaluation method.Result is shown in table 4 and table 5.
Table 4
Table 5
(note 1) spreadability: use the ボ ッ Network ス method cover butter fixture 1 of 4 shown in Fig. 1 to evaluate.In 4 ボ ッ Network ス method spreadability test fixtures 1,4 steel plates (10cm × 15cm) are configured with 2cm interval, in 4 steel plates, the steel plate of the leftmost side, the 2nd steel plate and the 3rd steel plate has the circular port 2 of diameter 8cm respectively from the left side from the left side.In addition, the face towards left side of the steel plate of the leftmost side is set as " A face ", is set as in " B face " towards the face on right side.Equally, the face of the left and right from left 2nd steel plate is set as in " C face " and " D face " respectively, the face of the left and right from left 3rd steel plate is set as in " E face " and " F face " respectively, the face of the left and right of the steel plate of the rightmost side is set as respectively " G face " and " H face ".Wherein, A face is set as " outside plate ", G face is set as " inner panel ".
Then, in the electrocoating paint bath 4 shown in Fig. 2, use the cover butter device 3 containing 4 ボ ッ Network ス method cover butter fixtures 1, power supply and opposite electrodes 5, in the temperature 30 DEG C of electrocoating paint bath 4, the interpole gap 10cm of A face and opposite electrode 5,3 minutes conduction time, carry out electrodeposition coating with the voltage that the solidification thickness of outside plate is 15 μm.Spreadability is evaluated with the solidification thickness of the solidification thick film of outside plate, inner panel and spreadability (%) (solidification thickness × 100 of the solidification thickness/outside plate of=inner panel).
The electrodeposition coating suitability of (note 2) alloy galvanized steel plate: will with パ Le ボ Application De #3020 (Japanese パ ー カ ラ イ ジ Application グ Inc., trade(brand)name, zinc phosphate treatment agent) alloy galvanized steel plate that carries out changing into 0.8 × 150 × 70mm the processed negative electrode of bathing as electrocoating paint and flooding, the interpole gap of steel plate and electrode is 10cm, in addition, under the condition identical with spreadability, electrodeposition coating is carried out.The film obtained is sintered 20 minutes at 170 DEG C, makes it solidify, count the pinhole number (test face: 150mm × 70mm) of the test specimen after sintering.
For each evaluation, be expressed as:
◎: do not have pin hole
Zero: little pin hole (ガ ス ヘ コ) is 1 (degree that in using, film can be sheltered)
△: pin hole is 2 ~ 9
×: pin hole is more than 10.
(note 3) finishability: carry out application under the condition identical with above-mentioned electrodeposition coating suitability, obtains the coated plate solidifying thickness 15 μm.Be benchmark with JISB0651 by the surface roughness of above-mentioned coated plate, use サ ー Off テ ス ト 301 (Co., Ltd. ミ Star ト ヨ Inc., trade(brand)name, surface roughness measurement machine) to evaluate as center line average roughness (Ra) value.
For each evaluation, be expressed as:
◎: Ra value is less than 0.23 μm
Zero: Ra value is more than 0.23 and is less than 0.30 μm
△: Ra value is more than 0.30 and is less than 0.40 μm
×: Ra value is more than 0.40 μm.
(note 4) non-corrosibility: carry out application under the condition that the electrodeposition coating suitability with above-mentioned alloy galvanized steel plate is identical, obtains the test board solidifying thickness 20 μm.Then, to the film on above-mentioned test board, carry out crosscut with the mode cutters arriving the substrate of test board and cut, based on JISZ-2371, carry out 840 hours 35 DEG C of salt-fog tests, evaluate the amplitude of rust from cutting part or protuberance.
For each evaluation, the maximum amplitude of rust or protuberance is expressed as follows:
◎: from cutting part to side below 2.5mm
Zero: from cutting part to side more than 2.5mm and be below 3.0mm
△: from cutting part to side more than 3.0mm and be below 3.5mm
×: from cutting part to side more than 3.5mm
(note 5) mechanical stability: evaluated by the UF device shown in Fig. 3.UF device 6 shown in Fig. 4 possesses circulation engine 7, circulation engine 8, UF film 9 and tubing.In addition, the arrow in Fig. 4 represents the flow direction of cation electrodeposition coating.And then symbol 10,11 and 12 represents the discharge pipe arrangement of the supply pipe arrangement of electrocoating paint, the discharge pipe arrangement of separated coating and separated filtrate respectively.In the present embodiment, as UF film 9, use the UF film NTU-212 (Dong electrician Inc., trade(brand)name, UF film) of laboratory experiment.
After cation electrodeposition coating is circulated 25 minutes, and then make the circulation of cation electrodeposition coating close 5 minutes, シ ェ ア is applied to UF film, measures the transit dose of filtrate.Then, with the cation electrodeposition coating after this mensuration, the cold-rolled steel sheet (horizontal part 5 × 5cm, vertical component effect 5 × 5cm, change into process) of L-shaped is carried out electrodeposition coating and reaches 20 μm to make the dry film thickness of horizontal part.Then, the film obtained is sintered 20 minutes at 170 DEG C, makes it solidify, count the number of " upspringing ", " depression " and " pit " of the test board horizontal part after sintering.
For each evaluation, be expressed as:
◎: do not upspring, cave in and pit
Zero: little depression is 1 (degree that in using, film can be sheltered)
△: upspring, cave in and pit add up to 2 ~ 9
×: upspring, cave in, pit add up to more than 10.
Utilizability in industry
The present invention can provide the coated article of electrodeposition coating suitability, finishability and non-corrosibility excellence on spreadability, alloy galvanized steel plate.
Claims (1)
1. a cation electric deposition paint composition, is characterized in that, it is the cation electric deposition paint composition containing following composition:
Make, in the monocarboxylic acid of carbon number more than 8 (a1), 1 molecule, there are more than 2 epoxy group(ing) and epoxy equivalent (weight) be 300 ~ 2500 epoxy resin (a2) and containing aminocompound (a3) reaction generates contain amino-modified epoxy resin (A);
Make epoxy equivalent (weight) be 180 ~ 2500 epoxy resin (b1), have phenolic hydroxyl group xylene formaldehyde resin (b2) and react containing aminocompound (b3) the xylene formaldehyde resin modification that generates and contains aminoepoxy resin (B); And
End-blocking polyisocyanate curing agent (C);
The total mass of dividing with their solid is benchmark, what contain 40 ~ 70 quality %, 1 ~ 40 quality % and 10 ~ 40 quality % respectively contains aminoepoxy resin (B) and end-blocking polyisocyanate curing agent (C) containing amino-modified epoxy resin (A), xylene formaldehyde resin modification
The monocarboxylic acid (a1) of described carbon number more than 8, for being selected from drying oil fatty acid, the monocarboxylic acid of at least a kind of carbon number more than 8 of semi-drying oil lipid acid, described drying oil fatty acid, semi-drying oil lipid acid is by being selected from by fish oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid, linseed fatty acid, soya fatty acid, sesame oil lipid acid, tori seed oil lipid acid, perilla oil lipid acid, hempseed oil lipid acid, rapeseed oil fatty acid, corn oil fatty acid, ready denier oil acid, Trisun Oil R 80 lipid acid, continuous seed oil fatty acid, walnut oil fat acid, and at least a kind of natural fats and oils in the group of coco-nut oil fatty acid composition obtained,
Described is the resin making to generate containing aminocompound (a3) and modified epoxy (A1) react containing amino-modified epoxy resin (A), described modified epoxy (A1) is generated by monocarboxylic acid (a1) and epoxy resin (a2) reaction
Described modified epoxy (A1) is that the ratio making monocarboxylic acid (a1) and epoxy resin (a2) reach 0.05 ~ 0.5 with the equivalence ratio of [carboxyl in monocarboxylic acid (a1)]/[epoxy group(ing) in epoxy resin (a2)] carries out reacting and the resin obtained.
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| JP2009-091977 | 2009-04-06 | ||
| JP2010022271A JP5610785B2 (en) | 2009-04-06 | 2010-02-03 | Cationic electrodeposition coating composition |
| JP2010-022271 | 2010-02-03 | ||
| CN2010101544974A CN101928505A (en) | 2009-04-06 | 2010-04-02 | Cation electro-deposition coating composition |
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| JP6012744B2 (en) * | 2012-10-02 | 2016-10-25 | 関西ペイント株式会社 | Cationic electrodeposition coating composition |
| EP2727968A1 (en) * | 2012-11-06 | 2014-05-07 | ALLNEX AUSTRIA GmbH | Multifunctional primary amine, process for its preparation, and use thereof |
| JP6026909B2 (en) * | 2013-02-08 | 2016-11-16 | 関西ペイント株式会社 | Cationic electrodeposition coating composition |
| EP2774957A1 (en) | 2013-03-06 | 2014-09-10 | ALLNEX AUSTRIA GmbH | Cationic Paint Additives |
| KR101858272B1 (en) * | 2013-05-16 | 2018-05-15 | 주식회사 케이씨씨 | Method for preparing urethane curing agent for electrodeposition paint, a cationic resin composition for electrodeposition paint and an electrodeposition paint composition comprising the same |
| WO2017038631A1 (en) * | 2015-09-04 | 2017-03-09 | 日本パーカライジング株式会社 | Amine-modified epoxy resin and cationic electrodeposition coating composition |
| WO2017117169A1 (en) | 2015-12-31 | 2017-07-06 | Henkel Ag & Co. Kgaa | Low bake autodeposition coatings |
| US11840598B2 (en) | 2019-08-27 | 2023-12-12 | Mitsubishi Gas Chemical Company, Inc. | Urethane resin |
| CN110791176A (en) * | 2019-11-13 | 2020-02-14 | 立邦涂料（中国）有限公司 | Cation electrophoretic paint main body resin and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0398756A2 (en) * | 1989-05-18 | 1990-11-22 | Nissan Motor Co., Ltd. | Composite paint film arrangement |
| CN1058054A (en) * | 1990-06-06 | 1992-01-22 | 巴斯福拉克和法本股份公司 | The method of coating electrically conductive matrix, water-based paint and contain the linking agent of masked isocyanate group |
| CN1346859A (en) * | 2000-10-11 | 2002-05-01 | 关西油漆株式会社 | Cationic paint composition |
| CN101386768A (en) * | 2007-09-11 | 2009-03-18 | 关西涂料株式会社 | Cationic electrodeposition paint compositions |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07126557A (en) * | 1993-11-05 | 1995-05-16 | Nippon Paint Co Ltd | Resin for improving surface smoothness of cationic electrodeposition coating material |
| JP3469868B2 (en) * | 2000-11-28 | 2003-11-25 | 関西ペイント株式会社 | Cationic paint composition |
| JP2002201408A (en) * | 2000-12-28 | 2002-07-19 | Nippon Paint Co Ltd | Aqueous coating resin, manufacturing method therefor and aqueous coating composition |
| JP3843250B2 (en) * | 2001-11-22 | 2006-11-08 | 関西ペイント株式会社 | Cationic coating composition |
| JP5342135B2 (en) * | 2006-12-07 | 2013-11-13 | 関西ペイント株式会社 | Cationic electrodeposition coating composition and articles coated with the electrodeposition coating |
| JP2008222751A (en) * | 2007-03-09 | 2008-09-25 | Kansai Paint Co Ltd | Cationic electrodeposition coating composition |
| JP2008308591A (en) * | 2007-06-15 | 2008-12-25 | Kansai Paint Co Ltd | Cationic electrodeposition coating composition |
-
2010
- 2010-02-03 JP JP2010022271A patent/JP5610785B2/en active Active
- 2010-04-02 CN CN2010101544974A patent/CN101928505A/en active Pending
- 2010-04-02 CN CN201510573638.9A patent/CN105038516A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0398756A2 (en) * | 1989-05-18 | 1990-11-22 | Nissan Motor Co., Ltd. | Composite paint film arrangement |
| CN1058054A (en) * | 1990-06-06 | 1992-01-22 | 巴斯福拉克和法本股份公司 | The method of coating electrically conductive matrix, water-based paint and contain the linking agent of masked isocyanate group |
| CN1346859A (en) * | 2000-10-11 | 2002-05-01 | 关西油漆株式会社 | Cationic paint composition |
| CN101386768A (en) * | 2007-09-11 | 2009-03-18 | 关西涂料株式会社 | Cationic electrodeposition paint compositions |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111621211A (en) * | 2019-02-28 | 2020-09-04 | 中国涂料株式会社 | Anticorrosive coating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010261011A (en) | 2010-11-18 |
| CN101928505A (en) | 2010-12-29 |
| JP5610785B2 (en) | 2014-10-22 |
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