CN103319976A - Thick-film high-antiseptic cathode electrophoretic coating - Google Patents
Thick-film high-antiseptic cathode electrophoretic coating Download PDFInfo
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Abstract
The invention relates to a thick-film high-antiseptic cathode electrophoretic coating which comprises an emulsion, the solid content of the emulsion is 30-35%, the PH value is 5.0-7.0, and the conductivity is 1000-2000 microseconds/cm; the solid content comprises the following components by mass percent for the total solid content: 30-70% of matrix resin, 20-40% of a curing agent, 0.1-10% of a filming auxiliary agent, 0.5-1.5% of a cosolvent, 20-50% of an antiseptic inhibitor, and the balance of an organic acid and deionized water; the matrix resin is an aminated modified epoxy resin capable of forming an ionic salt group with the organic acid; the filming auxiliary agent is a polyether at least containing three ether bonds on each molecule and does not contain any hydroxy after alkylation modification. After being coated with a film, the coating has a thickness within 35-40 micrometers, and has the advantages of large filming thickness and high edge coverage; the cation microgel with a high crosslinking density can greatly improve the phenomenon that edge shrinkage occurs in the coating curing process, thereby increasing the coating coverage of work piece edges, and especially improving the antiseptic performance of sharp edge parts of sharp workpieces.
Description
[technical field]
The present invention relates to the high anticorrosion cathode electrophoresis dope of thick-film type, a kind of specifically have higher thickness and a good anticorrosion cathode electrophoresis dope of anti-edge corrosion performance.
[background technology]
Since 20 century 70s, cathode electrophoresis dope is because the superiority of self has obtained more and more widely application in all conglomeraties especially automobile industry.As everyone knows, cathode electrophoresis dope is in the high bake solidification process, and the flowability of filming strengthens gradually, can produce the contraction of filming in the crosslinking curing process, cause the edge particularly the sharp edge position be coated with lepthymenia, thereby the non-corrosibility that causes these positions descends.Because the singularity of automobile commodity, automobile production manufacturer has higher requirement to the antiseptic property of body of a motor car and various parts.In order to improve the antiseptic property of electrophoretic paint, the edges cover rate that electrophoretic paint is filmed improves emphatically from suppressing to film contractions in many coating material production producer, thus the antiseptic property of raising coating; On the other hand, effectively increasing the thickness of filming also is one of effective ways that improve the whole antiseptic property of coating.
[summary of the invention]
The invention discloses the preparation method of the high anticorrosion cathode electrophoresis dope of a kind of thick-film type, specifically a kind of preparation method that can form the high anticorrosion cathode electrophoresis dope of higher thickness and edges cover rate.
Invent to achieve these goals the high anticorrosion cathode electrophoresis dope of a kind of thick-film type, comprise emulsion, it is characterized in that emulsion solids part content: 30%～35%, pH value: 5.0～7.0, specific conductivity 1000～2000 μ s/cm, wherein solid part is by the matrix resin that accounts for solid part total mass 30%～60%, 15%～40% solidifying agent, 0.1%～10% film coalescence aid, 0.5%～1.5% solubility promoter, 15%～50% anticorrosion inhibitor forms, all the other are organic acid and deionized water, described matrix resin refers to contain the amination modifying Resins, epoxy that can form with organic acid the ion salt group, and film coalescence aid refers to contain at least on each molecule three ehter bonds, and the polyethers that behind alkylation modification, does not contain any hydroxyl.
Also comprise mill base, emulsion and mill base quality are pressed 1:3～1:8 and are mixed.The mill base amount of solid content is 50%～60%, and solid part is comprised of the grind resin that accounts for solid part total mass 15～50%, 15～35% pigment, 20～50% filler, 0.5～3% dispersing auxiliary, 0.5%～1.5% solubility promoter, and all the other are deionized water.
Matrix resin refers to contain the amination modifying Resins, epoxy that can form with organic acid the ion salt group, it is normally take small molecules Resins, epoxy and chainextender as raw material, obtain first the macromole Resins, epoxy of epoxy equivalent (weight) between 1000-3000 by polymerization progressively, and then carry out ring-opening reaction with organic amine compound and obtain amination modifying Resins, epoxy, the synthetic method of this type resin discloses in European patent EP 0206071 and US Patent No. 4420574.Employed Resins, epoxy typically refers to and contains two 1 on each molecule in the building-up process, the aliphatics of 2-epoxide group, alicyclic, aromatic series or heterogeneous ring compound, the epoxy equivalent (weight) of described Resins, epoxy is between 50-600, specially suitable Resins, epoxy includes but not limited to, any one in bisphenol A type epoxy resin, bisphenol-s epoxy resin, bisphenol f type epoxy resin, polyethyleneglycol diglycidylether and the polypropylene glycol diglycidyl ether or any two kinds and two or more mixtures; Chainextender is poly carboxylic acid, polyvalent alcohol, polynary mercapto alcohol, polyphenol and the amine with two or more active hydrogens, the molecular weight of described chainextender is between 50-3000, specially suitable chainextender includes but not limited to, any one in di-carboxylic acid, dibasic alcohol, the pure and mild dihydric phenolic compounds of binary mercapto or any two kinds and two or more mixtures; Organic amine compound is to have the secondary amine compound of the protected primary amino by forming ketoimine and have HNR
3R
4In the structural formula compound any one or any two kinds and two or more mixtures, wherein R
3And R
4Can be identical group, also can be different groups, R
3And R
4Group is that carbon atom is any one in alkyl, hydroxyl alkyl and the hydroxyl alkylene of 2-12.In and the employed organic acid of amination modified epoxy be any one or any two kinds and two or more mixtures in the aliphatics that contains 1-20 carbon atom, alicyclic, aromatic series or the heterocycle monoprotic acid.
Solidifying agent refers to totally-enclosed isocyanate crosslinking, and it normally take polyisocyanates and the compound that contains reactive hydrogen as raw material, seals the NCO group under catalyst action.Employed polyisocyanates is the compound that contains two or more isocyanate group in the molecule in the solidifying agent building-up process, specially suitable polyisocyanates includes but not limited to, any one in aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, fat-aromatic diisocyanate, triisocyanate, tetraisocyanate and the polymeric polyisocyanate or any two kinds and two or more mixtures; Contain the compound of reactive hydrogen for generally containing alcohol, amine, carboxylic acid, oxime and the cyclic amide of 1-20 carbon atom, the specially suitable compound that contains reactive hydrogen includes but not limited to, any one in methyl alcohol, ethanol, propyl alcohol, hexalin, phenol, p-cresol, xylenol, chlorophenol, xylidine, aniline, n-Butyl Amine 99, Di-n-Butyl Amine, formic acid, acetic acid, propionic acid, sad, stearic acid, formyl amidoxime, acetoxime, methyl ethyl ketoxime, hexanolactam and the pyrrolidone or any two kinds and two or more mixtures; Catalyzer is the organic compound of the metals such as stanniferous, bismuth and zirconium, the specially suitable compound that contains reactive hydrogen includes but not limited to, a kind of or any two kinds and two or more mixtures in Dibutyltin oxide, dibutyl tin laurate, stannous octoate, bismuth lactate, Bismuth Octoate, the methyl ethyl diketone zirconium complex.
The polyethers that film coalescence aid refers to contain at least three ehter bonds on each molecule and do not contain any hydroxyl behind alkylation modification, this polyethers has following molecular structure: R
1O (CH
2CHR
2O)
nR
3, n 〉=2 wherein, R
2Be hydrogen atom or methyl, R
1And R
3It can be identical alkyl or aryl, it also can be different alkyl or aryls, specially suitable polyethers includes but not limited to, a kind of or any two kinds and two or more mixtures in tetraethylene-glycol two hexyl ethers, Triethylene glycol two hexyl ethers, tetraethylene-glycol dibenzyl ether, the Triethylene glycol dibenzyl ether.
Anticorrosion inhibitor refers to have the cationic microgel of high crosslink density.The preparation method of cationic microgel is described in " MicrogelSuspensions " book that the people such as Alberto write, and this patent is incorporated in their synthetic method and the application in electrophoretic paint thereof by reference into.
Grind resin refers to contain the Resins, epoxy of ion salt group, it is normally take small molecules Resins, epoxy and chainextender as raw material, obtain first the middle molecule epoxy resin of epoxy equivalent (weight) between 500-800 by polymerization progressively, and then and machine amine compound (or organo phosphorous compounds, organosulfur compound) join to have dissolved and carry out ion reaction in the organic acid deionized water.Employed Resins, epoxy typically refers to and contains two 1 on each molecule in the building-up process, the aliphatics of 2-epoxide group, alicyclic, aromatic series or heterogeneous ring compound, the epoxy equivalent (weight) of described Resins, epoxy is between 50-250, specially suitable Resins, epoxy includes but not limited to, any one in bisphenol A type epoxy resin, bisphenol-s epoxy resin, bisphenol f type epoxy resin, polyethyleneglycol diglycidylether and the polypropylene glycol diglycidyl ether or any two kinds and two or more mixtures; Chainextender is poly carboxylic acid, polyvalent alcohol, polynary mercapto alcohol, polyphenol and the amine with two or more active hydrogens, the molecular weight of described chainextender is between 50-250, specially suitable chainextender includes but not limited to, any one in di-carboxylic acid, dibasic alcohol, the pure and mild dihydric phenolic compounds of binary mercapto or any two kinds and two or more mixtures; Organic amine compound is to have the secondary amine compound of the protected primary amino by forming ketoimine and have HNR
3R
4In the structural formula compound any one or any two kinds and two or more mixtures, wherein R
3And R
4Can be identical group, also can be different groups, R
3And R
4Group is that carbon atom is any one in alkyl, hydroxyl alkyl and the hydroxyl alkylene of 2-12; Organo phosphorous compounds is for having PR
5R
6R
7In the structural formula compound any one or any two kinds and two or more mixtures, wherein R
5, R
6And R
7Can be identical group, also can be different groups, R
5, R
6And R
7Group is that carbon atom is any one in alkyl, hydroxyl alkyl and the hydroxyl alkylene of 2-12; Organosulfur compound is for having SR
8R
9In the structural formula compound any one or any two kinds and two or more mixtures, wherein R
8And R
9Can be identical group, also can be different groups, R
8And R
9Group is that carbon atom is any one in alkyl, hydroxyl alkyl and the hydroxyl alkylene of 2-12; Organic acid is any one or any two kinds and the two or more mixture in the aliphatics that contains 1-20 carbon atom, alicyclic, aromatic series or the heterocycle monoprotic acid.
Dispersing auxiliary refers to have the polymkeric substance of branched structure, and the preparation method of this polymkeric substance is described in US Patent No. 2002156230, and their synthetic method is incorporated this patent by reference into.
Solubility promoter refers to the high-boiling point alcohol ether solvent, specially suitable solubility promoter includes but not limited to, any one in ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the Diethylene Glycol monohexyl ether or any two kinds and two or more mixtures.
Beneficial effect of the present invention is:
1, the high anticorrosion cathode electrophoresis dope of thick-film type involved in the present invention has the high and high two kinds of advantages of edges cover rate of the thickness of filming, and has solved the shortcoming that conventional electrophoretic coating thickness and edges cover rate can not be taken into account;
2, the thickness of filming of the high anticorrosion cathode electrophoresis dope of thick-film type is higher than the thickness of conventional cathode electrophoresis dope far away at 35 μ m-40 μ m because the increase of thickness so that the antiseptic property of filming be improved;
3, the cationic microgel of high crosslink density can improve the cissing phenomenon that coating produces greatly in solidification process, thereby improves the fraction of coverage of edge of work coating, especially can improve the Corrosion Protection at sharp workpiece sharp edge position.
[embodiment]
In order to be easy to further understand the present invention, the following example has been set forth more specific details, but embodiments of the present invention are not limited to this.
The preparation of embodiment 1 matrix resin
* prepared according to mol ratio 1:2 reaction by diethylenetriamine and methyl iso-butyl ketone (MIBK), the solid content of final product is: 100%
In the reaction flask that thermometer, agitator and reflux condensing tube are housed, add successively 201 Resins, epoxy, dihydroxyphenyl propane and first part's methyl iso-butyl ketone (MIBK) of formula ratio.After reinforced complete, start stir and reaction system is warming up to 120 ℃ after insulation, after raw material dissolves fully and mixes, after adding triphenylphosphine temperature is risen to 150 ℃, and 2h is reacted in continuation under this temperature, when the reaction system epoxy equivalent (weight) reaches theoretical value (EEW=1140), stopped heating; When system temperature is down to below 90 ℃, N-Mono Methyl Ethanol Amine and ketoimine are joined in the reaction system, again be warming up to 120 ℃, under this temperature, continue reaction 2h; After reaction finishes reaction system is cooled to 70 ℃, adds the second section methyl iso-butyl ketone (MIBK), obtain final solid content and be 80.0% matrix resin.
The preparation of embodiment 2 matrix resins
* prepared according to mol ratio 1:2 reaction by diethylenetriamine and methyl iso-butyl ketone (MIBK), the solid content of final product is: 100%
In the reaction flask that thermometer, agitator and reflux condensing tube are housed, add successively 201 Resins, epoxy, dihydroxyphenyl propane and first part's methyl iso-butyl ketone (MIBK) of formula ratio.After reinforced complete, start stir and reaction system is warming up to 120 ℃ after insulation, after raw material dissolves fully and mixes, after adding triphenylphosphine temperature is risen to 150 ℃, and 3h is reacted in continuation under this temperature, when the reaction system epoxy equivalent (weight) reaches theoretical value (EEW=1600), stopped heating; When system temperature is down to below 90 ℃, N-Mono Methyl Ethanol Amine and ketoimine are joined in the reaction system, again be warming up to 120 ℃, under this temperature, continue reaction 2h; After reaction finishes reaction system is cooled to 70 ℃, adds the second section methyl iso-butyl ketone (MIBK), obtain final solid content and be 80.6% matrix resin.
The preparation of embodiment 3 totally-enclosed isocyanate crosslinkings
The tolylene diisocyanate and the Dibutyltin oxide that in the reaction flask that thermometer, agitator and reflux condensing tube are housed, add formula ratio, after being warming up to 70 ℃, stirring begins to drip methyl ethyl ketoxime, be no more than 75 ℃ with water-bath cooling and control temperature in the dropping process, dropwise rear continuation at 70 ℃ of lower reaction 2h, with residue isocyanato content in the standard Di-n-Butyl Amine back titration method analytical reaction system, when residue isocyanato content less than 0.5% the time, add methyl iso-butyl ketone (MIBK) and dilute, obtain final solid content and be 80% totally-enclosed isocyanate crosslinking.
The preparation of embodiment 4 totally-enclosed isocyanate crosslinkings
Thermometer is being housed, the hexamethylene diisocyanate trimer and the Dibutyltin oxide that add formula ratio in the reaction flask of agitator and reflux condensing tube, after being warming up to 80 ℃, stirring begins to drip ethylene glycol monobutyl ether, be no more than 85 ℃ with water-bath cooling and control temperature in the dropping process, dropwise rear continuation at 80 ℃ of lower reaction 4h, with residue isocyanato content in the standard Di-n-Butyl Amine back titration method analytical reaction system, when residue isocyanato content less than 0.5% the time, add methyl iso-butyl ketone (MIBK) and dilute, obtain final solid content and be 75% totally-enclosed isocyanate crosslinking.
The preparation of embodiment 5 totally-enclosed isocyanate crosslinkings
Thermometer is being housed, the tolylene diisocyanate that adds formula ratio in the reaction flask of agitator and reflux condensing tube, isophorone diisocyanate and Dibutyltin oxide, after being warming up to 70 ℃, stirring begins to drip methyl ethyl ketoxime, the mixture of hexanolactam and ethylene glycol ether, be no more than 75 ℃ with water-bath cooling and control temperature in the dropping process, dropwise rear continuation at 70 ℃ of lower reaction 5h, with residue isocyanato content in the standard Di-n-Butyl Amine back titration method analytical reaction system, when residue isocyanato content less than 0.5% the time, add methyl iso-butyl ketone (MIBK) and dilute, obtain final solid content and be 80% totally-enclosed isocyanate crosslinking.
The preparation of embodiment 6 high crosslink density microgels
In the reaction flask that thermometer, agitator, reflux condensing tube and nitrogen conduit are housed, add successively the T-2000 amino-polyether of formula ratio.Reinforced complete after, start stir and reaction system be warming up to 90 ℃ after, under this temperature, drip the methyl isobutyl ketone solution of 101 Resins, epoxy in the 1.5-2h.After dropwising, with reaction system be warming up to 125-130 ℃ continue reaction 3h after, reaction system is cooled to 70 ℃, the deionized water emulsion dispersion 30min that adds 88% lactic acid and first part, add at last remaining deionized water, obtain solid content and be 28.6% high crosslink density microgel water dispersion.
The preparation of embodiment 7 high crosslink density microgels
In the reaction flask that thermometer, agitator, reflux condensing tube and nitrogen conduit are housed, add successively the T-1000 amino-polyether of formula ratio.Reinforced complete after, start stir and reaction system be warming up to 90 ℃ after, under this temperature, drip the methyl isobutyl ketone solution of 101 Resins, epoxy in the 1.5-2h.After dropwising, with reaction system be warming up to 125-130 ℃ continue reaction 3h after, reaction system is cooled to 70 ℃, the deionized water emulsion dispersion 30min that adds 88% lactic acid and first part, add at last remaining deionized water, obtain solid content and be 30.4% high crosslink density microgel water dispersion.
The preparation of embodiment 8A emulsion
Embodiment 1 matrix resin, embodiment 3 solidifying agent, tetraethylene-glycol dibenzyl ether and the ethylene glycol monobutyl ether that in the reaction flask of agitator is housed, add formula ratio, start and stir and reaction system is mixed, then adding acetic acid neutralizes and makes the resin ionization, then add embodiment 6 high crosslink density microgels, add at last deionized water, the organic solvent in the emulsion is removed in underpressure distillation behind the emulsification 30min, namely gets solid content and be 34.2% the high anticorrosion cathode electrophoresis dope emulsion of thick-film type.
The preparation of comparative example 8B emulsion
Embodiment 1 matrix resin, embodiment 3 solidifying agent and the ethylene glycol monobutyl ether that in the reaction flask of agitator is housed, add formula ratio, start and stir and reaction system is mixed, then adding acetic acid neutralizes and makes the resin ionization, then add embodiment 6 high crosslink density microgels, add at last deionized water, the organic solvent in the emulsion is removed in underpressure distillation behind the emulsification 30min, namely gets solid content and be 34.2% conventional high anticorrosion cathode electrophoresis dope emulsion.
The preparation of comparative example 8C emulsion
Embodiment 1 matrix resin, embodiment 3 solidifying agent and the ethylene glycol monobutyl ether that in the reaction flask of agitator is housed, add formula ratio, start and stir and reaction system is mixed, then adding acetic acid neutralizes and makes the resin ionization, add at last deionized water, the organic solvent in the emulsion is removed in underpressure distillation behind the emulsification 30min, namely gets solid content and be 34.2% conventional Epoxy Cathodic Electrodeposition Coating emulsion.
The preparation of embodiment 9A emulsion
Embodiment 2 matrix resins, embodiment 4 solidifying agent, tetraethylene-glycol two hexyl ethers and the ethylene glycol monoethyl ether that in the reaction flask of agitator is housed, add formula ratio, start and stir and reaction system is mixed, then adding acetic acid neutralizes and makes the resin ionization, then add embodiment 7 high crosslink density microgels, add at last deionized water, the organic solvent in the emulsion is removed in underpressure distillation behind the emulsification 30min, namely gets solid content and be 34.2% the high anticorrosion cathode electrophoresis dope emulsion of thick-film type.
The preparation of comparative example 9B emulsion
Embodiment 2 matrix resins, embodiment 4 solidifying agent and the ethylene glycol monoethyl ether that in the reaction flask of agitator is housed, add formula ratio, start and stir and reaction system is mixed, then adding acetic acid neutralizes and makes the resin ionization, then add embodiment 7 high crosslink density microgels, add at last deionized water, the organic solvent in the emulsion is removed in underpressure distillation behind the emulsification 30min, namely gets solid content and be 34.2% conventional high anticorrosion cathode electrophoresis dope emulsion.
The preparation of comparative example 9C emulsion
Embodiment 2 matrix resins, embodiment 4 solidifying agent and the ethylene glycol monoethyl ether that in the reaction flask of agitator is housed, add formula ratio, start and stir and reaction system is mixed, then adding acetic acid neutralizes and makes the resin ionization, add at last deionized water, the organic solvent in the emulsion is removed in underpressure distillation behind the emulsification 30min, namely gets solid content and be 34.2% conventional Epoxy Cathodic Electrodeposition Coating emulsion.
The preparation of embodiment 10 grind resins
In the reaction flask that thermometer, agitator and reflux condensing tube are housed, add successively 201 Resins, epoxy, dihydroxyphenyl propane and first part's methyl iso-butyl ketone (MIBK) of formula ratio.After reinforced complete, start stir and reaction system is warming up to 120 ℃ after insulation, after raw material dissolves fully and mixes, after adding triphenylphosphine temperature is risen to 150 ℃, and 1h is reacted in continuation under this temperature, when the reaction system epoxy equivalent (weight) reaches theoretical value (EEW=570), stopped heating; When system temperature is down to below 70 ℃, with trihydroxyethyl phosphorus, 2,2-dimethylol propionic acid and deionized water join in the reaction system, again are warming up to 80 ℃, continue reaction 2h under this temperature, (the initial theoretical acid number of reaction system is sampling detection reaction system residue acid number: 63mg KOH/g), after acid number was less than 5, stopped reaction was cooled to 70 ℃ with reaction system, add the second section methyl iso-butyl ketone (MIBK), obtain final solid content and be 79.6% grind resin.
The preparation of embodiment 11 grind resins
In the reaction flask that thermometer, agitator and reflux condensing tube are housed, add successively 201 Resins, epoxy, dihydroxyphenyl propane and first part's methyl iso-butyl ketone (MIBK) of formula ratio.After reinforced complete, start stir and reaction system is warming up to 120 ℃ after insulation, after raw material dissolves fully and mixes, after adding triphenylphosphine temperature is risen to 150 ℃, and 1h is reacted in continuation under this temperature, when the reaction system epoxy equivalent (weight) reaches theoretical value (EEW=800), stopped heating; When system temperature is down to below 70 ℃, with trihydroxyethyl phosphorus, 2,2-dimethylol propionic acid and deionized water join in the reaction system, again are warming up to 80 ℃, continue reaction 2h under this temperature, (the initial theoretical acid number of reaction system is sampling detection reaction system residue acid number: 50mg KOH/g), after acid number was less than 5, stopped reaction was cooled to 70 ℃ with reaction system, add the second section methyl iso-butyl ketone (MIBK), obtain final solid content and be 78.9% grind resin.
The preparation of embodiment 12 dispersing auxiliaries
In the reaction flask that thermometer, agitator and reflux condensing tube are housed, add successively tetramethylolmethane four glycidyl ethers and the diethanolamine of formula ratio.After reinforced complete, start stirring and reaction system is warming up to 70 ℃, be accompanied by obvious exothermic phenomenon in the temperature-rise period, after heat release finishes, reaction system is continued reaction 2h under 70 ℃.When reaching theoretical value (244mgKOH/g), the system tertiary amine content adds methyl iso-butyl ketone (MIBK), then Tetra hydro Phthalic anhydride is divided to join for three times in the reaction system and with reaction system and be warming up to 120 ℃ of reaction 4h, at last 14 carbon glycidyl ethers are added, continuation is reacted 3h under this temperature, when reaction system acid number stopped reaction less than 5 time, obtain final solid content and be 90% dispersing auxiliary.
The preparation of embodiment 13 dispersing auxiliaries
In the reaction flask that thermometer, agitator and reflux condensing tube are housed, add successively tetramethylolmethane four glycidyl ethers and the N-Mono Methyl Ethanol Amine of formula ratio.After reinforced complete, start stirring and reaction system is warming up to 70 ℃, be accompanied by obvious exothermic phenomenon in the temperature-rise period, after heat release finishes, reaction system is continued reaction 2h under 70 ℃.When reaching theoretical value (216mgKOH/g), the system tertiary amine content adds methyl iso-butyl ketone (MIBK), then Tetra hydro Phthalic anhydride is divided to join for three times in the reaction system and with reaction system and be warming up to 120 ℃ of reaction 4h, at last 14 carbon glycidyl ethers are added, continuation is reacted 3h under this temperature, when reaction system acid number stopped reaction less than 5 time, obtain final solid content and be 89.2% dispersing auxiliary.
The preparation of embodiment 14 mill bases
In the sand milling tank of cooling system is housed, the grind resin, carbon black, silicon-dioxide, the embodiment 1(six that add successively formula ratio) in dispersing auxiliary and first part's deionized water, add complete after with the rotating speed of sand mill open to 4800rpm and under this rotating speed powerful sand milling 1h.Stop to disperse after the mill base fineness is less than 10 μ m, the deionized water with second section adds at last, obtains solid content and be 55% mill base.
The preparation of embodiment 15 mill bases
In the sand milling tank of cooling system is housed, the grind resin, carbon black, silicon-dioxide, the embodiment 1(six that add successively formula ratio) in dispersing auxiliary and first part's deionized water, add complete after with the rotating speed of sand mill open to 4800rpm and under this rotating speed powerful sand milling 1h.Stop to disperse after the mill base fineness is less than 10 μ m, the deionized water with second section adds at last, obtains solid content and be 55% mill base.
Preparation and the application of the high anticorrosion cathode electrophoresis dope tank liquor of embodiment 16 thick-film types
Be in the electrophoresis chamber of 1L at volume, add successively 300g embodiment 8A emulsion, 60g mill base and 600g deionized water, open mechanical stirring tank liquor is stirred.Behind tank liquor slaking 48h, tank liquor temperature is risen to 35 ℃, with the phosphatization plate immerse the groove temperature be in 35 ℃ the electrophoresis chamber under 180V voltage electrophoresis 40s.
Preparation and the application of embodiment 17 conventional high anticorrosion cathode electrophoresis dope tank liquors
Be in the electrophoresis chamber of 1L at volume, add successively 300g comparative example 8B emulsion, 60g mill base and 600g deionized water, open mechanical stirring tank liquor is stirred.Behind tank liquor slaking 48h, tank liquor temperature is risen to 35 ℃, with the phosphatization plate immerse the groove temperature be in 35 ℃ the electrophoresis chamber under 180V voltage electrophoresis 40s.
Preparation and the application of embodiment 18 conventional Epoxy Cathodic Electrodeposition Coating tank liquors
Be in the electrophoresis chamber of 1L at volume, add successively 300g comparative example 8C emulsion, 60g mill base and 600g deionized water, open mechanical stirring tank liquor is stirred.Behind tank liquor slaking 48h, tank liquor temperature is risen to 35 ℃, with the phosphatization plate immerse the groove temperature be in 35 ℃ the electrophoresis chamber under 180V voltage electrophoresis 40s.
Phosphatization plate behind the coating electrophoresis among embodiment 16, embodiment 17 and the embodiment 18 is carried out the corrosion resistance nature test, and correlation parameter sees Table 1.
The corrosion resistance nature contrast of table 1 embodiment 16, embodiment 17 and embodiment 18 coating
By table 1 data as seen, in the conventional high anticorrosion cathode electrophoresis dope (embodiment 16) because the adding of the microgel of high crosslink density, greatly improve the cissing phenomenon that coating produces in solidification process, thereby improve the fraction of coverage of sheet edge coating, improve the Corrosion Protection at sheet edge sharp edge position, so that the salt spray resistance of filming is far superior to conventional Epoxy Cathodic Electrodeposition Coating (embodiment 18), but because microgel has high crosslink density, so that add the coating of microgel, film properties variation on it, the thickness that gained is filmed is lower than conventional Epoxy Cathodic Electrodeposition Coating.In order to solve the poor defective of film on the conventional high anticorrosion cathode electrophoresis dope, the high anticorrosion cathode electrophoresis dope of thick-film type (embodiment 16) is on the high anticorrosion cathode electrophoresis dope of routine (embodiment 17) basis, by using film coalescence aid, on the basis of not losing sheet edge coating fraction of coverage, so that the thickness of filming can be greater than 35 μ m, because the increase of coating thickness is so that the salt fog performance of filming has had further raising.
After the long-time circulation of mortise liquid among embodiment 16, embodiment 17 and the embodiment 18, under the identical deposition condition (deposition condition: voltage 180V, 35 ℃ of groove temperature, electrophoresis time 40s), the thickness parameter that the phosphatization plate is coated behind the electrophoresis sees Table 2.
Film parameter comparison in the circulation of table 2 embodiment 16, embodiment 17 and embodiment 18 coating
By table 2 data as seen, in the conventional high anticorrosion cathode electrophoresis dope (embodiment 17) because the adding of high crosslink density microgel, so that the upper film ability that is circulated throughout coating in the rear mortise liquid more and more a little less than, the minimizing of coating thickness also directly affects the antiseptic property of filming, and especially affects the coating fraction of coverage of sheet edge; By using film coalescence aid, the high anticorrosion cathode electrophoresis dope of thick-film type (embodiment 16) is through after circulating for a long time, although the thickness of filming descends to some extent, coating thickness can remain on more than the 30 μ m all the time, thereby can remain higher antiseptic property so that film.
Claims (10)
1. the high anticorrosion cathode electrophoresis dope of a thick-film type, comprise emulsion, it is characterized in that emulsion solids part content: 30%～35%, pH value: 5.0～7.0, specific conductivity 1000～2000 μ s/cm, wherein solid part is by the matrix resin that accounts for solid part total mass 30%～60%, 15%～40% solidifying agent, 0.1%～10% film coalescence aid, 0.5%～1.5% solubility promoter, 15%～50% anticorrosion inhibitor forms, all the other are organic acid and deionized water, described matrix resin refers to contain the amination modifying Resins, epoxy that can form with organic acid the ion salt group, and film coalescence aid refers to contain at least on each molecule three ehter bonds, and the polyethers that behind alkylation modification, does not contain any hydroxyl.
2. the high anticorrosion cathode electrophoresis dope of thick-film type as claimed in claim 1 characterized by further comprising mill base, and emulsion and mill base quality are pressed 1:3～1:8 and mixed.
3. the high anticorrosion cathode electrophoresis dope of thick-film type as claimed in claim 2, it is characterized in that described mill base amount of solid content is 50%～60%, solid part is comprised of the grind resin that accounts for solid part total mass 15～50%, 15～35% pigment, 20～50% filler, 0.5～3% dispersing auxiliary, 0.5%～1.5% solubility promoter, and all the other are deionized water.
4. the high anticorrosion cathode electrophoresis dope of thick-film type as claimed in claim 1 or 2 is characterized in that described solidifying agent refers to totally-enclosed isocyanate crosslinking.
5. the high anticorrosion cathode electrophoresis dope of thick-film type as claimed in claim 1 or 2 is characterized in that described polyethers has following molecular structure: R
1O (CH
2CHR
2O) nR
3, n 〉=2 wherein, R
2Expression hydrogen atom or methyl, R
1And R
3Represent respectively alkyl or aryl.
6. the high anticorrosion cathode electrophoresis dope of thick-film type as claimed in claim 3 is characterized in that described anticorrosion inhibitor refers to have the microgel of high crosslink density.
7. the high anticorrosion cathode electrophoresis dope of thick-film type as claimed in claim 3 is characterized in that described grind resin refers to contain the Resins, epoxy of ion salt group.
8. such as the preparation method of the high anticorrosion cathode electrophoresis dope of a kind of thick-film type as described in the claim 1,2 or 3, it is characterized in that described dispersing auxiliary refers to have the polymkeric substance of branched structure.
9. such as claim 1, the high anticorrosion cathode electrophoresis dope of 2 or 3 described thick-film types, it is characterized in that described solubility promoter refers to the high-boiling point alcohol ether solvent.
10. one kind is adopted filming of the high anticorrosion cathode electrophoresis dope of claim 1 thick-film type, and the film thickness after it is characterized in that filming is in 35～40 μ m scopes.
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| CN103865360A (en) * | 2014-03-28 | 2014-06-18 | 湖南伟邦汽车涂料有限公司 | Acid-proof cathode electrophoretic paint as well as preparation method and application method |
| CN103911032A (en) * | 2014-04-17 | 2014-07-09 | 浩力森涂料（上海）有限公司 | Epoxy organic silicon, and leveling toughener and low-friction-factor electrophoresis paint thereof |
| CN106398469A (en) * | 2016-08-31 | 2017-02-15 | 浩力森涂料（上海）有限公司 | Microcapsule, self-healing electrophoretic coating containing microcapsule and preparation method of microcapsule |
| CN108467662A (en) * | 2018-04-17 | 2018-08-31 | 廊坊京磁精密材料有限公司 | Epoxy solution preparation method for neodymium iron boron magnetic body ability cathode electrophoresis |
| CN108715722A (en) * | 2017-03-10 | 2018-10-30 | 株式会社Kcc | Cationic electrodeposition coating composition |
| CN109504264A (en) * | 2018-12-02 | 2019-03-22 | 广州立邦涂料有限公司 | A kind of edge anti-corrosion electrodeposition coating composition, Preparation method and use |
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| CN103865360A (en) * | 2014-03-28 | 2014-06-18 | 湖南伟邦汽车涂料有限公司 | Acid-proof cathode electrophoretic paint as well as preparation method and application method |
| CN103911032A (en) * | 2014-04-17 | 2014-07-09 | 浩力森涂料（上海）有限公司 | Epoxy organic silicon, and leveling toughener and low-friction-factor electrophoresis paint thereof |
| CN106398469A (en) * | 2016-08-31 | 2017-02-15 | 浩力森涂料（上海）有限公司 | Microcapsule, self-healing electrophoretic coating containing microcapsule and preparation method of microcapsule |
| CN108715722A (en) * | 2017-03-10 | 2018-10-30 | 株式会社Kcc | Cationic electrodeposition coating composition |
| CN108715722B (en) * | 2017-03-10 | 2020-09-25 | 株式会社Kcc | Coating composition for cationic electrodeposition |
| CN108467662A (en) * | 2018-04-17 | 2018-08-31 | 廊坊京磁精密材料有限公司 | Epoxy solution preparation method for neodymium iron boron magnetic body ability cathode electrophoresis |
| CN108467662B (en) * | 2018-04-17 | 2020-03-06 | 廊坊京磁精密材料有限公司 | Preparation method of epoxy solution for neodymium iron boron magnet cathode electrophoresis |
| CN109504264A (en) * | 2018-12-02 | 2019-03-22 | 广州立邦涂料有限公司 | A kind of edge anti-corrosion electrodeposition coating composition, Preparation method and use |
| CN109504264B (en) * | 2018-12-02 | 2021-09-17 | 广州立邦涂料有限公司 | Edge anti-corrosion electrophoretic coating composition, preparation method and application |
| CN112322133A (en) * | 2020-12-03 | 2021-02-05 | 上海瑞君电泳涂料有限公司 | Thick film impact-resistant corrosion-resistant cathode electrophoretic coating and preparation process thereof |
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