CN103342943B - Method for preparing high-charge-density cathode electrophoretic paint - Google Patents
Method for preparing high-charge-density cathode electrophoretic paint Download PDFInfo
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Abstract
The invention relates to a method for preparing high-charge-density cathode electrophoretic paint. The method comprises the following steps: by using epoxy resin, carboxyl sealing cation polyurethane resin, a chain extender and an organic amine compound as raw materials, carrying out stepwise polymerization and ring-opening reaction to obtain aminated cation polyurethane modified epoxy resin; blending the resin with a totally-enclosed isocyanate crosslinking agent, and adding organic acid for neutralization after completely blending; and finally emulsifying and dispersing in an aqueous medium to obtain the high-charge-density cathode electrophoretic paint. Two ends of cation resin and a main chain of the epoxy electrophoretic paint have ion groups, and therefore the average charge density of each resin molecular chain is increased, and the throwing power of the paint is increased. The modified epoxy resin molecules contain a lot of carbamic acid ester chains, ester bonds, ether bonds, biuret bonds, allophanate bonds and the like, so that an electrophoretic paint film has good adhesive force, toughness, abrasive resistance and elasticity, high glossiness and good antiseptic property.
Description
[technical field]
The present invention relates to a kind of preparation method of high charge density cathode electrophoresis dope, one possesses higher throwing power specifically, the preparation method of the cathode electrophoresis dope of complex structure workpiece surface application can be met, wherein on the two ends of resin cation (R.C.) and main chain all with ionic group.
[background technology]
Since 20 century 70s, cathode electrophoresis dope is due to the superiority of self, such as: it has the uniform feature of each position application of workpiece to geometries complexity, and obtain increasing application in all conglomeraties, particularly automobile industry is widely used.In painting dressing automobiles, require that electrophoretic paint has high coating ability to automobile inner cavity position, because although electrophoresis coating technique can form a coating film at the workpiece surface of complexity, owing to easily producing shielding effect in electrophoresis process, make the film became uneven being coated workpiece surfaces externally and internally, especially inner surface coating is thin, thus affects the antiseptic property of whole workpiece.In order to improve the barrier propterty of the barrier propterty of Integral automobile, particularly inner chamber, the throwing power of coating just must be improved.Throwing power refers to the ability that the coated article surface electrophoresis making to deviate from electrode in electrophoretic painting process is coated.For the body of a motor car that high protection against corrosion requires, the electrophoretic paint of high throwing power can not only make to be coated the application that the recessed depths of workpiece, gap place and conductively-closed place obtain uniform film thickness, can also when improving internal surface thickness, reduce the thickness of outer surface of automobile, thus reduce the consumption of coating, save painting cost.
[summary of the invention]
In order to improve the throwing power of electrophoretic paint, thus the antiseptic power of workpiece after strengthening further electrophoresis, the invention provides a kind of preparation method of high charge density cathode electrophoresis dope, one possesses higher throwing power specifically, the preparation method of the cathode electrophoresis dope of complex structure workpiece surface application can be met, wherein on the two ends of resin cation (R.C.) and main chain all with ionic group.
The invention provides a kind of preparation method of high charge density cathode electrophoresis dope to achieve these goals, described method is made up of following steps:
Step one, progressively polymerization: in reaction vessel, add epoxy resin, carboxy blocking cationic polyurethane resin and chainextender successively, catalyzer is added after reaction system being warming up to 120 DEG C, 140 ~ 160 DEG C are warming up to after catalyzer adds, and continue reaction 1 ~ 5h at this temperature, after epoxy equivalent (weight) reaches theoretical value, stopped reaction obtains cation polyurethane modified epoxy;
Step 2, ring-opening reaction: join in reaction vessel by cation polyurethane modified epoxy and organic amine compound, react 1 ~ 4h after being warming up to 100 ~ 130 DEG C.Wherein, the epoxide group of cation polyurethane modified epoxy and the mol ratio of organic amine compound are 1:0.8 ~ 1:1.2, obtain the cation polyurethane modified epoxy after amination;
Cation polyurethane modified epoxy after step 3, amination and totally-enclosed isocyanate crosslinking carry out blended, blended completely after add organic acid and neutralize; Last emulsion dispersion in an aqueous medium obtains high charge density cathode electrophoresis dope.
Above-mentioned preparation method also has following prioritization scheme:
Prepare the amount of various raw material needed for above-mentioned cation polyurethane modified epoxy by carboxy blocking cationic polyurethane resin content (carboxy blocking cationic polyurethane resin accounts for the per-cent of cation polyurethane modified epoxy total solids quality), the amount of substance (the amount of substance * 2 of epoxy resin) of epoxide group, the amount of substance (the amount of substance * 2 of carboxy blocking cationic polyurethane resin and chainextender) of chain extension group and the design epoxy equivalent (weight) of cation polyurethane modified epoxy decide.Wherein, the epoxy equivalent (weight) scope of cation polyurethane modified epoxy is: 500 ~ 5000; The acid value of carboxy blocking cationic polyurethane resin is: 20 ~ 300; Carboxy blocking cationic polyurethane resin content range is: 5% ~ 40%; Described catalyzer is the one in triphenylphosphine or N, N-dimethyl benzylamine, and catalyst levels (catalyst quality accounts for the per-cent of epoxy resin total mass) scope is: 0.1% ~ 1%; Described modified resin total solids quality is the total mass of epoxy resin, carboxy blocking cationic polyurethane resin and chainextender.
Epoxy resin typically refers on each molecule containing two 1, the aliphatics of 2 ~ epoxide group, alicyclic, aromatic series or heterogeneous ring compound, the epoxy equivalent (weight) of described epoxy resin is between 50 ~ 2000, specially suitable epoxy resin includes but not limited to, any one or any two kinds and two or more mixtures in bisphenol A type epoxy resin, bisphenol-s epoxy resin, bisphenol f type epoxy resin, polyethyleneglycol diglycidylether and polypropylene glycol diglycidyl ether.
Chainextender is poly carboxylic acid, polyvalent alcohol, polynary mercapto alcohol, polyphenol and have the amine of 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 or any two kinds and two or more mixtures in di-carboxylic acid, dibasic alcohol, binary mercapto alcohol and dihydric phenolic compounds.
Carboxy blocking cationic polyurethane resin for raw material, obtains carboxy blocking cationic polyurethane resin through pre-polymerization and end capping with vulcabond, polymer polyatomic alcohol, hydrophilic chain extender, generally chainextender and end-capping reagent.The preparation process of carboxy blocking cationic polyurethane resin is: in reaction vessel, add vulcabond and polymer polyatomic alcohol, reacts 30 ~ 60min after being warming up to 50 ~ 80 DEG C; Then general chainextender is joined in reaction system, react 30 ~ 60min at 50 ~ 80 DEG C after; Then hydrophilic chain extender is joined in reaction system, at 50 ~ 80 DEG C, react isocyanate group content in 40 ~ 60min post analysis prepolymer; After isocyanate group content reaches theoretical value, wherein, isocyanate content theoretical value is 5% ~ 30%, finally end-capping reagent is joined in reaction system, react 30 ~ 60min at 50 ~ 80 DEG C after, termination reaction, obtain main chain containing ether, urethano and hydrophilic radical segment, two ends are the carboxy blocking cationic polyurethane resin of carboxy blocking.Wherein, in described vulcabond, in isocyanate group and polymer polyatomic alcohol, hydrophilic chain extender and general chainextender, the mol ratio of hydroxyl summation is: 10:1 ~ 2:1, in described end-capping reagent and prepolymer, the mol ratio of residual isocyanate base is: 1.2:1 ~ 1:1, and the content range of described hydrophilic radical is: 1% ~ 10%; Described hydrophilic radical content is the per-cent that the quality of hydrophilic chain extender accounts for total solids quality; Described total solids quality is the total mass of vulcabond, polymer polyatomic alcohol, hydrophilic chain extender, general chainextender and end-capping reagent.
In carboxy blocking cationic polyurethane resin process:
A) vulcabond is any one or any two kinds and the two or more mixture in tolylene diisocyanate, '-diphenylmethane diisocyanate, polymethylene polyphenyl vulcabond, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride isocyanic ester, trimethyl hexamethylene diisocyanate and hydrogenated tolylene diisocyanate.
B) polymer polyatomic alcohol is polyether glycol, any one or any two kinds and two or more mixtures in polyester polyol and polycarbonate polyol, the molecular weight of described polymer polyatomic alcohol is between 100 ~ 3000, wherein: (1) described polyether glycol is polytetrahydrofuran polyol, polyoxyethylated polyols, any one or any two kinds and two or more mixtures in polyoxypropylene polyol, or tetrahydrofuran (THF), ethylene oxide, propylene oxide is a kind of or any two kinds and two or more mixtures in both polyol arbitrarily, or tetrahydrofuran (THF), ethylene oxide, propylene oxide three polyol, (2) described polyester polyol is any one or any two kinds and the two or more mixture in poly-hexanodioic acid hexylene glycol ester, poly adipate succinic acid ester, polyethylene glycol adipate, polyneopentyl glycol adipate, poly-phthalic acid hexylene glycol ester, or by the polyester polyol of diprotic acid and dibasic alcohol condensation, or by the polyester polyol of lactone ring opening polymerization, (3) polycarbonate polyol described in is the oligopolymer containing two or more terminal hydroxy group carbonate-containing structures, is obtained by transesterify by carbonic diester and dibasic alcohol.
C) hydrophilic chain extender has [R
1r
2r
3s]
+r
4cOO
-any one or any two kinds and two or more mixtures, wherein R in structural formula compound
1and R
4can be identical group, also can be different groups, R
1and R
4group to be carbon atom be 2 ~ 20 alkyl, R
2and R
3for different groups, R
2and R
3to be carbon atom be 2 ~ 12 hydroxyl alkyl and hydroxyl alkylene in any one.
D) general chainextender is any one or any two kinds and the two or more mixture in ethylene glycol, propylene glycol, butyleneglycol, Diethylene Glycol, triethylene glycol, quadrol, propylene diamine, butanediamine and hexanediamine.
E) end-capping reagent has R
6r
5any one or any two kinds and two or more mixtures, wherein R in COOH structural formula compound
5group to be carbon atom be 2 ~ 20 alkyl, R
6group is any one in amino, hydroxyl and sulfydryl, wherein R
6group direct-connectedly receives R
5on group, and pass through R
5group is connected with carboxyl, and typical end-capping reagent comprises Thiovanic acid, thiohydracrylic acid, mercaptobutyric acid, glycine, phenylalanine and L-Ala etc.
Organic amine compound is the secondary amine compound that has by forming ketoimine and protected primary amino and has HNR
3r
4any one or any two kinds and two or more mixtures, wherein R in structural formula compound
3and R
4can be identical group, also can be different groups, R
3and R
4group to be carbon atom be 2 ~ 12 alkyl, any one in hydroxyl alkyl and hydroxyl alkylene, typical organic amine compound comprises diethylamine, dipropyl amine, dibutylamine, N-Mono Methyl Ethanol Amine, diethanolamine and diethylenetriamine type ketoimine etc.
Totally-enclosed isocyanate crosslinking is by polyisocyanates and the reaction of the compound containing reactive hydrogen preparation.Wherein, temperature of reaction is 50 ~ 90 DEG C, and the reaction times is 1 ~ 8h, and in polyisocyanates, isocyanate group is 1:1 ~ 1:1.5 with the mol ratio of the compound containing reactive hydrogen.Use in preparation process: (1) polyisocyanates includes but not limited to aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, aliphatic-aromatic vulcabond, triisocyanate, any one or any two kinds and two or more mixtures in tetraisocyanate and polymeric polyisocyanate, comprise tolylene diisocyanate, '-diphenylmethane diisocyanate, polymethylene polyphenyl vulcabond, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride isocyanic ester, trimethyl hexamethylene diisocyanate and hydrogenated tolylene diisocyanate etc., (2) compound containing reactive hydrogen is containing any one in the alcohol of 1 ~ 20 carbon atom, amine, carboxylic acid, oxime and cyclic amide or any two kinds and two or more mixtures, comprises 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 pyrrolidone etc.
Organic acid is any one or any two kinds and two or more mixtures in the aliphatics containing 1 ~ 20 carbon atom, alicyclic, aromatic series or heterocycle monoprotic acid, comprise formic acid, acetic acid, propionic acid, butyric acid, lactic acid, 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acids and phenylformic acid etc.
Beneficial effect of the present invention is:
1, cationic for main chain belt urethane resin is incorporated in epoxy resin by chemical bond goes, make on the two ends of modified epoxy electrophoretic paint cationic resin and main chain all with ionic group, thus the average charge density increased on every root molecular resin chain, the throwing power of coating is increased;
2, due to the introducing of urethane segment, make in modified epoxy molecule containing a large amount of carbamic acid ester chain, ester bond, ehter bond, biuret linkage and allophanic acid ester bond etc., therefore, make the paint film after electrophoresis have good sticking power, toughness, wear resistance, elasticity and high-luster, and there is excellent antiseptic property.
[embodiment]
For ease of understanding the present invention further, the following example has set forth details particularly, but embodiments of the present invention are not limited thereto.
Embodiment 1
One, the preparation of carboxy blocking cationic polyurethane resin
* R
1and R
4for methyl, R
2for hydroxyethyl, R
3for 2-hydroxypropyl
* NCO/OH=5:1, hydrophilic radical content: 4.34%
In the reaction flask that thermometer, agitator and reflux condensing tube are housed, add tolylene diisocyanate and the polyether Glycols of formula ratio successively, after being warming up to 70 DEG C, react 30min; Then add ethylene glycol, at same temperature, continue reaction 30min; Then hydrophilic chain extender is added, isocyanato content in prepolymer is analyzed with standard Di-n-Butyl Amine back titration method after continuing to react 40min at the same temperature, when isocyanato content reaches theoretical value 17.38%, add thiohydracrylic acid and carry out end-blocking, obtain the carboxy blocking cationic polyurethane resin that acid number is 232mgKOH/g.
Two, the preparation * * of the polyurethane modified epoxy resin of amination
* react preparation by diethylenetriamine and methyl iso-butyl ketone (MIBK) according to mol ratio 1:2, the solid content of final product is: 100%
* EEW=1140, carboxy blocking cationic polyurethane resin content=17.3%
In the reaction flask that thermometer, agitator and reflux condensing tube are housed, add the epoxy resin of formula ratio, carboxy blocking cationic polyurethane resin, dihydroxyphenyl propane and first part's methyl iso-butyl ketone (MIBK) successively; After reinforced, start and stir and be incubated after reaction system is warming up to 120 DEG C, after raw material dissolves completely and mixes, after adding triphenylphosphine, temperature is risen to 130 DEG C, and continue reaction 3h at this temperature, when reaction system epoxy equivalent (weight) reaches theoretical value, stop heating; When system temperature is down to below 90 DEG C, N-Mono Methyl Ethanol Amine and ketoimine are joined in reaction system, be again warming up to 120 DEG C, continue reaction 2h at this temperature; After reaction terminates, reaction system is cooled to 70 DEG C, adds second section methyl iso-butyl ketone (MIBK), obtaining final solid content is cation polyurethane modified epoxy after the amination of 80.0%.
Three, the preparation of totally-enclosed isocyanate crosslinking
The tolylene diisocyanate of formula ratio is added in the reaction flask that thermometer, agitator and reflux condensing tube are housed, stirring starts to drip methyl ethyl ketoxime after being warming up to 70 DEG C, in dropping process with water-bath cooling and control temperature be no more than 75 DEG C, dropwise rear continuation and react 2h at 70 DEG C, isocyanato content is remained with in standard Di-n-Butyl Amine back titration method analytical reaction system, when remaining isocyanato content and being less than 0.5%, add methyl iso-butyl ketone (MIBK) to dilute, obtain the totally-enclosed isocyanate crosslinking that final solid content is 80%.
Four, the preparation of high charge density cathode electrophoresis dope
The polyurethane modified epoxy resin of the amination of formula ratio and totally-enclosed isocyanate crosslinking is added in the reaction flask that agitator is housed, start and stir and reaction system is mixed, then add acetic acid carry out neutralizing and make resin reignition, finally add deionized water needed for each step successively, organic solvent after emulsification 30min in underpressure distillation removing emulsion, obtains the high charge density cathode electrophoresis dope that solid content is 33.7%.
After the high charge density cathode electrophoresis dope of above-mentioned preparation is joined groove slaking 48h, adopt the throwing power of four pieces of box methods to coating to test, and contrast with traditional Epoxy Cathodic Electrodeposition Coating, correlation parameter sees the following form.
The throwing power contrast of the different coating of table 1
Deposition condition: voltage 220V, groove temperature 30 DEG C, electrophoresis time 3min
As can be seen from the above data, the throwing power of the high charge density cathode electrophoresis dope in embodiment 1 is far superior to the throwing power of conventional epoxy cathode electrophoresis dope.
Embodiment 2
One, the preparation of carboxy blocking cationic polyurethane resin
* R
1for butyl, R
4for ethyl, R
2and R
3for 2-hydroxypropyl
* NCO/OH=3:1, hydrophilic radical content: 9.14%
In the reaction flask that thermometer, agitator and reflux condensing tube are housed, add the isophorone diisocyanate of formula ratio and the polyether Glycols of two kinds of different molecular weights successively, after being warming up to 80 DEG C, react 50min; Then add butyleneglycol, at same temperature, continue reaction 30min; Then hydrophilic chain extender is added, isocyanato content in prepolymer is analyzed with standard Di-n-Butyl Amine back titration method after continuing to react 35min at the same temperature, when isocyanato content reaches theoretical value 15.62%, add 6-aminocaprolc acid and carry out end-blocking, obtain the carboxy blocking cationic polyurethane resin that acid number is 140mgKOH/g.
Two, the preparation * * of the polyurethane modified epoxy resin of amination
* EEW=1800, carboxy blocking cationic polyurethane resin content=36.4%
In the reaction flask that thermometer, agitator and reflux condensing tube are housed, add the epoxy resin of formula ratio, carboxy blocking cationic polyurethane resin, dihydroxyphenyl propane and first part's methyl iso-butyl ketone (MIBK) successively; After reinforced, start and stir and be incubated after reaction system is warming up to 120 DEG C, after raw material dissolves completely and mixes, after adding triphenylphosphine, temperature is risen to 130 DEG C, and continue reaction 3h at this temperature, when reaction system epoxy equivalent (weight) reaches theoretical value, stop heating; When system temperature is down to below 90 DEG C, N-Mono Methyl Ethanol Amine and diethanolamine are joined in reaction system, be again warming up to 120 DEG C, continue reaction 2h at this temperature; After reaction terminates, reaction system is cooled to 70 DEG C, adds second section methyl iso-butyl ketone (MIBK), obtaining final solid content is cation polyurethane modified epoxy after the amination of 78.5%.
Three, the preparation of totally-enclosed isocyanate crosslinking
The hexamethylene diisocyanate trimer of formula ratio is added in the reaction flask that thermometer, agitator and reflux condensing tube are housed, stirring starts to drip ethylene glycol monobutyl ether after being warming up to 80 DEG C, in dropping process with water-bath cooling and control temperature be no more than 85 DEG C, dropwise rear continuation and react 4h at 80 DEG C, isocyanato content is remained with in standard Di-n-Butyl Amine back titration method analytical reaction system, when remaining isocyanato content and being less than 0.5%, add methyl iso-butyl ketone (MIBK) to dilute, obtain the totally-enclosed isocyanate crosslinking that final solid content is 75%.
Four, the preparation of high charge density cathode electrophoresis dope
The polyurethane modified epoxy resin of the amination of formula ratio and totally-enclosed isocyanate crosslinking is added in the reaction flask that agitator is housed, start and stir and reaction system is mixed, then add 88% lactic acid carry out neutralizing and make resin reignition, finally add deionized water needed for each step successively, organic solvent after emulsification 30min in underpressure distillation removing emulsion, obtains the high charge density cathode electrophoresis dope that solid content is 34.2%.
Embodiment 3
One, the preparation of carboxy blocking cationic polyurethane resin
* R
1for ethyl, R
2for hydroxyethyl, R
3for 3-propoxy--2-hydroxypropyl, R
4for butyl
* NCO/OH=2:1, hydrophilic radical content: 3.84%
In the reaction flask that thermometer, agitator and reflux condensing tube are housed, add diphenylmethanediisocyanate and the polyester diol of formula ratio successively, after being warming up to 60 DEG C, react 30min; Then add hexylene glycol, after being warming up to 70 DEG C, continue reaction 30min; Then hydrophilic chain extender is added, isocyanato content in prepolymer is analyzed with standard Di-n-Butyl Amine back titration method after continuing to react 35min at the same temperature, when isocyanato content reaches theoretical value 7.60%, add 2-mercaptobutyric acid and carry out end-blocking, obtain the carboxy blocking cationic polyurethane resin that acid number is 83.4mgKOH/g.
Two, the preparation * * of the polyurethane modified epoxy resin of amination
* react preparation by diethylenetriamine and methyl iso-butyl ketone (MIBK) according to mol ratio 1:2, the solid content of final product is: 100%
* EEW=900, carboxy blocking cationic polyurethane resin content=24.3%
In the reaction flask that thermometer, agitator and reflux condensing tube are housed, add the epoxy resin of formula ratio, carboxy blocking cationic polyurethane resin, dihydroxyphenyl propane and first part's methyl iso-butyl ketone (MIBK) successively; After reinforced, start and stir and be incubated after reaction system is warming up to 120 DEG C, after raw material dissolves completely and mixes, after adding triphenylphosphine, temperature is risen to 130 DEG C, and continue reaction 3h at this temperature, when reaction system epoxy equivalent (weight) reaches theoretical value, stop heating; When system temperature is down to below 90 DEG C, diethanolamine and ketoimine are joined in reaction system, be again warming up to 120 DEG C, continue reaction 2h at this temperature; After reaction terminates, reaction system is cooled to 70 DEG C, adds second section methyl iso-butyl ketone (MIBK), obtaining final solid content is cation polyurethane modified epoxy after the amination of 75%.
Three, the preparation of totally-enclosed isocyanate crosslinking
Thermometer is being housed, tolylene diisocyanate and the isophorone diisocyanate of formula ratio is added in the reaction flask of agitator and reflux condensing tube, stirring starts to drip methyl ethyl ketoxime after being warming up to 70 DEG C, the mixture of hexanolactam and ethylene glycol ether, in dropping process with water-bath cooling and control temperature be no more than 75 DEG C, dropwise rear continuation and react 5h at 70 DEG C, isocyanato content is remained with in standard Di-n-Butyl Amine back titration method analytical reaction system, when remaining isocyanato content and being less than 0.5%, add methyl iso-butyl ketone (MIBK) to dilute, obtain the totally-enclosed isocyanate crosslinking that final solid content is 80%.
Four, the preparation of high charge density cathode electrophoresis dope
The polyurethane modified epoxy resin of the amination of formula ratio and totally-enclosed isocyanate crosslinking is added in the reaction flask that agitator is housed, start and stir and reaction system is mixed, then 2 are added, the deionized water of 2-dimethylol propionic acid and first part carries out neutralizing and makes resin reignition, finally add deionized water needed for each step successively, organic solvent after emulsification 30min in underpressure distillation removing emulsion, obtains the high charge density cathode electrophoresis dope that solid content is 33.74%.
Claims (10)
1. a preparation method for high charge density cathode electrophoresis dope, is characterized in that described method is made up of following steps:
Step one, in reaction vessel, add epoxy resin, carboxy blocking cationic polyurethane resin and chainextender successively, catalyzer is added after reaction system being warming up to 120 DEG C, wherein, catalyst levels accounts for 0.1% ~ 1% of epoxy resin total mass, 140 ~ 160 DEG C are warming up to after catalyzer adds, and continue reaction 1 ~ 5h at this temperature, when epoxy equivalent (weight) reaches 500 ~ 2000, stopped reaction obtains cation polyurethane modified epoxy;
Step 2, cation polyurethane modified epoxy and organic amine compound are joined in reaction vessel, 1 ~ 4h is reacted after being warming up to 100 ~ 130 DEG C, wherein, the epoxide group of cation polyurethane modified epoxy and the mol ratio of organic amine compound are 1:0.8 ~ 1:1.2, obtain the cation polyurethane modified epoxy after amination;
Cation polyurethane modified epoxy after step 3, amination and totally-enclosed isocyanate crosslinking carry out blended, wherein, cation polyurethane modified epoxy after amination and the blended mass ratio of totally-enclosed isocyanate crosslinking are 2:1 ~ 4:1, blended completely after add organic acid and neutralize, finally emulsion dispersion obtains high charge density cathode electrophoresis dope in an aqueous medium.
2. the preparation method of high charge density cathode electrophoresis dope as claimed in claim 1, is characterized in that described epoxy resin is aliphatics containing two 1,2-epoxide groups on each molecule, alicyclic, aromatic series or heterogeneous ring compound.
3. the preparation method of high charge density cathode electrophoresis dope as claimed in claim 1, it is characterized in that the main chain of described carboxy blocking cationic polyurethane resin is containing ether, urethano and hydrophilic radical segment, two ends are carboxy blocking, and acid value is 20 ~ 300mgKOH/g; Consumption account for high charge density cathode electrophoresis dope total mass 5% ~ 40%.
4. the preparation method of high charge density cathode electrophoresis dope as claimed in claim 3, characterized by further comprising the preparation process of carboxy blocking cationic polyurethane resin:
Vulcabond and polymer polyatomic alcohol is added in reaction vessel, in vulcabond, in isocyanate group and polymer polyatomic alcohol, hydrophilic chain extender and general chainextender, the mol ratio of hydroxyl summation is 10:1 ~ 2:1, in described end-capping reagent and prepolymer, the mol ratio of residual isocyanate base is 1.2:1 ~ 1:1, and described hydrophilic radical content range is 1% ~ 10%;
30 ~ 60min is reacted after being warming up to 50 ~ 80 DEG C; Then general chainextender is joined in reaction system, react 30 ~ 60min at 50 ~ 80 DEG C after; Then hydrophilic chain extender is joined in reaction system, at 50 ~ 80 DEG C, react isocyanate group content in 40 ~ 60min post analysis prepolymer; When isocyanate group content reaches 5% ~ 30%, end-capping reagent is joined in reaction system, react 30 ~ 60min at 50 ~ 80 DEG C after, termination reaction.
5. the preparation method of high charge density cathode electrophoresis dope as claimed in claim 4, is characterized in that described polymer polyatomic alcohol is any one or multiple mixture in the polyether glycol of molecular weight between 100 ~ 3000, polyester polyol and polycarbonate polyol.
6. the preparation method of high charge density cathode electrophoresis dope as claimed in claim 4, is characterized in that described hydrophilic chain extender has [R
1r
2r
3s]
+r
4cOO
-one or more mixture in structural formula compound, R
1and R
4represent C respectively
2~ C
20alkyl, R
2and R
3for different groups, R
2and R
3represent C respectively
2~ C
12hydroxyl alkyl or hydroxyl alkylene.
7. the preparation method of high charge density cathode electrophoresis dope as claimed in claim 4, is characterized in that described end-capping reagent has R
6r
5one or more mixture in COOH structural formula compound, wherein R
5represent C
2~ C
20alkyl, R
6represent amino, hydroxyl or sulfydryl, wherein R
6group is directly connected to R
5on group, and pass through R
5group is connected with carboxyl.
8. the preparation method of high charge density cathode electrophoresis dope as claimed in claim 1, is characterized in that described organic amine compound has the secondary amine compound by forming ketoimine and protected primary amino and has HNR
3r
4one or more mixture in structural formula compound, wherein R
3and R
4c
2~ C
12alkyl, hydroxyl alkyl or hydroxyl alkylene.
9. the preparation method of high charge density cathode electrophoresis dope as claimed in claim 1, characterized by further comprising the preparation process of totally-enclosed isocyanate crosslinking:
By polyisocyanates and the reaction of the compound containing reactive hydrogen preparation, in polyisocyanates, isocyanate group is 1:1 ~ 1:1.5 with the mol ratio of the compound containing reactive hydrogen, and temperature of reaction is 50 ~ 90 DEG C, and the reaction times is 1 ~ 8h.
10. the preparation method of high charge density cathode electrophoresis dope as claimed in claim 9, is characterized in that the described compound containing reactive hydrogen is alcohol, amine, carboxylic acid, oxime or cyclic amide containing 1 ~ 20 carbon atom.
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| 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 |
| CN104371496A (en) * | 2014-11-07 | 2015-02-25 | 广德瑞邦涂料有限公司 | Cathodic water-soluble electrophoretic paint emulsion and preparation method thereof |
| CN104945590B (en) * | 2015-05-15 | 2018-11-16 | 武汉科利尔新材料有限公司 | Terminal hydroxy group modified polyurethane resin and its cataphoresis paint composition and preparation method |
| CN109384936B (en) * | 2018-09-26 | 2021-07-23 | 青岛科技大学 | Carbon nanotube grafted hydroxyl-terminated polyurethane electrophoretic resin, cathode polyurethane electrophoretic paint and preparation methods thereof |
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| EP1209207A1 (en) * | 2000-11-27 | 2002-05-29 | Nippon Paint Co., Ltd. | Resin composition and cationic electrodeposition coating composition |
| JP2006111765A (en) * | 2004-10-15 | 2006-04-27 | Kansai Paint Co Ltd | Anionic electrodeposition coating |
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Address after: No.158, Huiping Road, Nanxiang Town, Jiading District, Shanghai, 201802 Patentee after: HLS COATING (SHANGHAI) Co.,Ltd. Patentee after: HAOLISEN CHEMICAL TECHNOLOGY (JIANGSU) Co.,Ltd. Address before: No.158, Huiping Road, Nanxiang Town, Jiading District, Shanghai, 201802 Patentee before: HLS COATING (SHANGHAI) Co.,Ltd. Patentee before: HAOLISEN CHEMICAL TECHNOLOGY JIANGSU CO.,LTD. |
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